JP5724298B2 - Method for producing gas barrier film and method for forming gas barrier layer - Google Patents

Description

  The present invention relates to a method for producing a gas barrier film and a method for forming a gas barrier layer that are positioned as key parts applied to next-generation energy-saving products (for example, solar cells, power generation elements, display devices, lighting devices, etc.).

  The gas barrier film is preferably applied to devices such as organic EL elements, liquid crystal display elements, thin film transistors, solar cells, touch panels, electronic papers and the like in order to prevent permeation of chemical components such as oxygen or water vapor that degrade their performance. Yes. In particular, it has recently been positioned as a key part applied to next-generation energy-saving products (for example, solar cells, power generation elements, display devices, lighting devices, etc.). For this reason, gas barrier films are required to have high gas barrier properties as electronic devices have higher performance and higher quality. On the other hand, cost reduction is also demanded for the gas barrier film due to the demand for particularly low price.

  Some recent gas barrier films include a plastic film, an organic layer provided on the plastic film, and an inorganic layer provided on the organic layer. The organic layer is provided as a planarizing layer under the gas barrier inorganic layer, and plays a role of increasing the gas barrier property by reducing defects generated in the inorganic layer.

  Research and development of gas barrier films have been actively conducted. For example, in Patent Document 1, an adhesive inorganic compound layer, an organic resin layer, an inorganic compound are used for the purpose of reducing the influence of protrusions and pinholes on a base material. A gas barrier film in which layers are sequentially formed has been proposed. In this document, as a preferable constituent material of an organic resin layer that acts as a planarizing layer, an epoxy acrylate resin having a fluorene skeleton, a polybasic acid anhydride, a polyfunctional acrylate monomer, a polymerization initiator, and an epoxy group are contained in one molecule. A cardo polymer containing two or more epoxy resins as essential components has been proposed.

  Also in Patent Document 2, the order of stacking an inorganic layer such as silicon nitride used as a gas barrier layer and a planarizing layer made of a cardo polymer is used for the purpose of reducing the influence of protrusions and pinholes on the substrate. Arbitrary combinations of two-layer or three-layer gas barrier films have been proposed. Also in this document, a cardo polymer containing a resin having a fluorene skeleton derived from a bisphenol compound is proposed as a preferable constituent material of the planarization layer, as in the above-mentioned Patent Document 1.

  Recent gas barrier films are required to further reduce the cost while ensuring the necessary and sufficient gas barrier properties. However, when a proven cardo polymer is used as the planarizing layer and an inorganic layer is formed thereon, there is a problem that good gas barrier properties cannot be stably obtained.

JP 2005-324406 A (Examples and paragraphs 0049 to 0065) JP 2004-299233 A (Examples and paragraphs 0046 to 0049) JP 2010-94863 A (Comparative example 2 in paragraph 0055)

  In the course of studying organic resin materials other than cardo polymers, the present inventor examined a compound having a maleimide group described in Comparative Example 2 of Patent Document 3 already filed by the present applicant. Patent Document 3 proposes a mode in which an ultraviolet curable resin layer and a gas barrier inorganic compound layer are formed one by one in this order on a plastic film. In Comparative Example 2, it is described that “UVT-302” (a compound having a maleimide group) is used as a material for the ultraviolet curable resin layer.

  However, since “UVT-302” is a monomer compound having a maleimide group, the interval between maleimide groups as reaction sites is separated, and in particular when used alone, the curability was not good. Therefore, there is a problem that unreacted components remain in the organic layer, and the unreacted components move to the interface between the organic layer and the inorganic layer over time, thereby worsening the adhesion of the inorganic layer and worsening the barrier property. .

  The present inventor aims to obtain a gas barrier film suitably used for a display device such as a display or a power generation element such as a solar cell, has good moisture and heat resistance, can ensure a necessary and sufficient water vapor transmission rate, and more An object of the present invention is to realize a gas barrier layer that can achieve a low-cost gas barrier film even with two layers (stacking of an organic layer and an inorganic layer) using the monomer having the maleimide group.

The object of the present invention is to solve the above-mentioned problems, and provides a method for producing a gas barrier film and a method for forming a gas barrier layer, which have particularly good heat and moisture resistance, low cost, and good gas barrier properties. There is.

  The present inventor has studied to increase the gas barrier property using the monomer compound having a maleimide group described above. As a result, in order to reduce unreacted components in the organic layer, a sensitizer that sensitizes the dimerization reaction of the maleimide group is essential, thereby solving the above problems and completing the present invention. .

That is, a method for producing a gas barrier film according to the present invention for solving the above-described problems includes a monomer compound having a maleimide group represented by the following general formula (1), a polymerization initiator, and the maleimide on a plastic substrate. And a step of forming an organic layer with a composition containing a sensitizer that sensitizes the dimerization reaction of the group, and a step of forming an inorganic layer on the organic layer. However, in the general formula (1), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, or an aryl group, or R ¹ and R ² become one The hydrocarbon group which forms a member ring or a 6-membered ring is represented.

The monomer compound may be a compound having at least a maleimide group represented by the general formula (1). Therefore, “*” in the formula (1) is not particularly limited, and represents various hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, or aryl groups, cyclohexyl groups, phenyl groups, or halogen atoms, alkyl groups. , An alkenyl group or an aryl group added as a substituent may be included (the same applies hereinafter). The term “becomes one” means that the branches of R ¹ and R ² are bonded (the same applies hereinafter).

  According to this invention, the method includes a step of forming an organic layer with a composition containing the monomer compound, the polymerization initiator, and the sensitizer, so that the maleimide group that the monomer compound has is cured (at the time of ultraviolet irradiation). ) Sensitizes the photodimerization reaction and generates radicals. Therefore, since the polymerization of the monomer compound is promoted, the amount of the polymerization initiator used can be reduced. As a result, the polymerization initiator remaining in the cured organic layer can be reduced. If there is a polymerization initiator remaining in the organic layer, the polymerization initiator moves to the interface between the organic layer and the inorganic layer over time, resulting in a problem that the adhesion of the inorganic layer is deteriorated and the gas barrier property is deteriorated. However, this invention can suppress such problems.

  In addition, since it has a sensitizer that sensitizes the dimerization reaction of the maleimide group, the molecular weight of the monomer compound having a maleimide group is large, and even if the maleimide groups that are reaction sites are spaced apart, A good organic layer (cured film) with few reaction components can be obtained. As a result, it is possible to reduce a decrease in adhesion derived from unreacted components. As described above, the gas barrier layer obtained by laminating the organic layer obtained from the composition in which the monomer compound, the polymerization initiator, and the sensitizer are used together with the inorganic layer can maintain the adhesion over time. In addition, a gas barrier film excellent in moisture and heat resistance (durability) can be stably produced.

In the method for producing a gas barrier film according to the present invention, the monomer compound having a maleimide group is a monomer compound having a maleimide group represented by the following general formula (2). However, in General formula (2), R < ¹ > and R < ² > respectively independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, or an aryl group, or R < ¹ > and R < ² > are united and 5 The hydrocarbon group which forms a member ring or a 6-membered ring is represented. R ³ represents an alkylene group. n represents an integer of 1 to 6.

  According to the present invention, in the monomer compound having a maleimide group represented by the general formula (2), when the molecular weight is increased, the interval between maleimide groups tends to be separated. However, in such a monomer compound, the dimerization reaction of the maleimide group is increased. Sensitizing sensitizers are particularly effective. As a result, curability can be further enhanced.

  In the method for producing a gas barrier film according to the present invention, the sensitizer is preferably a triplet sensitizer. The triplet sensitizer is preferably benzophenones and / or thioxanthones.

  According to this invention, benzophenones and thioxanthones are triplet sensitizers, and such triplet sensitizers act effectively. In particular, thioxanthones are particularly effective because the lifetime of the triplet state is long.

  In the method for producing a gas barrier film according to the present invention, the organic layer and the inorganic layer are also provided in this order on the other surface of the substrate. According to this invention, since the organic layer and the inorganic layer are provided on the opposite surface of the base material, a stable gas barrier film having good adhesion and heat-and-moisture resistance can be produced.

  In the method for producing a gas barrier film according to the present invention, the base material is a polyethylene naphthalate film or a polyethylene terephthalate film, and the inorganic layer is selected from silicon oxide, silicon nitride, silicon oxynitride, and silicon oxide zinc. It is a layer composed of one kind or two or more kinds.

The method for forming a gas barrier layer according to the present invention for solving the above-described problem sensitizes the dimerization reaction of the monomer compound having a maleimide group represented by the general formula (1), a polymerization initiator, and the maleimide group. It has the process of forming an organic layer with the composition containing a sensitizer, and the process of forming an inorganic layer on the said organic layer, It is characterized by the above-mentioned. However, in the general formula (1), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, or an aryl group, or R ¹ and R ² become one. The hydrocarbon group which forms a 5-membered ring or a 6-membered ring is represented.

  According to this invention, it can be set as the formation method of the gas barrier layer which has an effect similar to the effect of the manufacturing method of an above-described gas barrier film.

  ADVANTAGE OF THE INVENTION According to this invention, the method of manufacturing the gas barrier film which has favorable heat-and-moisture resistance and shows favorable gas barrier property at low cost, and the method of forming a gas barrier layer can be provided at low cost. By these methods, it is possible to provide a device using a gas barrier film or a gas barrier layer exhibiting good gas barrier properties, and it is possible to provide a gas barrier film and gas barrier layer having good heat and moisture resistance and gas barrier properties. The gas barrier film and gas barrier layer thus obtained can be suitably used for display devices such as displays, power generation elements such as solar cells, and the like.

It is typical sectional drawing which shows an example of the gas barrier film obtained with the manufacturing method which concerns on this invention. It is typical sectional drawing which shows another example of the gas barrier film obtained by the manufacturing method which concerns on this invention.

  Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention. In the present application, the compound before the reaction is referred to as “monomer compound” regardless of the molecular weight.

[Method for producing gas barrier film and method for forming gas barrier layer]
The method for producing the gas barrier film 10 according to the present invention increases the dimerization reaction of a monomer compound having a maleimide group represented by the following general formula (1), a polymerization initiator, and the maleimide group on the plastic substrate 1. A step of forming the organic layer 2 with a composition containing a sensitizer to be sensitized (also referred to as an organic layer forming composition) and a step of forming the inorganic layer 3 on the organic layer 2. Similarly, the method for forming the gas barrier layer 4 according to the present invention includes a sensitizer that sensitizes a dimerization reaction of a monomer compound having a maleimide group represented by the following general formula (1), a polymerization initiator, and the maleimide group. The process of forming the organic layer 2 with the composition containing these, and the process of forming the inorganic layer 3 on the organic layer 2 are included.

In General Formula (1), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, or an aryl group, or R ¹ and R ² are combined to form a 5-membered ring Alternatively, it represents a hydrocarbon group forming a 6-membered ring. The monomer compound may be a compound having at least a maleimide group represented by the general formula (1). Therefore, “*” in the formula (1) is not particularly limited, and represents various hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, or aryl groups, cyclohexyl groups, phenyl groups, or halogen atoms, alkyl groups. , An alkenyl group or an aryl group added as a substituent may be included (the same applies hereinafter). The term “becomes one” means that the branches of R ¹ and R ² are bonded (the same applies hereinafter).

  As shown in FIGS. 1 and 2, the gas barrier film 10 obtained by such a method is provided on the plastic substrate 1, the organic layer 2 provided on the plastic substrate 1, and the organic layer 2. Inorganic layer 3 formed. And the organic layer 2 contains the monomer compound which has the maleimide group represented by the said General formula (1), a polymerization initiator, and the sensitizer which sensitizes the dimerization reaction of the said maleimide group. It is a layer formed by curing.

  Similarly, the gas barrier layer 4 obtained by such a method has an organic layer 2 and an inorganic layer 3 provided on the organic layer 2 as shown in FIG. 1 and FIG. It is a layer formed by curing a composition comprising a monomer compound having a maleimide group represented by the general formula (1), a polymerization initiator, and a sensitizer for sensitizing the dimerization reaction of the maleimide group. It is characterized by that.

  The organic layer 2 and the inorganic layer 3 (these two layers are also referred to as “gas barrier layer 4”) are provided at least in this order on one surface S1 of the plastic substrate 1 as shown in FIG. As shown in FIG. 2, an organic layer 2 ′ and an inorganic layer 3 ′ (these two layers are also referred to as “gas barrier layer 4 ′”) may be provided in this order on the other surface S2. Further, as shown in FIG. 1, neither the organic layer 2 'nor the inorganic layer 3' may be provided on the other surface S2, or the inorganic layer 3 'may be provided without providing the organic layer 2'. The gas barrier property may be further improved by providing an inorganic layer 3 ′ on the other surface S <b> 2 or providing a gas barrier layer 4 ′ (organic layer 2 ′ and inorganic layer 3 ′).

  Hereinafter, the components of the method for producing a gas barrier film and the method for forming a gas barrier layer will be described in detail.

<Plastic substrate>
The material of the plastic substrate 1 is not particularly limited, but a polyester resin can be preferably mentioned from the viewpoint of versatility and industrial property. Examples of the polyester resin include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), copolymers thereof, and polycyclohexanedimethylene terephthalate (PCT). Among the polyester resins, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and copolymers thereof are preferable.

  When a polyester-based resin is applied as the material of the plastic substrate 1, the whole may be a film-like substrate made of a polyester-based resin, or the side on which the organic layer 2 is formed (one side S 1 in FIG. 2 may be a film-like laminated base material in which at least a polyester-based resin layer is formed on both surfaces S1, S2). In this film-like laminated substrate, layers other than the polyester resin layer on which the organic layer 2 is formed may not be a polyester resin layer. In selecting a layer type other than the polyester-based resin layer, various resin layers are arbitrarily selected in consideration of heat resistance, thermal expansion, light transmittance, and the like.

  Although the thickness of the plastic base material 1 is not specifically limited, It is preferable that it is about 10 micrometers or more and 500 micrometers or less.

  The surface of the plastic substrate 1 may be subjected to surface treatment such as corona treatment, flame treatment, plasma treatment, glow discharge treatment, roughening treatment, heat treatment, chemical treatment, and easy adhesion treatment as necessary. . As a specific method of such surface treatment, a conventionally known method can be appropriately used. Moreover, you may provide another functional layer in the surface where the organic layer 2 is not directly formed. Examples of functional layers include matting agent layers, protective layers, antistatic layers, smoothing layers, adhesion improving layers, light shielding layers, antireflection layers, hard coat layers, stress relaxation layers, antifogging layers, antifouling layers, coatings. A printing layer, an easily bonding layer, etc. are mentioned.

<Formation of organic layer>
The organic layer is formed on a plastic substrate 1 by sensitizing a monomer compound having a maleimide group represented by the following general formula (1), a polymerization initiator, and a dimerization reaction of the maleimide group. And a composition (also referred to as an organic layer forming composition).

The organic layer 2 is provided on the plastic substrate 1 and constitutes a gas barrier layer 4 together with an inorganic layer 3 described later. In the present invention, the organic layer 2 includes a monomer compound having a maleimide group represented by the general formula (1), a polymerization initiator, and a sensitizer that sensitizes the dimerization reaction of the maleimide group. A layer formed by curing the composition is provided. In the general formula (1), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, or an aryl group, or R ¹ and R ² are one and five members. The hydrocarbon group which forms a ring or a 6-membered ring is represented.

(Monomer compound having a maleimide group)
The monomer compound having a maleimide group is as described in the general formula (1). In the general formula (1), the halogen atom constituting R ¹ and R ² is preferably fluorine, chlorine, bromine or the like, and the alkyl group is an alkyl group having 4 or less carbon atoms (methyl group, ethyl group, propyl group, Butyl group) is preferred, the alkenyl group is preferably an alkenyl group having 4 or less carbon atoms (vinyl group (CH ₂ ═CH—), allyl group (CH ₂ ═CHCH ₂ —), etc.), and the aryl group is a phenyl group. (C ₆ H ₅ —), tolyl group (CH ₃ C ₆ H ₄ —) and the like can be mentioned, and a phenyl group is preferred. Further, examples of the saturated hydrocarbon group in which R ¹ and R ² are combined to form a 5-membered ring or 6-membered ring include —CH ₂ CH ₂ CH ₂ — and —CH ₂ CH ₂ CH ₂ CH ₂ —. Examples of the unsaturated hydrocarbon group include —CH═CH—CH ₂ —, —CH═CH—CH ₂ CH ₂ —, —CH ₂ CH═CHCH ₂ — and the like. In addition, in the unsaturated hydrocarbon group, in order for the maleimide group to undergo a dimerization reaction, it is necessary to select a 5-membered ring or a 6-membered ring finally obtained which does not have aromaticity. As such a hydrocarbon group, a saturated hydrocarbon group is preferable.

  Preferred specific examples of the maleimide group in the general formula (1) are shown in the following formulas (3) to (8). Note that “*” in the general formulas (3) to (8) is the same as that in the general formula (1).

In each of these formulas, ^one of R ¹ and R ² is a hydrogen atom as shown in Formula (5) and the other is an alkyl group having 4 or less carbon atoms (for example, a methyl group), as shown in Formula (4). Are preferably an alkyl group having 4 or less carbon atoms (for example, a methyl group) and a saturated hydrocarbon group in which each forms a carbocyclic ring as shown in Formula (3).

  Further, among these, saturated hydrocarbon groups each forming a carbocyclic ring as shown in Formula (3) are more preferable in terms of excellent adhesion.

  An example in which a cyclohexyl group and a phenyl group are added is shown below. The molecular weights of the following monomer compounds are 179 for N-cyclohexylmaleimide (Nippon Shokubai Co., Ltd., trade name: Imirex-C) with a cyclohexyl group added, and N-phenylmaleimide with a phenyl group (Nippon Shokubai Co., Ltd.). , Trade name: Imilex-P) is 173.

  The monomer compound used in the present invention may have a maleimide group and an ethylenically unsaturated group other than the maleimide group. For example, a monomer compound having a maleimide group represented by the following general formula (2) and general formula (9) can be preferably used because it is easy to produce and excellent in curability. In addition, following formula (10) is the maleimide acrylate (The Toagosei Co., Ltd. make, brand name: M-145) of the example.

Here, in formulas (2) and (9), R ¹ and R ² have the same meaning as in formula (1) above. R ³ represents an alkylene group, R ⁴ represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 6. The alkylene group for R ³ may be linear or branched. More preferably, it is a C1-C6 alkylene group. Note that “*” in the general formulas (2) and (9) is the same as that in the general formula (1).

  The monomer compound having a maleimide group represented by the formulas (2) and (9) can be more preferably applied because it can further enhance curability. Such a monomer compound tends to have a high molecular weight and is difficult to cure, but in the present invention, since the sensitizer for sensitizing the dimerization reaction of the maleimide group is applied, the monomer compound having a large molecular weight and difficult to cure is used. Is particularly effective and can be cured sufficiently.

  When the monomer compound (monomer compound having a maleimide group) described above is used, the polarity of the maleimide group itself is high, and the adhesion with the inorganic layer 3 described later is improved. Furthermore, since maleimide groups are photodimerized and generate radicals when irradiated with ultraviolet rays, the use of a polymerization initiator can be reduced especially when a sensitizer that sensitizes the dimerization reaction of maleimide groups is used. 2 has the effect of reducing the residual initiator in 2. If the polymerization initiator remains in the organic layer 2, the remaining polymerization initiator moves to the interface between the organic layer 2 and the inorganic layer 3 over time, and the adhesion between the inorganic layer 3 deteriorates and the gas barrier Sexuality gets worse.

  About the molecular weight (weight average molecular weight) of a monomer compound, 150-40000 are preferable, More preferably, it is 5000-35000, More preferably, it is 10000-30000. If the weight average molecular weight is less than 1000, the organic layer obtained by curing becomes too hard, and the adhesion with the inorganic layer may be insufficient. On the other hand, when the weight average molecular weight exceeds 40000, the viscosity of the composition becomes too high, and the coatability may be lowered. The weight average molecular weight is a value obtained by converting the molecular weight measured by gel permeation chromatography using the molecular weight of polystyrene as a reference, using tetrahydrofuran as a solvent.

  Among these, those having a low molecular weight (for example, in the range of 150 to 1000) have high reactivity, so that the polymerization initiator can be reduced and the polymerization initiator remaining in the organic layer after curing can be reduced. There is an operational effect.

  On the other hand, when the molecular weight of the monomer compound is large (for example, in the range of 10,000 to 40,000), the film is more flexible than when the molecular weight is small (for example, 150 to 1,000). Therefore, the adhesiveness with the inorganic layer 3 is further improved. On the other hand, those having a large molecular weight tend to have a distance between maleimide groups which are reaction sites, so that the curability is not always good and uncured components may remain. However, in the present invention, in addition to the polymerization initiator, by using a sensitizer that sensitizes the dimerization reaction of the maleimide group in combination, even if the monomer compound having a maleimide group has a large molecular weight, the maleimide The dimerization reaction of the group is sensitized, and the reaction between the polymerization initiator and the monomer compound occurs sufficiently. Therefore, a good organic layer (cured film) with few unreacted components can be obtained. As a result, there exists an effect that the fall of the adhesiveness originating in the unreacted component can be reduced.

  A preferable blending ratio of the monomer compound is 5 to 60% by mass in the composition, and more preferably 10 to 50% by mass. When the blending ratio is within the above range, excellent wet heat resistance can be exhibited by excellent curability.

  As a specific example, in the case of the monomer compound represented by Formula (11) used in Example 1 described later, the ratio in the composition is 5 to 60% by mass, and preferably 10 to 50% by mass. Within this range, good wet heat resistance can be exhibited. Moreover, when using together the monomer compound which does not have a maleimide group like Example 2 mentioned later, the ratio in the composition of the monomer compound is 0-40 mass%, Preferably it is 10-30 mass%. is there. Even when a monomer compound having no maleimide group is used in combination, good moisture and heat resistance can be exhibited within this range.

(Polymerization initiator)
The polymerization initiator is not particularly limited, and a general polymerization initiator can be used. The reason why a sufficient cured film can be formed using a general polymerization initiator in the present invention is that a sensitizer that sensitizes a dimerization reaction of a maleimide group is used in combination with the polymerization initiator.

  Examples of the polymerization initiator include acetophenones, benzophenones, Michler benzoylbenzoate, α-amyloxime ester, tetramethylthiuram monosulfide, thioxanthones, and the like, and these can be arbitrarily applied. Specifically, as illustrated in the examples described later, for example, 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: IRGACURE (registered trademark) 184, BASF), 2,2-dimethoxy-1,2, -Diphenylethane-1-one (trade name: IRGACURE (registered trademark) 651, BASF), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (trade name: IRGACURE (registered trademark) 907, BASF Corporation), and the like. Of course, other polymerization initiators may be used.

  Although the preferable mixture ratio of a polymerization initiator is not specifically limited, From a viewpoint that favorable superposition | polymerization is performed, it is 1-10 mass% in the compounding ratio in a composition, Preferably it is 2-8 mass%. If the blending ratio is less than 1% by mass, even if a sensitizer that sensitizes the dimerization reaction of the maleimide group is used in combination, the polymerization initiation ability for the monomer compound is insufficient and the curing may be insufficient. On the other hand, if the blending ratio is more than 10% by mass, the remaining polymerization initiator increases even when a sensitizer for sensitizing the maleimide group dimerization reaction is used in combination. When the inorganic layer is vacuum-deposited, it is generated as outgas, which may inhibit the formation of the inorganic layer.

(Sensitizer)
The sensitizer is a compound that sensitizes the photodimerization reaction of the maleimide component. Specific examples include triplet sensitizers such as thioxanthones and benzophenones.

  Examples of thioxanthones include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, and the like. Specific examples of thioxanthone compounds include 2,4-dimethylthioxanthone (Nippon Kayaku Co., Ltd .: Kayacure RTX, Nippon Kayaku Co., Ltd .: Kayacure DETX-S, DKSH Japan, Inc .: SPEEDCURE DETX, etc.), 2-chlorothioxanthone (manufactured by Nippon Kayaku Co., Ltd .: Kayacure CTX), 2-isopropylthioxanthone (manufactured by Nippon Kayaku Co., Ltd .: Kayacure ITX), 1-chloro-4-propoxythioxanthone (manufactured by Nippon Shibel Hegner: Speedcure CPTX) 2-diisopropylthioxanthone (manufactured by Nippon Kayaku Co., Ltd .: Kayacure DITX), and the like.

  Examples of benzophenones include benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4,4′-dimethylbenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-bis (diethylamino) benzophenone, and the like. be able to. Specific examples of the benzophenone compounds include benzophenone (manufactured by DKSH Japan: SPEEDCURE BENZOPHENONE), 4-methylbenzophenone (manufactured by DKSH Japan: SPEEDCURE MBP), and the like.

  Examples of other sensitizers include coumarins and ketocoumarins. Examples of coumarins include coumarin 1, coumarin 338 and coumarin 102. Examples of ketocoumarins include 3,3′-carbonylbis. (7-diethylaminocoumarin) and the like. Further, n-butylamine, triethylamine, tri-n-butylphosphine and the like may be mixed with the triplet sensitizer.

  Among these, thioxanthones are particularly preferable because they have a long effect on the triplet state and are particularly effective.

  The preferred blending ratio of the sensitizer when a triplet sensitizer such as thioxanthone or benzophenone is used is in the range of 0.1 to 3% by mass, particularly preferably 0.3 to 2% in the composition. It is the range of mass%. The blending ratio of 3% by mass or less is preferable because yellowing of the organic layer after curing is reduced. Moreover, since it is excellent in sclerosis | hardenability, it is preferable that a mixture ratio is 0.1 mass% or more.

(Other)
A solvent is arbitrarily mixed according to the composition for organic layers from the viewpoint of viscosity adjustment of a coating liquid. Solvents include alcohols such as isopropyl alcohol, methanol and ethanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as ethyl acetate and butyl acetate; halogenated hydrocarbons; aromatic carbonization such as toluene and xylene Mention may be made of hydrogen; or mixtures thereof.

  Additives are appropriately added to the composition for an organic layer as needed within a range not impairing the effects of the present invention. Examples of additives include heat stabilizers, radical scavengers, plasticizers, surfactants, antistatic agents, antioxidants, ultraviolet absorbers, infrared absorbers, dyes (colored dyes, colored pigments), extender pigments, Examples thereof include a light diffusing agent.

<Formation of organic layer>
The organic layer 2 is formed by applying a composition for an organic layer containing the monomer compound, the polymerization initiator, and the sensitizer on the plastic substrate 1, and irradiating the coated film with ionizing radiation to crosslink. It is formed by polymerization or the like. At this time, the maleimide group generates a radical while the photodimerization reaction is promoted by the sensitizer during curing (at the time of irradiation with ionizing radiation). Therefore, since the polymerization of the monomer compound is promoted, the amount of the polymerization initiator used can be reduced. As a result, the polymerization initiator remaining in the organic layer after curing can be reduced.

  The organic layer forming composition is usually applied by coating the organic layer composition on the plastic substrate 1, irradiating the coating film with ionizing radiation (such as ultraviolet rays), and polymerizing and curing the organic layer composition. To form the organic layer 2.

  Examples of the coating method for the organic layer composition include a roll coating method, a gravure roll coating method, a kiss roll coating method, a reverse roll coating method, a Miya bar coating method, a gravure coating method, a spin coating method, and a die coating method. Can be mentioned.

  After apply | coating the composition for organic layers, it dries as needed. The drying temperature may be room temperature, but when the organic layer composition contains a solvent, the drying for removing the solvent is preferably performed at a temperature equal to or higher than the boiling point of the solvent. The ionizing radiation applied to the organic layer composition is as described above. However, when ultraviolet rays are applied as the ionizing radiation, for example, an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc lamp, a black light fluorescence A light source such as a lamp or a metal halide lamp is used.

  The organic layer 2 may be a single layer formed by one film formation, or two or more layers formed by two or more film formations. In the case of two or more layers, each layer may use the same organic layer composition or different organic layer compositions as long as the constituent elements of the present invention are satisfied. The thickness of the organic layer 2 is preferably 0.1 μm or more and 20 μm or less from the viewpoint of substrate deflection, regardless of whether it is a single layer or two or more layers, and 0.5 μm from the viewpoint of surface properties and productivity. More preferably, it is 10 μm or less.

  As described above, the organic layer 2 is formed using a composition in which a monomer compound having a maleimide group, a polymerization initiator, and a sensitizer are used in combination. Even if the maleimide groups that are sites are spaced apart, the reaction between the polymerization initiator and the monomer compound occurs sufficiently. Therefore, a good organic layer (cured film) with few unreacted components can be obtained. As a result, it is possible to reduce a decrease in adhesion derived from unreacted components. Moreover, the polarity of maleimide group itself is high, and adhesiveness with the inorganic layer 3 mentioned later becomes favorable. Furthermore, since maleimide groups are photodimerized and generate radicals when irradiated with ultraviolet rays, the use of a polymerization initiator can be reduced especially when a sensitizer that sensitizes the dimerization reaction of maleimide groups is used. 2 has the effect of reducing the residual initiator in 2. If the polymerization initiator remains in the organic layer 2, the remaining polymerization initiator moves to the interface between the organic layer 2 and the inorganic layer 3 over time, and the adhesion between the inorganic layer 3 deteriorates and the gas barrier Sexuality gets worse.

<Formation of inorganic layer>
The inorganic layer 3 is formed on the organic layer 2 as a functional layer that blocks gas such as water vapor. The inorganic layer 3 and the organic layer 2 constitute a gas barrier layer 4.

  Examples of the material for forming the inorganic layer 3 include one or more inorganic compounds selected from inorganic oxides, inorganic oxynitrides, inorganic nitrides, inorganic oxide carbides, inorganic oxycarbonitrides, silicon zinc oxides, and the like. Can be mentioned. Specific examples include inorganic compounds containing one or more elements selected from silicon, aluminum, magnesium, titanium, tin, indium, cerium, and zinc, and more specifically, silicon. Inorganic oxides such as oxides, aluminum oxides, magnesium oxides, titanium oxides, tin oxides, silicon zinc alloy oxides and indium alloy oxides; inorganics such as silicon nitrides, aluminum nitrides and titanium nitrides Nitrides; inorganic silicon oxynitrides such as silicon oxynitride; Particularly preferable examples include one or more inorganic compounds selected from silicon oxide, silicon nitride, silicon zinc oxide, and silicon oxynitride. The inorganic layer 3 may use the said material independently, and may mix and use the said material in arbitrary ratios within the range of the summary of this invention.

  As a method for forming the inorganic layer 3, for example, a physical vapor deposition method such as a vacuum deposition method, a sputtering method, an ion plating method, or a plasma chemical vapor deposition method can be preferably exemplified. The film forming conditions in these various forming methods may be adjusted by appropriately adjusting conventionally known film forming conditions in consideration of the physical properties and thickness of the inorganic layer 3 to be obtained.

  More specifically, (1) a vacuum vapor deposition method in which a raw material such as an inorganic oxide, inorganic nitride, inorganic oxynitride, or metal is heated and deposited on a substrate, and (2) oxygen gas is introduced into the raw material. Oxidation reaction vapor deposition method to oxidize and deposit on the substrate, (3) Sputtering method to deposit on the substrate by introducing argon gas and oxygen gas into the target material and sputtering, (4) Generate the material with plasma gun An ion plating method in which the substrate is heated with a plasma beam and deposited on a substrate, and (5) a plasma chemical vapor deposition method in which an organic silicon compound is used as a raw material and a silicon oxide film is deposited on the substrate. it can.

  The thickness of the inorganic layer 3 varies depending on the inorganic compound used, but is usually 5 nm or more, preferably 10 nm or more from the viewpoint of securing gas barrier properties, and usually 5000 nm or less from the viewpoint of suppressing the occurrence of cracks and the like. , Preferably 500 nm or less, more preferably 300 nm or less. Further, the inorganic layer 3 may be a single layer or two or more inorganic layers 3 having a total thickness within the above range. In the case of two or more inorganic layers 3, the same materials may be combined or different materials may be combined.

<Other configurations>
As described above, the gas barrier film 10 is composed of the plastic substrate 1, the organic layer 2, and the inorganic layer 3. For example, other layers are appropriately inserted between the organic layer 2 and the inorganic layer 3. Or may be laminated on the surface S2 of the plastic substrate 1 where the organic layer 2 is not formed, or may be laminated on the inorganic layer 3 or the inorganic layer 3 ′. As an optional layer, as long as the characteristics of the present invention are not impaired, for example, a conventionally known primer layer, matting agent layer, protective layer, antistatic layer, smoothing layer, adhesion improving layer, light shielding layer, antireflection layer, Examples include a hard coat layer, a stress relaxation layer, an antifogging layer, an antifouling layer, a printing layer, and an easy adhesion layer. Each of these layers optionally includes a step of forming each layer.

The gas barrier film 10 and the gas barrier layer 4 thus configured have a water vapor transmission rate of 0.05 g / m ² · day at the time of 500 hours at a temperature of 60 ° C. and a humidity of 90%, as shown in Examples described later. And had excellent wet heat resistance. In addition, the water vapor transmission rate was evaluated by the result of using a water vapor transmission rate measuring device (manufactured by MOCON, model name: PERMATRAN-W3 / 31).

  As described above, the gas barrier layer 4 formed by laminating the organic layer 2 and the inorganic layer 3 formed of the composition in which the monomer compound, the polymerization initiator, and the sensitizer are used together maintains the adhesion over time. Thus, a gas barrier film excellent in moisture and heat resistance (durability) can be stably produced.

[apparatus]
The apparatus here is a display apparatus or a power generation apparatus using the gas barrier film obtained by the production method according to the present invention or the gas barrier layer obtained by the formation method according to the present invention. Since the gas barrier film 10 and the gas barrier layer 4 described above both have good heat and moisture resistance and can stably realize good gas barrier properties, if the gas barrier film 10 or the gas barrier layer 4 is used, a display device and Contributes to cost reduction and high quality of power generation equipment. The gas barrier film or gas barrier layer used in such a device is positioned as a key part applied to next-generation energy-saving products (for example, solar cells, power generation elements, display devices, lighting devices, etc.).

  Examples of the display device include an organic EL element, a liquid crystal display element, a touch panel, and electronic paper. A thin film transistor that drives these display devices in an active matrix is also included in the display device. In addition, the configuration of each of these display devices is not particularly limited, and a conventionally known configuration can be appropriately adopted, and the sealing means by the gas barrier film 10 or the gas barrier layer 4 applied to each of such display devices is also particularly limited. Instead, a conventionally known means can be used.

  Specifically, for example, an organic EL element has a cathode and an anode on the gas barrier film 10 obtained by the production method according to the present invention, and an organic light emitting layer (simply referred to as “light emitting layer” between both electrodes). And also having an organic layer. As a lamination | stacking aspect of the organic layer containing a light emitting layer, the aspect laminated | stacked in order of the positive hole transport layer, the light emitting layer, and the electron carrying layer from the anode side is preferable. Furthermore, a charge blocking layer or the like may be provided between the hole transport layer and the light-emitting layer, or between the light-emitting layer and the electron transport layer. Further, a hole injection layer may be provided between the anode and the hole transport layer, and an electron injection layer may be provided between the cathode and the electron transport layer. Further, the light emitting layer may be only one layer, or the light emitting layer may be divided like a first light emitting layer, a second light emitting layer, a third light emitting layer, and the like. Furthermore, each layer may be divided into a plurality of secondary layers. Since the organic EL element is a light emitting element, at least one of the anode and the cathode is preferably transparent.

  Examples of the power generation device include a solar cell element (solar cell module). The configuration of the power generation device is not particularly limited, and a conventionally known configuration can be appropriately employed. Furthermore, the sealing means by the gas barrier film 10 or the gas barrier layer 4 applied to such a power generator is not particularly limited, and may be a conventionally known means. For example, the gas barrier film 10 can be used as a back surface protection sheet for solar cell elements.

  Specifically, for example, as a solar cell module, an example in which the gas barrier film 10 obtained by the production method according to the present invention is used as a solar cell backsheet can be given. Such solar cell modules are, in order from the sunlight side in the thickness direction, a front substrate (having high light transmittance such as glass or film), filler, solar cell element, lead wire, terminal, terminal box, solar In the configuration of the battery back sheet, they are fixed to exterior materials (such as aluminum frames) at both ends via a sealing material. As the solar cell backsheet, an example in which the gas barrier sheet 10 obtained by the production method according to the present invention is sandwiched between the back surface sealing film and the film disposed on the outer layer side is given. be able to. As the back surface sealing film, for example, a white polyester film having a high reflectivity is used so as to reflect sunlight on the solar cell module side and increase the conversion efficiency. Moreover, as a film arrange | positioned at the outer layer side, a weather resistance, a hydrolysis resistance film, etc. are used.

  EXAMPLES The present invention will be described more specifically with reference to examples. However, the present invention is not limited to the description of the following examples unless it exceeds the gist.

[Example 1]
As a plastic substrate 1, an organic layer forming composition A (for UV curable organic layer) adjusted to the following composition on one side of a 100 μm thick polyethylene terephthalate film (Toyobo Co., Ltd., Cosmo Shine A-4300) Ink) was applied by die coating, dried at 120 ° C. for 2 minutes, and then irradiated with ultraviolet rays under the condition of an integrated light quantity of 300 mJ / cm ² in a wavelength range of 260 nm to 400 nm to form an organic layer 2 having a thickness of 5 μm. .

(Composition of Composition A for Organic Layer Formation)
A monomer compound having a maleimide group represented by the following formula (11) (weight average molecular weight: 23000, manufactured by Toagosei Co., Ltd .: UVT-302, the component content of the maleimide group is about 30% by mass in the monomer compound) 38 2 parts by mass of polymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, trade name: IRGACURE (registered trademark) 184, BASF) ・ Sensitizer (2,4-dimethylthioxanthone, manufactured by DKSH Japan): SPEDCURE DETX) 1 part by mass ・ Solvent (toluene: methyl ethyl ketone = 1: 1) 60 parts by mass

The inorganic layer 3 was set in a hollow cathode type ion plating apparatus in such a direction that a plastic film having an organic layer 2 formed on one side of a polyethylene terephthalate film having a thickness of 100 μm was formed on the organic layer side. Then, silicon oxide (manufactured by High Purity Chemical Research Laboratory), which is an evaporation source material, was put into a crucible in a hollow cathode type ion plating apparatus, and then evacuated. After the degree of vacuum reached 5 × 10 ⁻⁴ Pa, 15 sccm of argon gas was introduced into the plasma gun, and plasma with a current of 110 A and a voltage of 90 V was generated. Plasma was bent in a predetermined direction by maintaining the inside of the chamber at 1 × 10 ⁻¹ Pa and magnetic force, and the evaporation source material was irradiated. It was confirmed that the evaporation source material in the crucible sublimates through a molten state. Ion plating was performed for 15 seconds to deposit on the substrate, thereby forming a silicon oxide layer having a thickness of 100 nm.

  The layer structure of the gas barrier film 10 of Example 1 obtained as described above is polyethylene terephthalate / organic layer / inorganic layer.

[Example 2]
A gas barrier film 10 of Example 2 was produced in the same manner as in Example 1 except that the organic layer forming composition B adjusted to the following composition was used.

(Composition of Composition B for Organic Layer Formation)
A monomer compound having a maleimide group represented by the above formula (11) (weight average molecular weight: 23000, manufactured by Toagosei Co., Ltd .: UVT-302) 19 parts by mass A compound of the following general formula (12) (R ¹ to R ⁶ = hydrogen atom, n ₁ + n ₂ = 2 manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester A-BPEF) 19 parts by mass Polymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, trade name) : IRGACURE (registered trademark) 184, BASF) 2 parts by mass-Sensitizer (2,4-dimethylthioxanthone, manufactured by DKSH Japan: 1 part by SPEDCURE DETX)-Solvent (toluene: methyl ethyl ketone = 1: 1) 60 parts by mass Part

[Example 3]
A gas barrier film 10 of Example 3 was produced in the same manner as in Example 1 except that the organic layer forming composition C adjusted to the following composition was used.

(Composition of the organic layer forming composition C)
-38 parts by mass of a monomer compound having a maleimide group represented by the above formula (11) (weight average molecular weight: 23000, manufactured by Toagosei Co., Ltd .: UVT-302)-Polymerization initiator (1-hydroxy-cyclohexyl-phenyl- Ketone, trade name: IRGACURE (registered trademark) 184, BASF) 2 parts by mass Sensitizer (2-chlorothioxanthone, Nippon Kayaku Co., Ltd .: Kayacure CTX) 1 part by mass Solvent (toluene: methyl ethyl ketone = 1) 1) 60 parts by mass

[Example 4]
A gas barrier film 10 of Example 4 was produced in the same manner as in Example 1 except that the organic layer forming composition D adjusted to the following composition was used.

(Composition of Composition D for Organic Layer Formation)
-38 parts by mass of a monomer compound having a maleimide group represented by the above formula (11) (weight average molecular weight: 23000, manufactured by Toagosei Co., Ltd .: UVT-302)-Polymerization initiator (1-hydroxy-cyclohexyl-phenyl- Ketone, trade name: IRGACURE (registered trademark) 184, BASF) 2 parts by mass Sensitizer (2-isopropylthioxanthone, Nippon Kayaku Co., Ltd .: Kayacure ITX) 1 part by mass Solvent (toluene: methyl ethyl ketone = 1) 1) 60 parts by mass

[Example 5]
A gas barrier film 10 of Example 5 was produced in the same manner as in Example 1 except that the organic layer forming composition E adjusted to the following composition was used.

(Composition of Composition E for Organic Layer Formation)
-38 parts by mass of a monomer compound having a maleimide group represented by the above formula (11) (weight average molecular weight: 23000, manufactured by Toagosei Co., Ltd .: UVT-302)-Polymerization initiator (1-hydroxy-cyclohexyl-phenyl- Ketone, trade name: IRGACURE (registered trademark) 184, BASF) 2 parts by mass-Sensitizer (benzophenone, manufactured by DKSH Japan: SPEDCURE BENZOPHENONE) 1 part by mass-Solvent (toluene: methyl ethyl ketone = 1: 1) 60 parts by mass

[Example 6]
A gas barrier film 10 of Example 6 was produced in the same manner as in Example 1 except that the organic layer forming composition F adjusted to the following composition was used.

(Composition of Composition F for Organic Layer Formation)
-38 parts by mass of a monomer compound having a maleimide group represented by the above formula (11) (weight average molecular weight: 23000, manufactured by Toagosei Co., Ltd .: UVT-302)-Polymerization initiator (1-hydroxy-cyclohexyl-phenyl- Ketone, trade name: IRGACURE (registered trademark) 184, BASF) 2 parts by mass-Sensitizer (4-methylbenzophenone, manufactured by DKSH Japan: SPEDCURE MBP) 1 part by mass-Solvent (toluene: methyl ethyl ketone = 1: 1) 60 parts by mass

[Comparative Example 1]
A gas barrier film 10 of Comparative Example 1 was produced in the same manner as in Example 1 except that the organic layer forming composition G adjusted to the following composition was used.

(Composition of Composition F for Organic Layer Formation)
Compound of the above general formula (12) (R ^{1 to} R ⁶ = hydrogen atom, n ₁ + n ₂ = 2 manufactured by Shin-Nakamura Chemical Co., Ltd., trade name: NK ester A-BPEF) 38 parts by mass Polymerization initiator (1-hydroxy-cyclohexyl-phenyl-ketone, trade name: IRGACURE (registered trademark) 184, BASF) 2 parts by mass Solvent (toluene: methyl ethyl ketone = 1: 1) 60 parts by mass

[Comparative Example 2]
A gas barrier film of Comparative Example 2 was produced in the same manner as in Example 1 except that the organic layer forming composition H adjusted to the following composition was used.

(Composition of Composition H for Organic Layer Formation)
-38 parts by mass of a monomer compound having a maleimide group represented by the above formula (11) (weight average molecular weight: 23000, manufactured by Toagosei Co., Ltd .: UVT-302)-Polymerization initiator (1-hydroxy-cyclohexyl-phenyl- Ketone, trade name: IRGACURE (registered trademark) 184, BASF) 2 parts by mass-Solvent (toluene: methyl ethyl ketone = 1: 1) 60 parts by mass

[Comparative Example 3]
A gas barrier film of Comparative Example 3 was produced in the same manner as in Example 1 except that the organic layer forming composition I adjusted to the following composition was used.

(Composition of Composition I for Organic Layer Formation)
-38 parts by mass of a monomer compound having a maleimide group represented by the above formula (11) (weight average molecular weight: 23000, manufactured by Toagosei Co., Ltd .: UVT-302)-Polymerization initiator (2,2-dimethoxy-1, 2-diphenylethane-1-one, trade name: IRGACURE (registered trademark) 651, BASF Corp.) 2 parts by mass • Solvent (toluene: methyl ethyl ketone = 1: 1) 60 parts by mass

[Comparative Example 4]
A gas barrier film of Comparative Example 4 was produced in the same manner as in Example 1 except that the organic layer forming composition J adjusted to the following composition was used.

(Composition of the organic layer forming composition J)
-38 parts by mass of a monomer compound having a maleimide group represented by the above formula (11) (weight average molecular weight: 23000, manufactured by Toagosei Co., Ltd .: UVT-302)-Polymerization initiator (2-methyl-1- [4 -(Methylthio) phenyl] -2-morpholinopropan-1-one), trade name: IRGACURE (registered trademark) 907, BASF Corp.) 2 parts by mass. Solvent (toluene: methyl ethyl ketone = 1: 1) 60 parts by mass

[Evaluation and results]
(Measurement method of gas barrier properties)
About the gas-barrier film obtained in Examples 1-6 and Comparative Examples 1-4, the water-vapor-permeation rate was measured. The measurement evaluated the initial stage after the production of the gas barrier film and the endurance test (moisture heat resistance test) after 500 hours at 60 ° C. and 90% humidity. The measurement conditions at the initial stage and after the endurance test were performed using a water vapor transmission rate measuring device (manufactured by MOCON, trade name: PERMATRAN-W3 / 31) under conditions of a temperature of 37.8 ° C. and a humidity of 100% RH. . The results are shown in Table 1.

(result)
As shown in Table 1, in Examples 1 to 6, the water vapor gas barrier property at the initial stage was good, and both were less than 0.05 g / m ² · day, indicating good water vapor gas barrier properties. Moreover, it was favorable after the durability test, and all were 0.08 g / m ² · day or less. Especially Examples 1-4 become less than 0.05 g / m < ² > * day even after an endurance test, and can be called the gas-barrier film especially excellent in heat-and-moisture resistance. On the other hand, Comparative Examples 1 to 4 had good water vapor gas barrier properties at the initial stage, but were inferior in water vapor gas barrier properties after the durability test.

DESCRIPTION OF SYMBOLS 1 Plastic base material 2, 2 'Organic layer 3, 3' Inorganic layer 4, 4 'Gas barrier layer 10, 10A, 10B Gas barrier film S1 One side of a plastic base material S2 Other side of a plastic base material

Claims (5)

An organic layer is formed on a plastic substrate with a composition comprising a monomer compound having a maleimide group represented by the general formula (1), a polymerization initiator and a sensitizer for sensitizing the dimerization reaction of the maleimide group. A method for producing a gas barrier film comprising: a step of forming; and a step of forming an inorganic layer on the organic layer,
The polymerization initiators are 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one and 2-methyl-1- [4- (methylthio) phenyl] -2- Selected from morpholinopropan-1-one,
The sensitizer method for producing a gas barrier film, wherein the Ru der those selected from thioxanthones and benzophenones. However, in the general formula (1), R ¹ and R ² each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, or an aryl group, or R ¹ and R ² become one The hydrocarbon group which forms a member ring or a 6-membered ring is represented.

The method for producing a gas barrier film according to claim 1, wherein the monomer compound having a maleimide group is a monomer compound having a maleimide group represented by the general formula (2). However, in General formula (2), R < ¹ > and R < ² > respectively independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, or an aryl group, or R < ¹ > and R < ² > are united and 5 The hydrocarbon group which forms a member ring or a 6-membered ring is represented. R ³ represents an alkylene group. n represents an integer of 1 to 6.

The manufacturing method of the gas barrier film of Claim 1 or 2 which provides the said organic layer and the said inorganic layer in that order also to the other surface of the said base material. The base material is a polyethylene naphthalate film or a polyethylene terephthalate film, and the inorganic layer is a layer composed of one or more selected from silicon oxide, silicon nitride, silicon oxynitride, and silicon zinc oxide. The manufacturing method of the gas-barrier film of any one of Claims 1-3 . Forming an organic layer with a composition comprising a monomer compound having a maleimide group represented by the general formula (1), a polymerization initiator and a sensitizer for sensitizing the dimerization reaction of the maleimide group; Forming an inorganic layer on the organic layer, and forming a gas barrier layer,
The polymerization initiators are 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one and 2-methyl-1- [4- (methylthio) phenyl] -2- Selected from morpholinopropan-1-one,
The method for forming a gas barrier layer, wherein the sensitizer is selected from thioxanthones and benzophenones. (However, in General formula (1), R < ¹ > and R < ² > represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, or an aryl group each independently, or R < ¹ > and R < ² > become one. (Represents a hydrocarbon group forming a 5-membered or 6-membered ring.)

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