JPWO2015186613A1 - Laminated film with matte layer - Google Patents

Abstract

Provided is a laminated film in which deterioration of film performance is suppressed by preventing mat dropping in a mat layer after film formation and further preventing transfer occurring during winding. A substrate, a mat layer disposed on one surface of the substrate, and a functional layer disposed on the other surface of the substrate, and the mat layer has an average particle size of 0.1 to 0.1. A laminated film containing a 7 μm filler, a urea bond-containing polymer, and a cured resin.

Description

  The present invention relates to a laminated film having a mat layer.

  Conventionally, a gas barrier film formed by laminating a plurality of layers including thin films of metal oxides such as aluminum oxide, magnesium oxide, and silicon oxide on the surface of a plastic substrate or film is used to block various gases such as water vapor and oxygen. For example, it is widely used for packaging of articles that require the use of, for example, packaging for preventing deterioration of foods, industrial products, pharmaceuticals, and the like. In addition to packaging applications, development to flexible electronic devices such as flexible solar cell elements, organic electroluminescence (EL) elements, liquid crystal display elements, etc. has been demanded, and many studies have been made.

  Recently, studies have been made on gas barrier films using a base material having a mat layer for the purpose of giving the feel of an electronic device and increasing the mechanical strength of the base material.

  In JP-A-2003-326651, a resin as a base material and a resin that forms a mat layer are coextruded and then stretched to obtain a laminated film, and the surface of the laminated film opposite to the mat layer is further disclosed. Discloses a method for producing a mat-like gas barrier laminate film in which a coating layer is formed.

  In the conventional laminated film having a mat layer, there is a problem that the mat layer is largely dropped after film formation due to the aggregation and poor dispersion of the filler, and the appearance of the film is impaired. Furthermore, when the film is wound at the time of manufacture, the filler is detached from the film, causing the film surface to be pressed or scratched. The film surface was pressed or scratched, leading to film failure or cracking, and consequently to a decrease in the performance of the entire film.

  As a method for eliminating the aggregation and poor dispersion of the filler, it is known to add an additive for improving the dispersibility of the filler in the coating liquid for the mat layer.

  However, although the above method is effective for removing the mat after film formation, when the film is wound, the transfer of the additive to the adjacent surface occurs, and the influence of the decrease in the functional layer of the film Since problems occurred, it was insufficient to solve the above problems.

  Then, this invention provides the means which suppresses the fall of the performance of a film in the laminated film which has a base material provided with a mat layer, and a functional layer.

  The present inventor has intensively studied to solve the above problems. As a result, in a laminated film having a mat layer on one surface of the substrate and a functional layer on the other surface of the substrate, the mat layer has a certain type of bond with a filler having a certain particle size. It has been found that the above problems can be solved by including a polymer, and the present invention has been completed.

  That is, in order to realize the above object of the present invention, a laminated film reflecting one aspect of the present invention has the following.

  1. A substrate, a mat layer disposed on one surface of the substrate, and a functional layer disposed on the other surface of the substrate, and the mat layer has an average particle size of 0.1 to 0.1. A laminated film containing a 7 μm filler, a urea bond-containing polymer, and a cured resin.

  2. The functional layer is a gas barrier layer; A laminated film according to 1.

  3. 1. The curable resin is a UV curable resin. Or 2. A laminated film according to 1.

  4). 1. The filler is a crosslinked acrylic resin particle. ~ 3. The laminated film according to any one of the above.

  5. The average particle diameter is 0.5 to 3.5 μm. ~ 4. The laminated film according to any one of the above.

  6). The urea bond-containing polymer is contained in an amount of 20 to 70% by mass with respect to the filler. ~ 5. The laminated film according to any one of the above.

  7). The urea bond-containing polymer is contained in an amount of 0.5 to 2.0% by mass with respect to the cured resin. ~ 6. A laminated film according to any one of the above.

It is a schematic sectional drawing which shows the basic composition which shows an example of the laminated film which concerns on this invention. In FIG. 1, F is a laminated film, F1 is a resin substrate, F2 is a mat layer, and F3 is a functional layer. It is a schematic diagram which shows an example of the manufacturing apparatus which can be utilized suitably in order to manufacture the gas barrier layer which is a functional layer. In FIG. 2, 1 is a gas barrier film, 2 is a base material, 3 is a gas barrier layer, 31 is a production apparatus, 32 is a delivery roller, 33, 34, 35 and 36 are transport rollers, 39 and 40 are film forming rollers, 41 Is a gas supply pipe, 42 is a plasma generating power source, 43 and 44 are magnetic field generators, and 45 is a winding roller.

  One embodiment of the present invention includes a base material, a mat layer disposed on one surface of the base material, and a functional layer disposed on the other surface of the base material. A laminated film containing a filler having a diameter of 0.1 to 7 μm and a urea bond-containing polymer. According to the laminated film according to one embodiment of the present invention having such a configuration, the filler is prevented from dropping from the mat layer after film formation, and the transfer of the additive generated during winding to the adjacent surface is prevented. It is possible to suppress the deterioration of the film performance.

  In other words, in this embodiment, the urea bond portion of the additive is reduced by limiting the average particle size of the filler to the range of 0.1 to 7 μm and using the urea bond-containing polymer as an additive for dispersing the filler. By interacting with the filler, the urea-bonded polymer is taken into the cured resin network together with the filler, preventing the filler from detaching from the film surface, and further preventing the polymer additive from being transferred to the film surface. This is considered to have led to the prevention of deterioration of the performance of the laminated film.

  Hereinafter, the component of the laminated film which concerns on this invention, and the form and aspect for implementing this invention are demonstrated in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. Unless otherwise specified, measurement of operation and physical properties is performed under conditions of room temperature (20 to 25 ° C.) / Relative humidity 40 to 50%.

<< Laminated film >>
FIG. 1 is a schematic cross-sectional view showing an example of a basic configuration of a laminated film according to the present invention.

  As shown in FIG. 1, the laminated film F according to the present invention is arranged on a base material F1 as a support, a mat layer F2 arranged on one surface of the base material F1, and the other surface of the base material F1. Gas barrier layer F3 as a functional layer. The mat layer F2 includes a filler having an average particle diameter of 0.1 to 7 μm, a urea bond-containing polymer, and a cured resin.

<Base material>
The laminated film according to the present invention has a substrate.

  The substrate is preferably transparent, and various resin films can be used. For example, polyolefin film (polyethylene, polypropylene, etc.), polyester film (polyethylene terephthalate, polyethylene naphthalate, etc.), polyvinyl chloride, cellulose triacetate, polyimide, polybutyral film, cycloolefin polymer film, transparent cellulose nanofiber film, etc. Can be used. Among these, it is preferable to use a polyester film.

  Among the polyester films, from the viewpoint of transparency, mechanical strength, dimensional stability and the like, dicarboxylic acid components such as terephthalic acid and 2,6-naphthalenedicarboxylic acid, and diols such as ethylene glycol and 1,4-cyclohexanedimethanol It is preferable that it is polyester which has the film formation property which makes a component a main structural component. Of these, polyesters mainly composed of polyethylene terephthalate and polyethylene naphthalate, copolymerized polyesters composed of terephthalic acid, 2,6-naphthalenedicarboxylic acid and ethylene glycol, and mixtures of two or more of these polyesters are mainly used. Polyester as a constituent component is preferable.

  The material and film thickness of the substrate are preferably set so that the value obtained by dividing the thermal shrinkage rate of the laminated film by the thermal shrinkage rate of the substrate is in the range of 1 to 3.

  Especially, it is preferable that the film thickness of a base material is 30-200 micrometers, It is more preferable that it is 30-150 micrometers, It is most preferable that it is 35-125 micrometers. It is preferable that the thickness of the substrate is 30 μm or more because wrinkles during handling are less likely to occur. On the other hand, when the thickness of the substrate is 200 μm or less, for example, when the substrate is bonded to the transparent substrate, the followability to the curved transparent substrate is improved and wrinkles are less likely to occur.

  The substrate is preferably a biaxially oriented polyester film, but an unstretched or at least one stretched polyester film can also be used. A stretched film is preferable from the viewpoint of improving strength and suppressing thermal expansion.

<Matte layer>
The laminated film according to the present invention has a mat layer including a filler having an average particle size of 0.1 to 7 μm, a urea bond-containing polymer, and a cured resin on one surface of the substrate. The mat layer plays a role of increasing the mechanical strength of the base material, and can also play a role of giving the texture of the electronic device, a light diffusing effect, and a slipperiness (reduction of dynamic friction coefficient).

[Filler]
By adding a filler to the mat layer, it is possible to improve the slipping between the mat surface and the functional layer surface when the film is rolled, and to prevent the film from being damaged, and in combination with a urea bond-containing polymer Thus, transfer of the additive can be suppressed.

  Fillers include particles such as polyethylene particles (PE particles), inorganic particles such as silica particles, alumina particles, cerium oxide particles, and zirconia particles, or organic materials such as crosslinked acrylic particles, PMMA (polymethyl methacrylate), and polystyrene. Particles. These can be used alone or in combination. From the viewpoint of dispersibility of the filler, crosslinked acrylic resin particles and silica particles are preferable, from the viewpoint of slipperiness and prevention of scratches, more preferably crosslinked acrylic resin particles, and crosslinked polymethyl methacrylate resin particles. More preferred.

  The cross-linked acrylic resin is a resin of a copolymer of an acrylate ester and a polyfunctional monomer. Examples of the acrylate ester include methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like. A polyfunctional monomer is a substance having two or more functional groups that can form a bond with other molecules by a chemical reaction other than a vinyl group. Examples of the functional group include a hydroxyl group, a carboxyl group, Examples thereof include an epoxy group, an amide group, an amino group, a methylol group, a sulfonic acid group, a sulfamic acid group, and a (phosphite) ester group. The polyfunctional monomer is not particularly limited, and examples thereof include ethylene glycol dimethacrylate, ethylene glycol bismethacrylate, propylene glycol diacrylate, trimethylolpropane trimethacrylate, and pentaerythritol tetramethacrylate. The cross-linked acrylic resin may have a monomer unit derived from a known vinyl monomer such as ethylene or styrene.

  Commercially available products may be used as the cross-linked acrylic resin particles. Examples of commercially available products include Techpolymer MBX-5, SSX-101, 102, 103, 104, 105 (above, manufactured by Sekisui Plastics), MX. -80H3wT, MX-150, MX-180TA, MX-300, MX-500, MX-500H (above, manufactured by Soken Chemical Co., Ltd.), Eposter (registered trademark) MA series, MX series (manufactured by Nippon Shokubai Co., Ltd.), etc. It is done.

  The addition amount of the filler is preferably 0.5 to 3.5% by mass from the viewpoint of the degree of matte (appearance) and coatability with respect to the following cured resin, and is 0.5 to 2% by mass. More preferably.

  The average particle diameter of the filler is 0.1 to 7 μm. When the filler has an average particle size of 0.1 to 7 μm, the urea bond-containing polymer is taken together with the filler into the network structure of the cured resin when used in combination with the above-described urea bond-containing polymer that can be contained in the matte layer. Thus, detachment of the filler from the film surface, that is, mat removal can be efficiently prevented. The average particle size of the filler is preferably 3.5 μm or less from the viewpoint of further preventing the mat from dropping, and preferably 0.5 μm or more from the viewpoint of improving the slipperiness and preventing the transfer of the additive. 0.5 to 3.5 μm is more preferable, and 0.75 to 1.5 μm is even more preferable.

  The average particle diameter can be measured by using an LS particle size distribution measuring device (Beckman Coulter) for particles, for example, about 10 mg of particles. Moreover, the particle | grains which appeared in the film cross section are observed with an electron microscope (TEM or SEM), the particle size of 10 arbitrary particles is measured, and it calculates | requires as the simple average value (number average). Here, the particle diameter of each particle is represented by a diameter assuming a circle equal to the projected area.

[Urea bond-containing polymer]
The mat layer contains a urea bond-containing polymer. A urea bond-containing polymer means a polymer containing a urea bond in the molecule.

  The urea bond-containing polymer can be obtained by polycondensation of polyisocyanate and polyamine.

The “urea bond” is represented by the general formula: —NR ₁ CONR ₂ —.

Here, R ₁ and R ₂ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, cyclohexyl group). Etc., preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or a methyl group.

  The urea bond may be formed by any means, but can be obtained by a reaction between an isocyanate and an amine. In addition, a hydroxyl group at the end or a group such as 1,3-bis (2-aminoethyl) urea, 1,3-bis (2-hydroxyethyl) urea, 1,3-bis (2-hydroxypropyl) urea, etc. A urea compound substituted with an alkyl group having an amino group may be used as a raw material.

  The isocyanate used as a raw material is not particularly limited as long as it is a polyisocyanate having two or more isocyanate groups in the molecule, but is preferably an alkyl polyisocyanate or an aromatic polyisocyanate, and more preferably an alkyl diisocyanate or an aromatic diisocyanate. Moreover, you may use asymmetrical diisocyanate (for example, p-isocyanate benzyl isocyanate etc.) together as a raw material.

  Alkyl polyisocyanate is a compound in which a plurality of isocyanate groups are all present through an alkyl chain. For example, 1,3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate , Pentamethylene diisocyanate, hexamethylene diisocyanate, 1,3-cyclopentane diisocyanate and the like.

  An aromatic polyisocyanate is a compound in which a plurality of isocyanate groups are all directly bonded to an aromatic ring. For example, 9H-fluorene-2,7-diisocyanate, 9H-fluoren-9-one-2,7- Diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, tolylene-2,4-diisocyanate, tolylene-2,6-diisocyanate, 1,3-bis (isocyanatomethyl) ) Cyclohexane, 2,2-bis (4-isocyanatophenyl) hexafluoropropane, 1,5-diisocyanatonaphthalene and the like.

  The amine used as a raw material is preferably a polyamine having two or more amino groups in the molecule, and most preferably a diamine. Examples of polyamines include 2,7-diamino-9H-fluorene, 3,6-diaminoacridine, acriflavine, acridine yellow, 2,2-bis (4-aminophenyl) hexafluoropropane, and 4,4′-diaminobenzophenone. Bis (4-aminophenyl) sulfone, 4,4′-diaminodiphenyl ether, bis (4-aminophenyl) sulfide, 1,1-bis (4-aminophenyl) cyclohexane, 4,4′-diaminodiphenylmethane, 3, 3'-diaminodiphenylmethane, 3,3'-diaminobenzophenone, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 4- (phenyldiazenyl) benzene-1,3-diamine, 1,5-diaminonaphthalene, 1,3-phenylenediamine, 2,4-dia Not toluene, 2,6-diaminotoluene, 1,8-diaminonaphthalene, 1,3-diaminopropane, 1,3-diaminopentane, 2,2-dimethyl-1,3-propanediamine, 1,5-diaminopentane, 2-methyl-1,5-diaminopentane, 1,7-diaminoheptane, N, N-bis (3-aminopropyl) methylamine, 1,3-diamino-2-propanol, diethylene glycol bis (3-aminopropyl) ) Ether, m-xylylenediamine, tetraethylenepentamine, 1,3-bis (aminomethyl) cyclohexane, benzoguanamine, 2,4-diamino-1,3,5-triazine, 2,4-diamino-6-methyl -1,3,5-triazine, 6-chloro-2,4-diaminopyrimidine, 2-chloro-4,6-dia Examples include mino-1,3,5-triazine. These polyamines may be reacted with phosgene, triphosgene or thiophosgene to synthesize polyisocyanates or polyisothiocyanates (hereinafter referred to as polyiso (thio) cyanates) and used as macromonomer raw materials. It may be used as an extender.

  The reaction between polyisocyanate and polyamine may be performed by solution polymerization, vapor deposition polymerization, or polymerization without solvent, but solution polymerization or polymerization without solvent is preferred.

  In the polymerization of polyisocyanate and polyamine, when the molar ratio at the time of polymerization is equimolar, the degree of polymerization becomes high and the solubility in a solvent is remarkably lowered. Therefore, either polyamine or polyisocyanate is reacted in an excessive system. It is preferable that one is 1.5 times mole to 10 times mole, and more preferably 2.0 times mole to 5 times mole relative to the other raw material. At this time, when excess polyisocyanate is used as a raw material, a urea bond-containing polymer whose main terminal group is an isocyanate group can be obtained. On the other hand, when an excess of polyamine is used as a raw material, a urea bond-containing polymer whose main terminal group is an amino group can be obtained.

  As the solvent used in the reaction, it is necessary to use a highly polar solvent in order that the target urea bond-containing polymer is highly polar and the polymerization proceeds efficiently. For example, it is preferable to select a highly polar aprotic solvent such as DMF (N, N-dimethylformamide), DMAc (N, N-dimethylacetamide), DMSO (dimethylsulfoxide), NMP (N-methylpyrrolidone), As long as the reaction substrate and target compound dissolve well, aliphatic hydrocarbons such as cyclohexane, pentane and hexane, aromatic hydrocarbons such as benzene, toluene and chlorobenzene, THF (tetrahydrofuran), diethyl ether, ethylene glycol diethyl It may be a solvent such as ethers such as ether, ketones such as acetone, methyl ethyl ketone, 4-methyl-2-pentanone, esters such as methyl propionate, ethyl acetate, butyl acetate, etc. May be.

  The polymerization temperature may be any temperature as long as the reaction proceeds, but is preferably -50 ° C to 50 ° C, more preferably -20 ° C to 30 ° C, and particularly preferably -20 ° C to 15 ° C.

  The urea bond-containing polymer may be isolated and purified, and is preferably a method of performing isolation and purification by reprecipitation.

  Any means may be used for the reprecipitation purification of the urea bond-containing polymer, but a method of dropping the reaction solution into a poor solvent and precipitating the solution by adding a poor solvent to the reaction solution is preferable. The poor solvent may be any solvent as long as it does not dissolve the urea bond-containing polymer, but is an aliphatic hydrocarbon such as cyclohexane, pentane or hexane, an aromatic hydrocarbon such as benzene, toluene or chlorobenzene, Mention may be made of ethers such as diethyl ether and ethylene glycol diethyl ether, esters such as methyl propionate, ethyl acetate and butyl acetate, and alcohols such as methanol, ethanol and propanol.

  In addition, the measurement of molecular weight and molecular weight distribution can be performed based on the following method and conditions.

Solvent: 30 mM LiBr in N-methylpyrrolidone Device: HLC-8220GPC (manufactured by Tosoh Corporation)
Column: TSKgel Super AWM-H x 2 (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Sample concentration: 1.0 g / L
Injection volume: 40 μl Flow rate: 0.5 ml / min
Calibration curve: Standard polystyrene: PS-1 (manufactured by Polymer Laboratories) Mw = 580 to 2,560,000 calibration curves with 9 samples are used.

  As the bond-containing polymer having a urea group, a commercially available product may be used. For example, a compound having a medium polar group or a low polar group at its terminal (BIC Chemie Japan, trade name: BYK-410 (specially modified urea) 411 (modified urea), 420 (modified urea), 425 (urea modified urethane), 428 (polyurethane), 430 (urea modified polyamide), 431 (urea modified polyamide), LPR20320 (special modified urea), P104, P105, etc. ).

  From the viewpoint of more manifesting the effects of the present invention, the compound having a urea group is preferably a urea compound having a medium polar group or a low polarity group at the terminal, and preferably a urea compound having a medium polar group at the terminal. More preferred. BYK-410 etc. are mentioned as a commercial item of the urea compound which has a medium polar group at the terminal.

  The urea bond-containing polymer contained in the mat layer is preferably 20 to 100% by mass with respect to the filler, and 20% by mass with respect to the filler from the viewpoint of preventing mat dropping by efficiently interacting with the filler. % From the viewpoint of further preventing transfer of the additive, more preferably 20 to 70% by mass, and further from the viewpoint of durability, 30 to 70% by mass. Is more preferable.

  Further, the urea bond-containing polymer contained in the mat layer is preferably contained in an amount of 0.1 to 5% by mass with respect to the following cured resin, and the urea bond-containing polymer at the time of winding after forming the laminated film Is more preferably contained in an amount of 0.5 to 2.0% by mass with respect to the following cured resin from the viewpoint of preventing the transfer to the adjacent surface and optical characteristics.

[Curing resin]
The mat layer contains a cured resin.

  The curable resin according to the present invention refers to a curable resin that has been chemically changed from a liquid to a solid (that is, cured) by energy applied from the outside. This cured resin does not include the urea bond-containing polymer.

  The curable resin is an active energy ray curable resin that is cured by irradiating an active energy ray curable resin with an active energy ray such as an ultraviolet ray (UV), a thermosetting resin that is cured by heating the thermosetting resin, or the like. In particular, from the viewpoint of facilitating the formation of the mat layer, an ultraviolet (UV) curable resin is preferable. These curable resins may be used alone or in combination of two or more.

  The UV curable resin according to the present invention refers to a UV curable resin cured by irradiating UV.

  Examples of the UV curable resin for obtaining the UV curable resin include a UV curable urethane acrylate resin, a UV curable polyester acrylate resin, a UV curable epoxy acrylate resin, a UV curable polyol acrylate resin, and a UV curable epoxy resin. Etc. are preferably used. Of these, UV curable acrylate resins are preferable, and UV curable urethane acrylate resins are more preferable.

  The UV curable urethane acrylate resin generally includes 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate (hereinafter referred to as acrylate) in addition to a product obtained by reacting a polyester polyol with an isocyanate monomer or a prepolymer. It can be easily obtained by reacting an acrylate monomer having a hydroxy group such as 2-hydroxypropyl acrylate. For example, those described in JP-A-59-151110 can be used. For example, a mixture of 100 parts by mass of Unidic (registered trademark) 17-806 (manufactured by DIC Corporation) and 1 part by mass of Coronate (registered trademark) L (manufactured by Nippon Polyurethane Co., Ltd.) is preferably used. The UV curable urethane acrylate resin is commercially available. Specifically, the purple light series UV-1400B, UV-1700B, UV-6300B, UV-7550B, UV-7600B, UV-7605B manufactured by Nippon Synthetic Chemical Industry Co., Ltd. , UV-7610B, UV-7620EA, UV-7630B, UV-7640B, UV-6630B, UV-7000B, UV7510B, UV-7461TE, UV-2000B, UV-2010B, UV-2250EA, UV-2750B, manufactured by DIC Unidic series V-4000BA, V-4005, V-4018, V-4025, V-4026, V-4075, V-4200-70, V-4205, V-4260, V-4263, 15-829, 17-813, 17-806, S2-371, U-4HA, U-6HA, U-6LPA, UA-1100H, UA-53H, UA-33H manufactured by Nakamura Chemical Co., Ltd., EBECRYL series 204, 206, 220, 264, 265, 1259K, 1259K manufactured by Daicel Cytec Co., Ltd. , 5129, 8201, 8210, 8301, 294 / 25HD, 4820, 8405, UA-306H, UA-306I, UA-306T, UA-510H, manufactured by Kyoeisha Chemical Co., Ltd., beam set series manufactured by Arakawa Chemical Industries, Ltd., Toagosei OT-1000 series manufactured by Hitachi, Ltd., Teslac series manufactured by Hitachi Chemical Co., Ltd., CN series manufactured by Sartomer, and the like.

  Examples of the UV curable polyester acrylate resin include those that are easily formed when 2-hydroxyethyl acrylate and 2-hydroxy acrylate monomers are generally reacted with a polyester polyol, as disclosed in JP-A-59-151112. Can be used.

  Specific examples of the UV curable epoxy acrylate resin include an epoxy acrylate as an oligomer, and a reactive diluent and a photopolymerization initiator added thereto to react with each other. Can be used.

  Specific examples of the UV curable polyol acrylate resin include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, alkyl-modified dipentaerythritol pentaacrylate, and the like. be able to.

  Specific examples of photopolymerization initiators for these UV curable resins include benzoin and its derivatives, acetophenone, benzophenone, hydroxybenzophenone, Michler's ketone, α-amyloxime ester, thioxanthone, and derivatives thereof. You may use with a photosensitizer. The photopolymerization initiator can also be used as a photosensitizer. In addition, when using an epoxy acrylate photopolymerization initiator, a sensitizer such as n-butylamine, triethylamine, tri-n-butylphosphine can be used. The photopolymerization initiator or photosensitizer used in the UV curable resin composition is 0.1 to 15 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the composition.

  As a monomer of the UV curable resin, for example, a monomer having an unsaturated double bond is a common monomer such as methyl acrylate, ethyl acrylate, butyl acrylate, benzyl acrylate, cyclohexyl acrylate, vinyl acetate, or styrene. Can be mentioned. Further, as monomers having two or more unsaturated double bonds, ethylene glycol diacrylate, propylene glycol diacrylate, divinylbenzene, 1,4-cyclohexane diacrylate, 1,4-cyclohexyldimethyl adiacrylate, trimethylolpropane triacrylate, Examples include pentaerythritol tetraacrylic ester. Commercially available products include Adekaoptomer (registered trademark) KR / BY series: KR-400, KR-410, KR-550, KR-566, KR-567, BY-320B (above, manufactured by ADEKA Corporation); Hard A-101-KK, A-101-WS, C-302, C-401-N, C-501, M-101, M-102, T-102, D-102, NS-101, FT-102Q8 MAG-1-P20, AG-106, M-101-C (manufactured by Guangei Chemical Co., Ltd.); Seika Beam (registered trademark) PHC2210 (S), PHCX-9 (K-3), PHC2213, DP-10 , DP-20, DP-30, P1000, P1100, P1200, P1300, P1400, P1500, P1600, SCR900 (above, Dainichi Chemical Industries KRM7033, KRM7039, KRM7130, KRM7131, UVECRYL29201, UVECRYL29202 (above, manufactured by Daicel UC Corporation); RC-5015, RC-5016, RC-5020, RC-5031, RC-5100, RC- 5102, RC-5120, RC-5122, RC-5152, RC-5171, RC-5180, RC-5181 (manufactured by DIC Corporation); 340 clear (above, manufactured by China Paint Co., Ltd.); Sunrad (registered trademark) H-601, RC-750, RC-700, RC-600, RC-500, RC-611, RC-612 (Sanyo Chemical Industries, Ltd.) SP-1509, SP-1507 (above, Showa Polymer Co., Ltd.); RCC-15C (above, Grace Japan Co., Ltd.), Aronix (registered trademark) M-6100, M-8030, M- 8060 (manufactured by Toagosei Co., Ltd.), NK hard B-420, NK ester A-DOG, NK ester A-IBD-2E (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like can be appropriately selected and used.

  Examples of more specific compounds include trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dioxane glycol acrylate, ethoxylated acrylate, alkyl-modified dipenta Examples include erythritol pentaacrylate.

  Examples of the thermosetting resin include thermosetting urethane resin composed of acrylic polyol and isocyanate prepolymer, phenol resin, urea melamine resin, bisphenol F type epoxy resin, polyfunctional epoxy resin, brominated epoxy resin, glycidyl. Examples thereof include epoxy resins such as ester type epoxy resins and biphenyl type epoxy resins, unsaturated polyester resins, and silicon resins.

  Polysilazane can also be suitably used as a thermosetting resin or an ultraviolet (UV) curable resin by a curing method. Although it does not restrict | limit especially as polysilazane, For example, it is preferable that it is a compound which has the main frame | skeleton which consists of a unit represented by the following general formula (I).

In the general formula (I), R ¹ , R ² , and R ³ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group, or an alkoxy group. Represents a group.

The polysilazane is more preferably perhydropolysilazane (hereinafter also referred to as “PHPS”) in which all of R ¹ , R ² , and R ³ are hydrogen atoms.

  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 (polystyrene conversion) in terms of number average molecular weight (Mn), and can be a liquid or solid substance depending on the molecular weight. As the perhydropolysilazane, a commercially available product may be used. As the commercially available product, NN120-10, NN120-20, NAX120-20, NN110, NAX120, NAX110, NL120A, NL110A, NL150A, NP110, NP140 (or more, AZ Electronic Materials Co., Ltd.).

  As another example of polysilazane, a silicon alkoxide-added polysilazane obtained by reacting a silicon alkoxide with the polysilazane represented by the above general formula (I) (for example, JP-A-5-238827) or glycidol is reacted. Glycidol-added polysilazane (for example, JP-A-6-122852) obtained by reaction, alcohol-added polysilazane (for example, JP-A-6-240208) obtained by reacting alcohol, and metal carboxylate Metal silicic acid salt-added polysilazane (for example, JP-A-6-299118), acetylacetonate complex-added polysilazane (for example, JP-A-6-306329) obtained by reacting a metal-containing acetylacetonate complex, metal Gold obtained by adding fine particles Particles added polysilazane (e.g., JP-A-7-196986 JP), and the like.

  These curable resins may be used alone or in combination of two or more. Moreover, the copolymer of these resin may be sufficient.

[Other ingredients]
The mat layer of the present invention may further contain other components such as an organic solvent, an antioxidant, and a surfactant as long as the effects of the present invention are not impaired. Hereinafter, the organic solvent and antioxidant which are other preferable components will be described.

《Organic solvent》
The mat layer of the present invention may contain an organic solvent. Examples of the organic solvent contained in the composition include hydrocarbons (toluene, xylene), alcohols (methanol, ethanol, isopropanol, butanol, cyclohexanol), ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone), These may be appropriately selected from esters (methyl acetate, ethyl acetate, methyl lactate), glycol ethers, and other organic solvents, or may be used by mixing them.

"Antioxidant"
The mat layer of the present invention can contain an antioxidant. As the antioxidant used in the present invention, various known compounds can be used, and examples thereof include L-ascorbic acid and its ester, D-ascorbic acid and its ester, α-tocopherol, sezamol and the like. In addition, hindered phenol antioxidants can also be used. Specific examples include 2-methylphenol, 2,6-dimethylphenol, 2,4,6-trimethylphenol, and 2,6-dimethyl-4- Octylphenol, 2-t-butylphenol, 2,6-di-t-butylphenol, 2,4,6-tri-t-butylphenol, 2,6-di-t-butyl-4-octylphenol, triethylene glycol bis [3 -(3-t-butyl-5-methyl-4-hydroxyphenyl) pionate], 1,6-hexanediol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2 , 4-Bis (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine Pentaerythrityltetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxy) Phenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxycinna Mido), 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4 -Hydroxybenzyl) benzene, tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 2,4-bis [(octylthio) methyl]- - cresol, N, N'-bis [3- (3,5-di -t- butyl-4-hydroxyphenyl) propionyl] hydrazine and the like.

  These antioxidants can be used alone or in admixture of two or more.

  The addition amount of the antioxidant is preferably 0.1 to 20% by mass, and more preferably 0.5 to 10% by mass with respect to the total mass of the mat layer.

[Mat layer forming method]
The mat layer as described above is blended with the above components and prepared as a coating solution by using a diluent solvent as necessary, and the coating solution is applied to the surface of the substrate by a conventionally known coating method such as a spin coating method, It can be applied by a die coating method, a roll coating method, a flow coating method, an ink jet method, a spray coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method, a gravure printing method, or the like. Further, after applying the coating solution, the mat layer can be formed by curing by a conventionally known method, for example, ultraviolet irradiation, heating or the like. In addition, as a method of irradiating ultraviolet rays, xenon arc lamps, metal halide lamps, excimer lamps, UV light lasers, etc. are used, preferably by irradiating ultraviolet rays in the wavelength region of 200 to 380 nm, more preferably 280 to 380 nm. It can be carried out.

Irradiation energy amount in the case of using the ultraviolet (irradiation amount) is not particularly limited, is preferably from 100 to 800 mJ / cm ^2, more preferably 200~500mJ / cm ^2.

<Functional layer>
The laminated film which concerns on this invention has a functional layer arrange | positioned on the other surface with respect to one surface of the base material with which the said mat | matte layer is arrange | positioned. The functional layer varies depending on the use of the laminated film according to the present invention, and may be a gas barrier layer, a transparent conductive layer, or various optical films.

[Gas barrier layer]
The functional layer may be a gas barrier layer.

The gas barrier layer referred to in the present invention means a layer having gas barrier properties. From the viewpoint of application to an electronic device, the water vapor permeability (WVTR) of the gas barrier layer according to the present invention is preferably 0.1 g / (m ² · 24 h) or less, and 0.01 / (m ² · 24h) or less is more preferable.

The gas barrier layer is not particularly limited, and examples thereof include a layer containing metal oxide, metal nitride, metal carbide, metal oxynitride, or metal oxycarbide. Specifically, the gas barrier layer includes silicon oxide (SiO ₂ ), silicon nitride, silicon oxynitride (SiON), silicon oxycarbide (SiOC), silicon carbide, silicon oxynitride carbide (SiONC), and aluminum silicate (SiAlO). It is preferable to include at least one selected from the group consisting of A method for forming the gas barrier layer is not particularly limited, and a CVD method, a PVD method, a method of performing a modification treatment after applying a coating solution containing a silicon compound as described in US Patent Publication No. 2013/236710, and the like. Can be mentioned.

  Among these, the gas barrier layer is preferably a layer containing silicon, oxygen, and carbon. Further, the gas barrier layer preferably satisfies at least one of the following conditions (i) to (iii), more preferably satisfies at least two conditions, and satisfies the three conditions. It is even more preferable that everything is satisfied.

  (I) The relationship between the distance (L) from the gas barrier layer surface in the film thickness direction of the gas barrier layer and the ratio of the amount of silicon atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (the atomic ratio of silicon) A silicon distribution curve showing the relationship between the L and the ratio of the amount of oxygen atoms to the total amount of silicon atoms, oxygen atoms, and carbon atoms (atomic ratio of oxygen), and the L, silicon atoms, oxygen In the carbon distribution curve showing the relationship between the atoms and the ratio of the amount of carbon atoms to the total amount of carbon atoms (the atomic ratio of carbon), in the region of 90% or more (upper limit: 100%) of the film thickness of the gas barrier layer, (Atom ratio of oxygen), (Atom ratio of silicon) and (Atom ratio of carbon) increase in this order (atomic ratio is O> Si> C).

  When this condition (i) is satisfied, the resulting gas barrier film has better gas barrier properties and flexibility. Here, in the carbon distribution curve, the relationship between the above (atomic ratio of oxygen), (atomic ratio of silicon) and (atomic ratio of carbon) is at least 90% or more (upper limit: 100%) of the film thickness of the gas barrier layer. ) And more preferably at least 93% or more (upper limit: 100%). 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.

  (Ii) The carbon distribution curve has at least two extreme values. The carbon distribution curve preferably has at least three extreme values, more preferably at least four extreme values, but may have five or more.

  When the extreme value of the carbon distribution curve is 2 or more, the gas barrier property when the obtained gas barrier film is bent is improved. The upper limit of the extreme value of the carbon distribution curve is not particularly limited, but is preferably 30 or less, more preferably 25 or less, for example. However, since the number of extreme values is also caused by the film thickness of the gas barrier layer, it cannot be specified unconditionally.

  In the present specification, the “extreme value” refers to the maximum value or the minimum value of the atomic ratio of the element to the distance (L) from the surface of the gas barrier layer in the film thickness direction of the gas barrier layer. Further, in this specification, the “maximum value” is a point where the value of the atomic ratio of an element (oxygen, silicon or carbon) changes from increase to decrease when the distance from the surface of the gas barrier layer is changed, And the value of the atomic ratio of the element at the position where the distance from the surface of the gas barrier layer in the thickness direction of the gas barrier layer from the point is further changed in the range of 4 to 20 nm, rather than the value of the atomic ratio of the element at that point. It means a point that decreases 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. Similarly, the “minimum value” in this specification is a point in which the value of the atomic ratio of an element (oxygen, silicon, or carbon) changes from decrease to increase when the distance from the surface of the gas barrier layer is changed. In addition, the atomic ratio value of the element at a position where the distance from the point in the thickness direction of the gas barrier layer from the point to the surface of the gas barrier layer is further changed by 4 to 20 nm is 3 at%. This is the point that increases. 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.

(Iii) The absolute value of the difference between the maximum value and the minimum value of the carbon atomic ratio in the carbon distribution curve (hereinafter, also simply referred to as “C _max −C _min difference”) is 3 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 further improved. The C _max -C _min difference is preferably 5 at% or more, more preferably 7 at% or more, and particularly preferably 10 at% or more. By setting the C _max −C _min difference, the gas barrier property can be further improved. In the present specification, the “maximum value” is the atomic ratio of each element that is maximum in the distribution curve of each element, and is the highest value among the maximum values. Similarly, in this specification, the “minimum value” is the atomic ratio of each element that is the minimum in the distribution curve of each element, and is the lowest value among the minimum values. Here, the upper limit of the C _max -C _min difference is not particularly limited, but it is preferably 50 at% or less, and 40 at% or less in consideration of the effect of suppressing / preventing crack generation when the gas barrier film is bent. It is more preferable that

  The thickness of the gas barrier layer is usually in the range of 5 to 500 nm, preferably 10 to 200 nm.

  The silicon distribution curve, the oxygen distribution curve, the carbon distribution curve, and the oxygen carbon distribution curve are obtained by using X-ray photoelectron spectroscopy (XPS) measurement and rare gas ion sputtering such as argon in combination. Thus, it can be created by so-called XPS depth profile measurement in which 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 having the horizontal axis as the etching time in this way, the etching time is generally correlated with the distance (L) from the surface of the gas barrier layer in the film thickness direction of the barrier layer in the film thickness direction. , “Distance from the surface of the gas barrier layer in the film thickness direction of the barrier layer” is the distance from the surface of the barrier layer calculated from the relationship between the etching rate and the etching time employed in the XPS depth profile measurement. be able to. In the present invention, the silicon distribution curve, oxygen distribution curve, carbon distribution curve, and oxygen carbon distribution curve are created under the following measurement conditions.

(Measurement condition)
Etching ion species: Argon (Ar ⁺ );
Etching rate (converted to SiO ₂ thermal oxide film): 0.05 nm / sec;
Etching interval (SiO ₂ equivalent value): 10 nm;
X-ray photoelectron spectrometer: Model name "VG Theta Probe", manufactured by Thermo Fisher Scientific;
Irradiation X-ray: Single crystal spectroscopy AlKα
X-ray spot and its size: 800 × 400 μm oval.

  The gas barrier layer may be a single layer or two or more layers. When composed of two or more layers, each gas barrier layer preferably has a thickness as described above. Further, the thickness of the entire gas barrier layer when the gas barrier layer is composed of two or more layers is not particularly limited.

  In the present invention, the gas barrier layer may be formed by a chemical vapor deposition method. The chemical vapor deposition method is also called chemical vapor deposition method or CVD method. In particular, the gas barrier layer is preferably formed by plasma CVD (plasma-enhanced chemical vapor deposition (PECVD), hereinafter, also simply referred to as “plasma CVD method”). Most preferably, the substrate is formed by a plasma CVD method in which a substrate is disposed on a pair of film forming rollers, and plasma is generated by discharging between the pair of film forming rollers. Hereinafter, a method for forming a gas barrier layer using the plasma CVD method preferably used in the present invention will be described.

[Preferred Method for Forming Gas Barrier Layer]
As described above, as a method of forming the gas barrier layer on the surface of the base material, it is preferable to employ a plasma CVD method from the viewpoint of gas barrier properties. The plasma CVD method may be a Penning discharge plasma type plasma CVD method.

  Further, when plasma is generated in the plasma CVD method, it is preferable to generate plasma discharge in a space between a plurality of film forming rollers. A pair of film forming rollers is used, and each of the pair of film forming rollers is used. More preferably, the substrate is disposed and discharged between a pair of film forming rollers to generate plasma. In this way, by using a pair of film forming rollers, placing a base material on the pair of film forming rollers, and discharging between the pair of film forming rollers, one film forming roller It is possible not only to produce a thin film efficiently because it is possible to form a film on the surface part of the base material existing in the film while simultaneously forming a film on the surface part of the base material present on the other film forming roller. The film formation rate can be doubled compared to the plasma CVD method without using any roller, and a film having substantially the same structure can be formed, so that the extreme value in the carbon distribution curve can be at least doubled. It is possible to form a layer that satisfies at least one 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 a gas barrier layer on the surface of a 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 the rollers. For example, it is possible to manufacture by a roll-to-roll method using a plasma CVD method.

  Hereinafter, the gas barrier layer forming method according to the present invention will be described in more detail with reference to FIG. FIG. 2 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.

  The manufacturing apparatus 31 shown in FIG. 2 includes a delivery roller 32, transport rollers 33, 34, 35, and 36, film formation rollers 39 and 40, a gas supply pipe 41, a plasma generation power source 42, and a film formation 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.

  The specific description and suitable conditions of the apparatus shown in FIG. 2 are described in International Publication No. 2014/119754, [0099] to [0109], and can be referred to by reference.

  Using such a manufacturing apparatus 31 shown in FIG. 2, 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. 2, a discharge is generated between the 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 A point of the film-forming roller 39 and B point of the film-forming roller 40 in FIG. 2, 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 in FIG. 2 and the points C3 and C4 of the film forming roller 40, the minimum value of the carbon distribution curve is formed in the gas barrier layer. Is done. 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 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 a film forming gas (such as a source gas) supplied from the gas supply pipe 41 to the facing space, a source gas, a reaction gas, a carrier gas, and a 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 those described in [0111] of International Publication No. 2014/119754, such as hexamethyldisiloxane (HMDSO). Among these organosilicon compounds, hexamethyldisiloxane and 1,1,3,3-tetramethyldisiloxane are preferable from the viewpoints of characteristics such as handling of the compound and gas barrier properties of the resulting 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.

As a 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. In the case of producing an oxygen-based thin film, suitable ratios of the raw material gas and the reactive gas in the film forming gas are described in [0116] to [0118] of International Publication No. 2014/119754, see Can be quoted.

  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 the plasma CVD method 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 electronic devices and the like.

<Hard coat layer>
The laminated film according to the present invention may have a hard coat layer. By arranging the hard coat layer, for example, when the laminated film according to the present invention is used as a sealing film for an electronic device, the long-term reliability of the device can be improved. The hard coat layer may also have a function of preventing scratches on the surface of the electronic device. The hard coat layer may be disposed between the base material and the functional layer from the viewpoint of improving the smoothness of the base material, or may be disposed on the surface of the base material opposite to the functional layer.

  The hard coat layer contains a curable resin. The curable resin is not particularly limited, and the active energy ray curable resin or the thermosetting material obtained by irradiating the active energy ray curable material with an active energy ray such as ultraviolet ray to be cured is heated. The thermosetting resin etc. which are obtained by curing by the above method. These curable resins may be used alone or in combination of two or more. Specific examples of such a curable resin are the same as those of the mat layer.

  The method for forming the hard coat layer is not particularly limited, but a coating solution containing a curable material is applied to a spin coating method, a spray method, a blade coating method, a dipping method, a wet coating method such as a gravure printing method, or a vapor deposition method. After coating by a dry coating method to form a coating film, the coating film is irradiated with active energy rays such as visible rays, infrared rays, ultraviolet rays, X rays, α rays, β rays, γ rays, and electron beams and / or heated. A method of forming by curing is preferred. As a method of irradiating active energy rays, for example, an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a metal halide lamp or the like is preferably used to irradiate ultraviolet rays in a wavelength region of 100 to 400 nm, more preferably 200 to 400 nm Alternatively, a method of irradiating an electron beam having a wavelength region of 100 nm or less emitted from a scanning or curtain type electron beam accelerator can be used.

  The thickness of the hard coat layer is preferably 0.2 to 15 μm, more preferably 0.5 to 10 μm. When the thickness of the hard coat layer is a value within such a range, it is possible to achieve a laminated film having excellent flexibility, and it is easy to control the value of warpage (curl) described later within a suitable range, preferable.

  The pencil hardness of the hard coat layer is preferably HB or higher. The pencil hardness is 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H in order from the softest. If the pencil hardness is equal to or higher than HB, scratch resistance on the surface of the electronic device can be sufficiently achieved. The pencil hardness is preferably F or more, more preferably H or more. The upper limit of the pencil hardness of the hard coat layer is not particularly limited, but is preferably 10H or less, and more preferably 8H or less. The pencil hardness can be measured by the method described in JIS K5600-5-4: 1999. When measuring pencil hardness of 10H, 7B, 8B, 9B, 10B, use 10H, 7B, 8B, 9B, 10B pencils made by Mitsubishi Pencil Co., Ltd. Measure.

<Primer layer (smooth layer)>
The laminated film of the present invention may have a primer layer (smooth layer) on the surface of the substrate, preferably between the substrate and the functional layer. The primer layer is provided for flattening the rough surface of the substrate on which protrusions and the like exist. Such a primer layer is basically formed by curing an active energy ray-curable material or a thermosetting material. The primer layer may basically have the same configuration as the hard coat layer as long as it has the above function.

  Examples of the active energy ray-curable material and the thermosetting material, and the method for forming the primer layer are the same as those described in the column of the hard coat layer, and thus the description thereof is omitted here.

  The smoothness of the primer layer is a value expressed by the surface roughness specified in JIS B0601: 2001, and the maximum cross-sectional height Rt (p) is preferably 10 nm or more and 30 nm or less. Note that the lower limit of the maximum cross-sectional height Rt (p) is not particularly limited and is 0 nm, but it may normally be 0.5 nm or more. The thickness of the primer layer is not particularly limited but is preferably in the range of 0.1 to 10 μm.

<Anchor coat layer>
On the surface of the base material according to the present invention, an anchor coat layer may be formed as an easy adhesion layer for the purpose of improving adhesiveness (adhesion). Examples of the anchor coating agent used in this anchor coat layer include polyester resin, isocyanate resin, urethane resin, acrylic resin, ethylene vinyl alcohol resin, vinyl modified resin, epoxy resin, modified styrene resin, modified silicon resin, and alkyl titanate. One type or two or more types can be used in combination. A commercially available product may be used as the anchor coating agent. Specifically, a siloxane-based UV curable polymer solution (manufactured by Shin-Etsu Chemical Co., Ltd., 3% isopropyl alcohol solution of “X-12-2400”) can be used.

Conventionally known additives can be added to these anchor coating agents. The above-mentioned anchor coating agent is coated on a substrate by a known method such as roll coating, gravure coating, knife coating, dip coating, spray coating, and the like, and is coated by drying and removing the solvent, diluent, etc. Can do. The application amount of the anchor coating agent is preferably about 0.1 to 5 g / m ² (dry state). A commercially available base material with an easy-adhesion layer may be used.

  Alternatively, the anchor coat layer can be formed by a vapor phase method such as physical vapor deposition or chemical vapor deposition. For example, as described in JP-A-2008-142941, an inorganic film mainly composed of silicon oxide can be formed for the purpose of improving adhesion and the like.

  The thickness of the anchor coat layer is not particularly limited, but is preferably about 0.5 to 10.0 μm.

  The laminated film of the present invention can be further provided with functionalized layers such as another organic layer, a protective layer, a hygroscopic layer, and an antistatic layer as necessary.

<Laminated film with protective film>
According to the other form of this invention, the laminated | multilayer film with a protective film by which the protective film was arrange | positioned at the laminated film mentioned above are also provided. At this time, the protective film may be disposed on one outermost surface of the laminated film, or may be disposed on both outermost surfaces. By providing the protective film, it is effective to protect the laminated film surface from damage.

  Although there is no restriction | limiting in particular as a protective film, The film which consists of a resin material at least is mentioned. The protective film may be wound into a roll before being bonded to the laminated film. Moreover, the protective film may be arrange | positioned at the laminated | multilayer film through the adhesion layer.

  The resin material used for the protective film is not particularly limited, but is a polyolefin film such as polyethylene film or polypropylene film; a polyester film such as polyethylene terephthalate or polybutylene terephthalate; a polyamide film such as hexamethylene adipamide; Halogen-containing films such as chloride, polyvinylidene chloride, and polyfluoroethylene; plastic films such as polyvinyl acetate, polyvinyl acetate such as polyvinyl acetate, polyvinyl alcohol, and ethylene acetate pinyl copolymer, and their derivative films are different from paper in that they generate fine dust. It is preferable because it does not occur. In the present invention, a polyethylene terephthalate film is preferably used from the viewpoints of heat resistance and availability.

  The thickness of the protective film is not particularly limited, but for example, a thickness of 10 μm to 300 μm is used. Preferably it is a thing of 25 micrometers-150 micrometers. If it is 10 μm or more, the film is sufficiently thick and easy to handle, and if it is 300 μm or less, it is sufficiently flexible and has excellent transportability and adhesion to a roll.

  When the protective film is disposed on the laminated film via the adhesive layer, the type of the adhesive used for the adhesive layer is not particularly limited. For example, an acrylic adhesive, a rubber adhesive, a urethane adhesive, Examples include silicone adhesives, UV curable adhesives, polyolefin adhesives, ethylene vinyl acetate copolymer (EVA) adhesives, etc., selected from acrylic adhesives, silicon adhesives, and rubber adhesives It is preferable that it is at least one kind.

<Application example of laminated film>
The laminated film of the present invention as described above provides a laminated film in which deterioration of the film performance is suppressed by preventing mat dropping in the mat layer after film formation and further preventing transfer occurring during winding. For this reason, the laminated | multilayer film of this invention can be used for various uses, such as an optical film in an electronic device, and a functional member film.

  Hereinafter, the present invention will be specifically described using examples and comparative examples. However, the present invention is not limited to these. In the following examples and comparative examples, “part” or “%” is used, and “part by mass” or “% by mass” is expressed unless otherwise specified.

[Example 1: Production of gas barrier film 101]
(Preparation of resin base material)
Polyethylene terephthalate (PET) (KEL86W manufactured by Teijin DuPont Co., Ltd .: thickness 125 μm) was used as the roll base material.

(Formation of mat layer by coating method)
<Adjustment of coating solution>
Esdrimer (registered trademark) LU-102 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) as a thermosetting resin was diluted in the solvent methyl ethyl ketone (MEK) to adjust the solid content to 35%. To this solution, Sea Hoster (registered trademark) KE-P30 (average particle size 0.3 μm: amorphous silica) (manufactured by Nippon Shokubai Co., Ltd.) was added as a filler so as to be 1% with respect to the amount of the thermosetting resin.

  Next, in this solution, BYK-410 (manufactured by Big Chemie Japan Co., Ltd .; solid content 52%) as a urea bond-containing polymer is 1% in solid content with respect to the amount of the curable resin, and 100% with respect to the amount of filler added. % And stirred at room temperature for 15 minutes to prepare a coating solution.

<Formation of mat layer>
The coating liquid was applied to the surface of the previously formed substrate so that the (average) film thickness after drying was 1 μm, dried at 90 ° C., and then dried at 120 ° C. for 10 seconds to form a mat layer.

<Formation of functional layer (gas barrier layer (hereinafter also simply referred to as barrier layer))>
Next, a functional layer (barrier layer) having a thickness of 100 nm is formed on the other base material surface of the base material surface on which the mat layer is formed using the plasma CVD apparatus of FIG. Was completed.

[Plasma deposition conditions]
<Film forming conditions>
-Film transport speed: 0.5 m / min
・ Supply amount of source 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: 80 kHz.

[Example 2: Production of gas barrier film 102]
A gas barrier film 102 was produced in the same manner as the gas barrier film 101 except for the following steps.

<Adjustment of coating solution>
Unidic V-4025 (manufactured by DIC, urethane acrylate resin) as a UV curable resin was diluted in a solvent propylene glycol monomethyl ether (PGME) to adjust the solid content to 35%. To this solution, Seahoster (registered trademark) KE-P30 (average particle size 0.3 μm) (manufactured by Nippon Shokubai Co., Ltd.) was added as a filler so as to be 3% based on the amount of the curable resin. Next, BYK-410 (manufactured by Big Chemie) as a urea bond-containing polymer was added to this solution so as to be 1% with respect to the amount of the curable resin, and a coating solution was prepared by stirring at room temperature for 15 minutes.

<Formation of mat layer>
The above-mentioned coating solution is applied to the surface of the previously formed substrate so that the (average) film thickness after drying is 1 μm, and is dried by treatment at 90 ° C. for 1 minute in an atmosphere of temperature 25 ° C. and humidity 60% RH. Then, UV irradiation with an integrated light amount of 500 mJ / cm ² was performed with a UV effect device to form a mat layer.

[Example 3: Production of gas barrier film 103]
The addition amount of the urea bond-containing polymer is 0.5% with respect to the UV curable resin, and the type of filler is crosslinked acrylic resin particles (Epester (registered trademark) MX100W (manufactured by Nippon Shokubai Co., Ltd.) average particle size 0.2 μm) A gas barrier film 103 was produced in the same manner as the gas barrier film 102 except that.

[Example 4: Production of gas barrier film 104]
Except for using cross-linked acrylic resin particles (trade name: SSX-103, cross-linked polymethyl methacrylate, manufactured by Sekisui Plastics Co., Ltd.) having an average particle size of 3 μm as the filler, A gas barrier film 104 was produced.

[Example 5: Production of gas barrier film 105]
The addition amount of the urea bond-containing polymer is 2.0% with respect to the UV curable resin, and the average particle size of the filler is 5 μm (cross-linked acrylic resin particles, trade name: MBX-5, cross-linked polymethyl methacrylate, sekisui A gas barrier film 105 was produced in the same manner as the gas barrier film 104 except that the product was manufactured by Kosei Kogyo Co., Ltd.

[Example 6: Production of gas barrier film 106]
The gas barrier film 106 was formed in the same manner as the gas barrier film 105 except that the average particle size of the filler (crosslinked acrylic) was 1.5 μm (crosslinked acrylic resin particles, trade name: MX-150, manufactured by Soken Chemical Co., Ltd.). Produced.

[Example 7: Production of gas barrier film 107]
A gas barrier film 107 was produced in the same manner as the gas barrier film 106 except that the addition amount of the urea bond-containing polymer was 2.5% with respect to the UV curable resin.

[Comparative Example 1: Production of gas barrier film 108]
A gas barrier film 108 was produced in the same manner as the gas barrier film 106 except that no additive was added to the mat layer.

[Comparative Example 2: Production of gas barrier film 109]
The additive is not added to the mat layer, and the type of filler is a cross-linked acrylic resin particle (trade name: MX-180TA, manufactured by Soken Chemical Co., Ltd.) (average particle size is 1.8 μm). A gas barrier film 109 was produced in the same manner as the gas barrier film 101 except for 3%.

[Comparative Example 3: Production of Gas Barrier Film 110]
A gas barrier film 110 was produced in the same manner as the gas barrier film 102 except that no filler was added to the mat layer.

[Comparative Example 4: Production of Gas Barrier Film 111]
The gas barrier film 106 except that the additive was changed from a urea bond-containing polymer to a water-added castor oil system (ITO Oil Co., Ltd. A-SA-VF-1) and the amount added to the curable resin was 1%. Similarly, a gas barrier film 111 was produced.

[Comparative Example 5: Production of gas barrier film 112]
A gas barrier film 112 was produced in the same manner as the gas barrier film 111 except that the additive was changed to an acrylic polymer (BR-87 manufactured by Mitsubishi Rayon Co., Ltd.).

[Comparative Example 6: Production of gas barrier film 113]
A gas barrier film 113 was produced in the same manner as the gas barrier film 111 except that the additive was changed to a higher fatty acid amide (Ito Oil Co., Ltd. T-300-20AK).

[Comparative Example 7: Production of gas barrier film 114]
A gas barrier film 114 was produced in the same manner as the gas barrier film 111 except that the additive was changed to polyethylene oxide (DISPARLON 4200-20 manufactured by Enomoto Kasei Co., Ltd.).

<Evaluation method>
《Matte drop》
The mat fall of the gas barrier film prepared above was measured. The measurement is performed by cutting a test piece from the above-mentioned gas barrier film into a size of 30 mm in length and 30 mm in width, and measuring the surface of the mat layer using a light interference type surface shape roughness measurement system (Veeco WYKO-NT9000 series). The number of dents with a filler diameter of ± 10% was measured.
Rank 1: 30 or more 2: 15 or more and less than 30 3: 5 or more and less than 15 4: 1 or more and less than 5 5: 0
A test piece was cut out from the gas barrier film with a size of 30 mm in length and 30 mm in width, the mat layer of the test piece was opposed to the functional layer (barrier layer), and a 3 kg weight was placed thereon and held for 3 hours. Thereafter, the water contact angle of the functional layer (barrier layer) of the test piece was measured using an automatic contact angle meter DMs-401 (manufactured by Kyowa Interface Chemical Co., Ltd.), and the average value of 10 measurement results was calculated.
1: 15 ° or more 2: 10 ° or more and less than 15 ° 3: 5 ° or more and less than 10 ° 4: 2 ° or more and less than 5 ° 5: less than 2 ° << Evaluation of water vapor barrier property (water vapor transmission rate (WVTR)) >>
About the gas barrier film produced above, water vapor barrier property was measured. The measurement was performed based on JIS standard K7129 method (temperature 40 ° C., humidity 90% RH) using PERMATRAN-W3 / 33 manufactured by MOCON according to the Mocon method.

  The results are shown in Table 1.

  In addition, in Table 1 above, the addition amount (vs. filler amount) is obtained by rounding off the first decimal place from the calculated value calculated from the addition amount of the additive to the curable resin and the addition amount of the filler to the curable resin amount. It is.

  As is clear from the results in Table 1 above, Examples 1-7 are superior to Comparative Examples 1-7 in mat removal, transfer evaluation, and water vapor transmission rate.

  In particular, when Examples 1 to 7 and Comparative Examples 4 to 7 are compared, when the mat layer contains a urea bond-containing polymer as an additive, mat removal and transfer are efficiently prevented, and water vapor permeability is also excellent. I understand that. From this result, the urea bond portion of the additive interacts with the filler, and the urea bond-containing polymer is taken together with the filler in the network structure of the cured resin. This is considered to be the main factor of the water vapor transmission rate.

<Evaluation method>
<Dynamic friction coefficient measurement>
The mat layer and the functional layer were opposed to each other, and the dynamic friction coefficient was measured. The measurement is performed by cutting a test piece from the above gas barrier film into a size of 13 cm in length and 15 cm in width, using a friction measuring device TR-2 (manufactured by Toyo Seiki Seisakusho), fixing the functional layer, and rubbing the surfaces. went.
Rank 1: Not measurable 2: 1.0 or more and less than 1.5 3: 0.7 or more and less than 1.0 4: 0.4 or more and less than 0.7 5: Less than 0.4

  From the results in Table 2, it can be seen that the contact between the back surface and the barrier surface at the time of roll winding is reduced by adding a filler, particularly by comparison with Comparative Example 3. From the results of Tables 1 and 2, it can be seen that the films of the examples can prevent mat dropping and transfer while maintaining the reduction of the dynamic friction coefficient by the addition of such fillers.

  In Comparative Example 3, the evaluation of the mat removal item as “−” means that no mat removal occurs because no filler is added.

  Furthermore, from the results of Table 1 and Table 2, when Example 6 is compared with other examples, the particle size of the filler is 0.5 to 3.5 μm, and the urea bond-containing polymer is 20 to 20 When 70% by mass is contained, and when the urea bond-containing polymer is contained by 0.5 to 2.0% by mass with respect to the cured resin, excellent lamination in all of mat removal, coefficient of dynamic friction, transfer evaluation, and water vapor transmission rate It has been found that a film is provided.

  That is, according to the present invention, it is expected to provide a laminated film in which deterioration of film performance is suppressed by preventing mat dropping in the mat layer after film formation and further preventing transfer occurring during winding. The

  The application of the present invention is not limited to the above-described embodiment, and can be appropriately changed without departing from the spirit of the present invention.

  This application is based on Japanese Patent Application No. 2014-116124 filed on June 4, 2014, the disclosure of which is referred to and incorporated in its entirety.

Claims (7)

A substrate, a mat layer disposed on one surface of the substrate, and a functional layer disposed on the other surface of the substrate,
A laminated film in which the mat layer contains a filler having an average particle size of 0.1 to 7 μm, a urea bond-containing polymer, and a cured resin.   The laminated film according to claim 1, wherein the functional layer is a gas barrier layer.   The laminated film according to claim 1 or 2, wherein the curable resin is a UV curable resin.   The laminated film according to any one of claims 1 to 3, wherein the filler is crosslinked acrylic resin particles.   The laminated film according to any one of claims 1 to 4, wherein the average particle diameter is 0.5 to 3.5 µm.   The laminated film according to any one of claims 1 to 5, wherein the urea bond-containing polymer is contained in an amount of 20 to 70 mass% with respect to the filler.   The laminated film according to any one of claims 1 to 6, wherein the urea bond-containing polymer is contained in an amount of 0.5 to 2.0 mass% with respect to the cured resin.