JP2014091057A - Manufacturing method of gas barrier film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a gas barrier film excellent in a gas barrier.SOLUTION: The manufacturing method of a gas barrier film comprises a process of providing a reactive composition including (A) alkoxy silane and (B) a hydrolyzate of the alkoxy silane, by adding water to a raw material composition including (A) the alkoxy silane having two or more of alkoxy groups and one or more of radical polymerizable groups and (B) alkoxy silane having two or more of alkoxy groups and having no radical polymerizable group and a process of forming a gas barrier resin layer by dehydrating-condensing a radical polymer and the hydrolyzate of (B) the alkoxy silane, after executing radical main polymerization on the hydrolyzate of (A) the alkoxy silane, by further irradiating an activation energy ray, by coating the reactive composition on a base material, after executing radical preliminary polymerization on the hydrolyzate of (A) the alkoxy silane by irradiating the activation energy ray to the reactive composition.

Description

  The present invention relates to a gas barrier film excellent in gas barrier properties against oxygen, water vapor and the like, and a method for producing the same.

  Gas barrier films are used in food and pharmaceutical packaging bags in order to prevent the influence of oxygen, water vapor, and the like that cause the quality of the contents to change. In addition, the gas barrier film is used to prevent the elements used in solar cell modules, liquid crystal display panels, organic EL (electroluminescence) display panels, etc. from touching oxygen or water vapor to deteriorate the performance. It is also used as a part of these or as a packaging material for these elements.

  Polyvinyl alcohol films and ethylene vinyl alcohol copolymer films are also used as such gas barrier films, but these have insufficient water vapor barrier properties, and oxygen barrier properties are reduced under high humidity conditions. Has a problem.

  Therefore, a vapor deposition layer of a metal oxide such as silicon oxide or aluminum oxide and a gas barrier resin layer obtained by curing a composition containing a silane coupling agent and a synthetic resin or a synthetic resin monomer are laminated on a plastic sheet. An integrated gas barrier film has been proposed (for example, Patent Documents 1 to 3).

Japanese Patent No. 3403882 Japanese Patent No. 3974219 JP 2010-000677 A

  However, in the gas barrier film disclosed in Patent Documents 1 to 3, the gas barrier film is only made to be improved by thickening the gas barrier film using the gas barrier resin layer, and is also used for the gas barrier resin layer. The resulting silane coupling agent merely improves the adhesion between the gas barrier resin layer and another layer adjacent thereto. For this reason, the gas barrier films of Patent Documents 1 to 3 still have a problem that the gas barrier properties such as oxygen and water vapor are insufficient.

  Accordingly, an object of the present invention is to provide a method for producing a gas barrier film having excellent gas barrier properties against oxygen, water vapor and the like.

The method for producing a gas barrier film of the present invention comprises:
100 parts by weight of alkoxysilane (A) having two or more alkoxy groups and one or more radical polymerizable groups in the molecule, and two or more alkoxy groups in the molecule and having radical polymerizable groups The raw material composition containing 25 to 200 parts by weight of alkoxysilane (B) is added with 10 to 100 parts by weight of water to hydrolyze the alkoxy group of the alkoxysilane (A) and the alkoxy group of the alkoxysilane (B). A hydrolysis step of obtaining a reaction composition containing a hydrolyzate of the alkoxysilane (A) and a hydrolyzate of the alkoxysilane (B) by decomposing,
Radiation polymerization of the hydrolyzate of the alkoxysilane (A) until the reaction composition is irradiated with active energy rays and the polymerization conversion rate of the hydrolyzate of the alkoxysilane (A) becomes 1 to 60%. A prepolymerization step of performing
The reaction composition irradiated with active energy rays is applied onto a substrate, and the reaction composition is further irradiated with active energy rays, whereby the polymerization conversion rate of the hydrolyzate of alkoxysilane (A) is 80. % Of the alkoxysilane (A) hydrolyzate to obtain a radical polymer of the alkoxysilane (A), and then the radical polymer and the alkoxysilane (B A main polymerization step of forming a gas barrier resin layer by dehydration condensation with the hydrolyzate of
An inorganic compound film forming step of forming an inorganic compound film on the gas barrier resin layer;
It is characterized by having.

[Hydrolysis step]
First, in the method of the present invention, 100 parts by weight of alkoxysilane (A) having two or more alkoxy groups and one or more radical polymerizable groups in the molecule, and two or more alkoxy groups in the molecule. And 10 to 100 parts by weight of water is added to a raw material composition containing 25 to 200 parts by weight of alkoxysilane (B) having no radical polymerizable group, and the alkoxy group of alkoxysilane (A) and the alkoxysilane. The hydrolysis process of obtaining the reaction composition containing the hydrolyzate of the said alkoxysilane (A) and the hydrolyzate of the said alkoxysilane (B) is implemented by hydrolyzing the alkoxy group of (B).

(Alkoxysilane (A))
The alkoxysilane (A) has two or more alkoxy groups and one or more radically polymerizable groups in the molecule.

In the present invention, the radical polymerizable group means a group capable of addition polymerization by a radical. Examples of the radically polymerizable group of the alkoxysilane (A) include a group having an unsaturated double bond, specifically, an allyl group, an isopropenyl group, a maleoyl group, a styryl group, a vinylbenzyl group, (Meth) acryloxy group, (meth) acryloxyalkyl group, vinyl group and the like can be mentioned. The (meth) acryloxy group means an acryloxy group (CH ₂ ═CHC (O) O—) or a methacryloxy group (CH ₂ ═C (CH ₃ ) C (O) O—).

  Preferred examples of the radical polymerizable group possessed by the alkoxysilane (A) include a (meth) acryloxy group, a (meth) acryloxyalkyl group, and a vinyl group. Examples of (meth) acryloxyalkyl groups include (meth) acryloxymethyl groups having 4 to 9 carbon atoms such as (meth) acryloxymethyl groups, 2- (meth) acryloxyethyl groups, and 3- (meth) acryloxypropyl groups. Preferred is a loxyalkyl group. The alkoxysilane (A) having a (meth) acryloxy group, a (meth) acryloxyalkyl group, or a vinyl group is excellent in radical polymerization reactivity and can be highly polymerized, and has a polymer chain having a dense network structure. It is possible to form a gas barrier resin layer having excellent gas barrier properties.

  As alkoxysilane (A), the alkoxysilane shown by following General formula (1) is mentioned preferably.

（式中、Ｒ¹は炭素数４〜９の（メタ）アクリロキシアルキル基又はビニル基を表し、Ｒ²は炭素数１〜８のアルキル基を表し、Ｒ³は炭素数１〜４のアルキル基を表し、且つｎは０又は１である。）

(In the formula, R ¹ represents a (meth) acryloxyalkyl group having 4 to 9 carbon atoms or a vinyl group, R ² represents an alkyl group having 1 to 8 carbon atoms, and R ³ represents an alkyl having 1 to 4 carbon atoms. Represents a group, and n is 0 or 1.)

In R ¹ of the general formula (1), as the (meth) acryloxyalkyl group having 4 to 9 carbon atoms, a (meth) acryloxymethyl group, a 2- (meth) acryloxyethyl group, and a 3- (meth) ) An acryloxypropyl group is preferred.

R ^{2 in the} general formula (1) is an alkyl group having 1 to 8 carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. , Heptyl group, octyl group and the like.

  Specific examples of the alkoxysilane represented by the general formula (1) include vinyltriethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3 -Acryloxypropyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, and 3-methacryloxy An example is propylmethyldiethoxysilane. These alkoxysilanes (A) may be used individually by 1 type, and may use 2 or more types together. Of these, vinyltriethoxysilane, vinyltrimethoxysilane, and 3- (meth) acryloxypropyltrimethoxysilane are preferred because of excellent radical polymerization reactivity.

（式中、Ｒ^４及びＲ^５はそれぞれ炭素数１〜８のアルキル基を表し、ｍは０〜２の整数である。） (Alkoxysilane (B))
The alkoxysilane (B) has two or more alkoxy groups in the molecule and does not have a radical polymerizable group. As such an alkoxysilane (B), an alkoxysilane represented by the following general formula (II) is preferably used.

(In the formula, R ⁴ and R ⁵ each represent an alkyl group having 1 to 8 carbon atoms, and m is an integer of 0 to 2.)

R ⁴ and R ^{5 in} the general formula (II) are each an alkyl group having 1 to 8 carbon atoms, and preferably an alkyl group having 1 to 4 carbon atoms. Examples of R ⁴ and R ⁵ include a methyl group, an ethyl group, a propyl group, and a butyl group. m is preferably 0.

  The alkoxysilane (B) represented by the general formula (II) can give a crosslinked structure between the main chains of the polymer obtained by radical polymerization of the alkoxysilane (A), and is excellent in the resulting gas barrier film. It is possible to impart gas barrier properties.

  Among these, as alkoxysilane (B), since a dense cross-linked structure can be uniformly formed between the main chains of the alkoxysilane (A) polymer, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and Tetrabutoxysilane is preferred. These alkoxysilanes (B) may be used individually by 1 type, and may use 2 or more types together.

  Although content of alkoxysilane (B) in a raw material composition is limited to 25-200 weight part with respect to 100 weight part of alkoxysilane (A), 40-150 weight part is preferable and 60-100 weight is preferable. Part is more preferred. If the content of the alkoxysilane (B) in the raw material composition is too small, there is a possibility that a sufficient crosslinked structure cannot be formed between the main chains of the alkoxysilane (A) radical polymer described later. Moreover, when there is too much content of the alkoxysilane (B) in a raw material composition, there exists a possibility that the gas barrier resin layer obtained may become white and transparency may fall.

  The raw material composition may further contain inorganic particles, a solvent, and the like. The content of the inorganic particles in the raw material composition is preferably 5 parts by weight or less with respect to 100 parts by weight of the alkoxysilane (A). Moreover, it is preferable that content of the solvent in a raw material composition is 100 weight part or less with respect to 100 weight part of alkoxysilane (A).

(water)
In the method of the present invention, by adding water to the raw material composition, the alkoxy group of alkoxysilane (A) or alkoxysilane (B) is hydrolyzed to form a silanol group. Thereby, the hydrolyzate of the alkoxysilane (A) which has a silanol group, and the hydrolyzate of the alkoxysilane (B) which has a silanol group are obtained. The silanol group means a hydroxy group (≡Si—OH) bonded directly to a silicon atom.

  Although the addition amount of the water added to a raw material composition is limited to 10-100 weight part with respect to 100 weight part of alkoxysilane (A), 20-75 weight part is preferable. If the amount of water added is too small, the alkoxy group of the alkoxysilane (A) or alkoxysilane (B) may not be sufficiently hydrolyzed. Moreover, when there is too much addition amount of water, after the hydrolysis reaction of the alkoxy group which alkoxysilane (A) or alkoxysilane (B) has, the excess amount of water which did not contribute to the said reaction exists in the reaction composition. Will be. This excessive amount of water may inhibit the dehydration condensation reaction of the alkoxysilane (A) and alkoxysilane (B) subjected to hydrolysis reaction in the subsequent step.

(Acid catalyst)
It is preferable to further add an acid catalyst to the raw material composition. The acid catalyst is used to promote the hydrolysis reaction of the alkoxy group that the alkoxysilane (A) or the alkoxysilane (B) has.

  Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid, and organic acids such as formic acid and acetic acid. Of these, nitric acid is preferably used because hydrolysis of the alkoxy group can be promoted moderately.

  The amount of the acid catalyst added to the raw material composition is preferably 0.0001 to 0.01 parts by weight, more preferably 0.001 to 0.005 parts by weight, based on 100 parts by weight of the alkoxysilane (A). If the amount of the acid catalyst added is too small, the effect obtained by adding the acid catalyst may not be sufficient. Moreover, when there is too much addition amount of an acid catalyst, there exists a possibility that the acidity of a gas-barrier resin layer may become high. A gas barrier film containing a gas barrier resin layer having a high acidity may be deteriorated at an early stage.

  By adding water to the raw material composition containing the alkoxysilane (A) and the alkoxysilane (B) described above, the alkoxy group of the alkoxysilane (A) and the alkoxysilane (B) is hydrolyzed. In order to sufficiently perform the hydrolysis reaction of the alkoxy groups of the alkoxysilane (A) and the alkoxysilane (B), it is preferable to sufficiently stir the mixture obtained by adding water to the raw material composition. The stirring time of the mixture is preferably 1 to 24 hours, and more preferably 3 to 10 hours. Moreover, when stirring a mixture, 15-35 degreeC is preferable and the temperature of a mixture has more preferable 20-30 degreeC. If the temperature of the mixture exceeds 35 ° C., water contained in the mixture may evaporate and the alkoxy group may not be sufficiently hydrolyzed, or silanol groups generated by the hydrolysis of the alkoxy group may undergo dehydration condensation. There is.

The formation of silanol groups in the mixture can be confirmed by measuring an infrared absorption spectrum of the mixture. In the infrared absorption spectrum, absorption peaks derived from the Si—O—C portion of alkoxysilane (A) and alkoxysilane (B) appear in the vicinity of wave numbers 812 cm ⁻¹ , 1088 cm ⁻¹ , and 2840 cm ⁻¹ . Therefore, if the infrared absorption spectrum of the mixture is measured before and after the hydrolysis reaction of the alkoxy group, and the absorption peak derived from the Si—O—C portion of the alkoxysilane (A) and the alkoxysilane (B) decreases, It can be determined that the alkoxy group possessed by the alkoxysilane (A) and the alkoxysilane (B) is reduced by hydrolysis, thereby forming a silanol group.

[Preliminary polymerization step]
Next, in the method of the present invention, the reaction composition obtained by the hydrolysis step described above is irradiated with active energy rays, and the polymerization conversion rate of the hydrolyzate of the alkoxysilane (A) is 1 to 60%. Until it becomes, the prepolymerization process which performs radical polymerization of the hydrolyzate of the said alkoxysilane (A) is implemented.

(Photopolymerization initiator)
The reaction composition preferably contains a photopolymerization initiator. By using the photopolymerization initiator, the radical polymerization reaction can be performed rapidly. Therefore, it is preferable to add a photopolymerization initiator to the reaction composition in advance before performing radical polymerization.

  The photopolymerization initiator is not particularly limited as long as it generates radicals by light irradiation. For example, α-hydroxyketone compound, acetophenone compound, benzophenone compound, benzoin compound, benzoin ether compound, benzyl ketal compound, acyl Examples thereof include phosphine oxide compounds, thioxanthone compounds, diacetyl and derivatives thereof, anthraquinone and derivatives thereof, diphenyl disulfide and derivatives thereof, and organic disulfides such as tetramethylthiuram disulfide and dibenzoyl disulfide. Examples of the photopolymerization initiator include 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one and 2,2-dimethoxy-1,2-diphenylethane-1-one. preferable. In addition, a photoinitiator may be used independently or 2 or more types may be used together.

  The content of the photopolymerization initiator in the reaction composition is preferably 0.01 to 0.5 parts by weight, preferably 0.08 to 100 parts by weight with respect to 100 parts by weight of the alkoxysilane (A) contained in the raw material composition. 0.4 parts by weight is more preferable. When there is too little content of the photoinitiator in a reaction composition, there exists a possibility that the effect acquired by addition of a photoinitiator may not be enough. Moreover, when there is too much content of the photoinitiator in a reaction composition, there exists a possibility that an aggregate may arise in the reaction composition irradiated with the active energy ray. The reaction composition containing aggregates may not be applied with a uniform thickness.

  In the prepolymerization step, the active composition is irradiated with active energy rays before the reaction composition containing each of the above-described components is applied to a substrate described later, and the radicals of the alkoxysilane (A) hydrolyzate have. The hydrolyzate of alkoxysilane (A) is radically polymerized until the polymerization conversion of the polymerizable group becomes 1 to 60%.

  Examples of active energy rays applied to the reaction composition include ultraviolet rays, electron beams, α rays, β rays, and γ rays. Of these, ultraviolet rays are preferred.

When irradiating the ultraviolet ray, the irradiation amount of ultraviolet rays to the reaction composition is preferably ^{500~5000mJ / cm 2, 1000~3000mJ / cm} 2 is more preferable. By irradiating ultraviolet rays at such an irradiation amount, the hydrolyzate of alkoxysilane (A) can be sufficiently radically polymerized to a predetermined polymerization conversion rate. Further, the ultraviolet irradiation may be performed using a normal ultraviolet lamp such as a metal halide lamp, a xenon lamp, a carbon arc lamp, a chemical lamp, a low pressure mercury lamp, or a high pressure mercury lamp.

  While the active energy rays are irradiated to the reaction composition in the prepolymerization step, the surface temperature of the reaction composition is preferably 80 ° C. or less, and more preferably 10 to 50 ° C. If the temperature of the reaction composition exceeds 80 ° C. during irradiation with active energy rays, hydrolysis of the alkoxy group of alkoxysilane (A) or alkoxysilane (B) proceeds, resulting in gas barrier properties. There is a possibility that an excellent gas barrier resin layer cannot be obtained.

  In the prepolymerization step, the polymerization conversion rate of the hydrolyzate of alkoxysilane (A) is 1 to 60%, preferably 3 to 57%, more preferably 5 to 55 by irradiation of active energy rays to the reaction composition. The radical polymerization of the hydrolyzate of alkoxysilane (A) is carried out until it reaches%. When the polymerization conversion rate of the hydrolyzate of alkoxysilane (A) is less than 1%, the flexibility of the obtained gas barrier resin layer is lowered, and the gas barrier property is obtained when the gas barrier film is bent or bent. Cracks may occur in the resin layer, and as a result, the gas barrier property of the gas barrier film may be reduced. Moreover, when the polymerization conversion rate of the hydrolyzate of alkoxysilane (A) exceeds 60%, a gel-like aggregate is generated in the reaction composition after irradiation with active energy rays, and the reaction composition is coated. There is a possibility that the gas barrier property of the resulting gas barrier resin layer may be deteriorated due to a decrease in the property, and the hydrolysis reaction and dehydration condensation reaction of the alkoxy group become insufficient.

  In the present invention, the polymerization conversion rate of the hydrolyzate of alkoxysilane (A) refers to the alkoxysilane (A) relative to the weight of the hydrolyzate of alkoxysilane (A) contained in the reaction composition before the start of radical polymerization. ) Of the polymer formed by radical polymerization.

And the measurement of the polymerization conversion rate of the hydrolyzate of alkoxysilane (A) can be performed as follows. First, the same amount of water as that of the reaction composition is added to the reaction composition irradiated with active energy rays to obtain a mixed solution, and the mixed solution is kept at a temperature of 20 ° C. for 1 hour. Stir. Thereafter, the stirred liquid mixture is allowed to stand for 1 hour while adjusting the liquid temperature to 20 ° C., and then the weight W ₂ (g) of the solid content settled in the liquid mixture is measured. The value obtained by dividing the weight W ₂ (g) of the solid sentence by the weight W ₁ (g) of the hydrolyzate of alkoxysilane (A) contained in the reaction composition before the start of radical polymerization is 100. By multiplying, [(W ₂ / W ₁ ) × 100], the polymerization conversion rate [%] of the radical polymerizable group possessed by the alkoxysilane (A) can be calculated.

In addition, the weight of the hydrolyzate of alkoxysilane (A) contained in the reaction composition before the start of radical polymerization is such that all alkoxyl groups are hydrolyzed in the hydrolyzate of alkoxysilane (A) to form silanol groups. Assuming that it is formed, the hydrolyzate of alkoxysilane (A) with respect to the molecular weight (M ₀ ) of alkoxysilane (A) is added to the weight W ₀ (g) of alkoxysilane (A) used in the raw material composition. The molecular weight (M ₁ ) ratio (M ₁ / M ₀ ) is multiplied to obtain a calculated value. Further, the mixture weight W ₂ was solids settling in (g), the weight of the polymer formed by radical polymerization of the alkoxysilane (A).

[Main polymerization process]
Next, in the method of the present invention, the reaction composition irradiated with active energy rays is applied onto a substrate, and the reaction composition is further irradiated with active energy rays, whereby the alkoxysilane (A). After obtaining the radical polymer of the alkoxysilane (A) by performing radical polymerization of the hydrolyzate of the alkoxysilane (A) so that the polymerization conversion rate of the hydrolyzate is 80% or more, A main polymerization step for forming a gas barrier resin layer is performed by dehydrating and condensing the radical polymer and the hydrolyzate of the alkoxysilane (B).

(Base material)
What is necessary is just to determine the base material used for the method of this invention according to the use for which a gas-barrier film is used. A synthetic resin film is mentioned as a base material. A synthetic resin film having an inorganic compound film formed on at least one surface can also be used as a substrate.

  As a material for the synthetic resin film, a transparent thermoplastic resin is preferably used. Examples of transparent thermoplastic resins include polyolefin resins such as polyethylene and polypropylene; polyester resins such as polyethylene terephthalate, polyethylene terephthalate, polyethylene isophthalate, polyethylene-2,6-naphthalate, and polybutylene terephthalate; polyoxymethylene Polyether resins such as Nylon-6, Nylon-6, 6, etc .; Vinyl resins such as polyvinyl alcohol and ethylene-vinyl acetate copolymer saponified products; Polycarbonate resins; Polyimides; Polyetherimides; Polyether sulfone; polysulfone; polyether ether ketone; polyether ketone ketone, and the like can be used. These thermoplastic resins may be a homopolymer or a copolymer. Moreover, these thermoplastic resins may be used independently and can also use 2 or more types together.

  Especially, as a material of a synthetic resin film, since it is excellent in adhesiveness with a gas barrier resin layer, a polyester-type resin is preferable and a polyethylene terephthalate is more preferable.

  The synthetic resin film may contain known additives such as an antistatic agent, an ultraviolet absorber, a plasticizer, a lubricant, and a colorant as necessary. Further, the surface of the synthetic resin film may be subjected to surface modification treatment such as corona treatment, ozone treatment or plasma treatment. Thereby, adhesiveness with a gas barrier resin layer or an inorganic compound film can be improved. The thickness of the synthetic resin film is preferably 3 to 300 μm, more preferably 12 to 300 μm, and particularly preferably 50 to 200 μm.

  In addition, since the inorganic compound film | membrane used for a base material has the structure similar to the inorganic compound film | membrane formed on the gas barrier resin layer mentioned later, detailed description is abbreviate | omitted here.

  As a method of coating the reaction composition on the substrate, a roll coater method, a spin coater method, a dipping method, a bar coater method, a floating knife coater method, a die coater method, a gravure coater method, a curtain coater method, a blade coater method , And spray method.

  Until the polymerization conversion rate of the hydrolyzate of alkoxysilane (A) is 80% or more, preferably 98 to 100% by irradiation of active energy rays to the reaction composition coated on the synthetic resin film The radical polymerization of the hydrolyzate (A) is further performed. If the polymerization conversion rate of the hydrolyzate of alkoxysilane (A) is less than 80%, the flexibility of the resulting gas barrier resin layer may be reduced.

  Examples of the active energy rays applied to the reaction composition coated on the substrate include ultraviolet rays, electron beams, α rays, β rays, and γ rays. Of these, an electron beam is preferable.

  When irradiating an electron beam to a reaction composition, 30-200 kV is preferable and, as for the acceleration voltage of an electron beam, 70-180 kV is more preferable. Moreover, 10-200 kGy is preferable and, as for the irradiation dose of an electron beam, 100-175 kGy is more preferable.

  During irradiation of active energy rays to the reaction composition in the radical polymerization step, the surface temperature of the reaction composition is preferably 80 ° C. or less, and more preferably 10 to 50 ° C. If the temperature of the reaction composition exceeds 80 ° C. during irradiation with active energy rays, hydrolysis of the alkoxy group of alkoxysilane (A) or alkoxysilane (B) proceeds in the radical polymerization step. There is a possibility that a gas barrier resin layer having excellent gas barrier properties cannot be obtained.

  In the main polymerization step, the radical composition of the alkoxysilane (A) is obtained by irradiating the reaction composition coated on the substrate with active energy rays and performing radical polymerization of the hydrolyzate of the alkoxysilane (A). Then, dehydration condensation between the radical polymer and the hydrolyzate of alkoxysilane (B) is performed. The radical polymer has a silanol group derived from the hydrolyzate of alkoxysilane (A). A gas barrier resin layer is obtained by dehydrating and condensing the silanol group possessed by such a radical polymer and the silanol group possessed by the hydrolyzate of alkoxysilane (B).

  The dehydration condensation between the radical polymer and the hydrolyzate of alkoxysilane (B) is preferably performed by heating the reaction composition irradiated with active energy rays after being coated on the substrate. By heating the composition, water contained in the composition is removed and dried to promote dehydration condensation.

  Specifically, the reaction composition irradiated with active energy rays after being coated on the substrate is preferably heated to 90 to 150 ° C, more preferably 100 to 130 ° C. The heating time is preferably 0.05 to 0.5 hours, and more preferably 0.1 to 0.3 hours.

  The thickness of the gas barrier resin layer is preferably 0.01 to 100 μm, more preferably 0.1 to 50 μm, and particularly preferably 1 to 10 μm. A gas barrier resin layer having a thickness of less than 0.01 μm may not have sufficient gas barrier properties. In addition, in the gas barrier resin layer having a thickness exceeding 100 μm, the rigidity becomes too high, and the handleability of the gas barrier film may be reduced.

  In the method of the present invention, as described above, first, the alkoxy group of the alkoxysilane (A) and the alkoxysilane (B) is hydrolyzed to form a silanol group, and then the alkoxysilane (A) is hydrolyzed. After radically polymerizing the product, dehydration condensation between the radical polymer derived from the hydrolyzate of alkoxysilane (A) and the hydrolyzate of alkoxysilane (B) is performed. Even after the hydrolyzate of alkoxysilane (A) is radically polymerized after the formation of the silanol group, a part of the silanol group may cause a dehydration condensation reaction. However, the reaction rate of dehydration condensation of silanol groups is very slow. For this reason, the radical polymerization mentioned above preferentially occurs over the dehydration condensation reaction of silanol groups. Therefore, almost no dehydration condensation reaction of silanol groups occurring during radical polymerization occurs and can be ignored. After radical polymerization, radical weight derived from the hydrolyzate of alkoxysilane (A) is ignored. Most of the silanol groups possessed by the coalescence and the hydrolyzate of alkoxysilane (B) will undergo dehydration condensation.

  In the gas barrier resin layer obtained by the method of the present invention, the alkoxysilane (A) possessed by the radical polymer is cross-linked between the main chains of the radical polymer derived from the hydrolyzate of the alkoxysilane (A). A siloxane bond (-Si-O-Si-) is formed by dehydration condensation between the silanol group derived from the hydrolyzate of A) and the silanol group possessed by the hydrolyzate of alkoxysilane (B). The finally obtained polymer forms a complex network structure.

  In addition, by preferentially increasing the molecular weight of the hydrolyzate of alkoxysilane (A) prior to dehydration condensation, the main chains of the radical polymers adjacent to each other are brought close to each other. In this way, in the state where the main chains of the radical polymer are close to each other, the silanol group possessed by the radical polymer, and the silanol group possessed by the hydrolyzate of alkoxysilane (B) Thus, a dense network structure in which siloxane bonds are cross-linked between the main chains of the radical polymer can be formed.

  Such a gas barrier resin layer has a complex and dense network structure in which siloxane bonds are cross-linked between the main chains of the radical polymer, thereby preventing high transmission of gases such as oxygen and water vapor. It is possible to impart excellent gas barrier properties to the resulting gas barrier film.

  Further, the alkoxysilane (A) hydrolyzate is preliminarily polymerized until the polymerization conversion rate becomes 1 to 60%, and then subjected to main polymerization so that the polymerization addition rate becomes 80% or more, whereby the alkoxysilane (A In the gas barrier resin layer obtained, the radical chain of the radical polymer and the siloxane bond that crosslinks between them can be uniformly dispersed in the resulting gas barrier resin layer. . Thereby, the softness | flexibility and tough gas-barrier resin layer are obtained by the outstanding softness | flexibility resulting from the principal chain part of a radical polymer, and the outstanding hardness derived from a siloxane bond being provided.

  Such a gas barrier resin layer can disperse the external force uniformly even when an external force due to deformation such as bending or thermal expansion is applied, and can greatly reduce the occurrence of breakage such as cracks. Therefore, since the gas barrier film using the gas barrier resin layer is excellent in flexibility and flexibility, the gas barrier film can be bent and installed or used at high temperatures. Excellent gas barrier properties can be maintained.

[Inorganic compound film forming step]
And in the method of this invention, the inorganic compound film | membrane formation process which forms an inorganic compound film | membrane on the gas barrier resin layer formed as mentioned above is implemented. By using the inorganic compound film, the gas barrier property of the gas barrier film can be improved.

  Examples of the material constituting the inorganic compound film include metal oxides and metal nitrides. Specific examples include metal oxides such as silicon oxide, aluminum oxide, calcium oxide, magnesium oxide, zirconium oxide, and titanium oxide, and metal nitrides such as silicon nitride and titanium nitride. Among these, metal oxides are preferable because inorganic compound films having excellent gas barrier properties can be formed, and silicon oxide, aluminum oxide, calcium oxide, magnesium oxide, zirconium oxide, and titanium oxide are more preferable, and silicon oxide and aluminum oxide are preferable. Is more preferable, and silicon oxide is particularly preferable.

  The inorganic compound film containing silicon oxide may contain other metal atoms such as aluminum, magnesium, calcium, potassium, sodium, titanium, zirconium, and yttrium, and nonmetal atoms such as carbon, boron, nitrogen, and fluorine. .

  When the thickness of the inorganic compound film is too thin, there is a possibility that a gas barrier film having a sufficient gas barrier property against oxygen or water vapor cannot be provided. If the inorganic compound film is too thick, cracks are likely to occur due to the difference in shrinkage between the gas barrier resin layer and the barrier film against oxygen and water vapor in the gas barrier film. There is a risk that the performance will be reduced. Therefore, the thickness of the inorganic compound film is preferably 5 nm to 10 μm, and more preferably 10 nm to 5 μm.

  Examples of the method for forming the inorganic compound film include a physical vapor deposition method (PVD) such as a sputtering method, a vapor deposition method, and an ion plating method, a chemical vapor deposition method (CVD), and the like. Is preferred.

  A schematic cross-sectional view of a gas barrier film obtained by the method of the present invention described above is shown in FIG. In the gas barrier film shown in FIG. 1, a gas barrier resin layer 20 and an inorganic compound film 20 are laminated and integrated in this order on a substrate 10.

  Examples of uses in which the gas barrier film obtained by the method of the present invention is used include packaging of articles that require blocking of various gases such as water vapor and oxygen, packaging for preventing deterioration of food, industrial products, pharmaceuticals, and the like. Can be used. In addition to such packaging applications, the gas barrier film of the present invention is such that elements used in solar cell modules, liquid crystal display panels, organic EL (electroluminescence) display panels, etc. are exposed to oxygen and water vapor. Therefore, it can be used as a part of the product structure or as a packaging material for these elements. Especially, since the gas barrier film of the present invention has excellent gas barrier properties, flexibility, and bending resistance, it can be used as a back surface side protective sheet or a light receiving surface side protective sheet of a solar cell module. Is preferred. The back surface side protective sheet and the light receiving surface side protective sheet are used for protecting the power generating element and a sealing resin such as an ethylene-vinyl acetate copolymer in the solar cell module.

  According to the method of the present invention, it is possible to produce a gas barrier film excellent in gas barrier properties against oxygen, water vapor and the like. Even when an external force due to deformation such as bending or thermal expansion is applied to the gas barrier film obtained by the above method, the occurrence of breakage such as cracks in the gas barrier resin layer is highly reduced. Therefore, the gas barrier film of the present invention can maintain excellent gas barrier properties even when it is bent and installed or used at high temperatures.

It is a schematic cross section of the gas barrier film obtained by the method of the present invention.

  Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

[Example 1]
1. Hydrolysis step: Adding 54 parts by weight of water and 0.002 parts by weight of nitric acid to a raw material composition containing 100 parts by weight of 3-methacryloxypropyltrimethoxysilane (A1) and 94 parts by weight of tetraethoxysilane (B). Gave a mixture. By stirring the mixture at 25 ° C. for 3 hours, the methoxy group of 3-methacryloxypropyltrimethoxysilane (A1) and the ethoxy group of tetraethoxysilane (B) are each hydrolyzed to produce silanol groups. Formed. Thereby, the reaction composition containing the hydrolyzate of 3-methacryloxypropyl trimethoxysilane (A1) and the hydrolyzate of tetraethoxysilane (B) was obtained.

2. Prepolymerization step To the total amount of the reaction composition, a photopolymerization initiator (2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, manufactured by Ciba Specialty Chemicals, Inc., trade name “ Irgacure 907 ") After adding 0.2 parts by weight, the reaction composition was irradiated with ultraviolet rays at an irradiation dose of 1400 mJ / cm ² using an ultraviolet lamp (9 W) for 15 minutes to give 3-methacryloxypropyltrimethoxy. Until the polymerization conversion of the hydrolyzate of silane (A1) reaches 32%, radical polymerization of the 3-methacryloxypropyl group of the hydrolyzate of 3-methacryloxypropyltrimethoxysilane (A1) is performed. It was.

3. Main Polymerization Step The reaction composition irradiated with ultraviolet rays was applied to one surface of a polyethylene terephthalate (PET) film (thickness 50 μm) with a gravure coater. Next, the reaction composition applied to one surface of the PET film is irradiated with an electron beam under the conditions of an acceleration voltage of 175 kV and an irradiation dose of 150 kGy using an electron beam irradiation apparatus (product name EC300 / 165/800 manufactured by ESI). By doing so, the hydrolyzate of 3-methacryloxypropyltrimethoxysilane (A1) has until the polymerization conversion rate of the hydrolyzate of 3-methacryloxypropyltrimethoxysilane (A1) reaches 99%. A radical polymer was obtained by performing radical polymerization of a 3-methacryloxypropyl group. Then, the hydrolyzate of 3-methacryloxypropyltrimethoxysilane (A1) in the radical polymer by heating the PET film coated with the reaction composition in an oven at a temperature of 120 ° C. for 0.2 hours. The silanol group derived from the above and the silanol group contained in the hydrolyzate of tetraethoxysilane (B) were subjected to dehydration condensation to form a siloxane bond that cross-links between the radical polymers. Thereby, a gas barrier resin layer (thickness 8 μm) was formed on one surface of the PET film.

4). Inorganic compound film forming step Inorganic compound consisting of silicon oxide on one side of gas barrier resin layer by RF magnetron sputtering using a target made of silicon oxide while maintaining the temperature of PET film and gas barrier resin layer at 60 ° C A film (thickness 80 nm) was formed directly. As a result, a gas barrier film in which a gas barrier resin layer and an inorganic compound film were laminated and integrated in this order on one surface of the PET film was obtained.

[Examples 2 to 5]
The amount of tetraethoxysilane (B), water and nitric acid in the production of the reaction composition, the amount of photopolymerization initiator added to the reaction composition, and 3-methacryloxypropyltrimethoxysilane (A1) in the prepolymerization step A gas barrier film was produced in the same manner as in Example 1 except that the polymerization conversion rate of each hydrolyzate was changed as shown in Table 1.

[Example 6]
1. Hydrolysis step A mixture is obtained by adding 32 parts by weight of water and 0.001 part by weight of nitric acid to a raw material composition containing 100 parts by weight of vinyltrimethoxysilane (A2) and 70 parts by weight of tetraethoxysilane (B). It was. By stirring the mixture at 20 ° C. for 3 hours, the methoxy group of vinyltrimethoxysilane (A2) and the ethoxy group of tetraethoxysilane (B) were each hydrolyzed to form silanol groups. . Thereby, the reaction composition containing the hydrolyzate of vinyltrimethoxysilane (A2) and the hydrolyzate of tetraethoxysilane (B) was obtained.

2. Prepolymerization step To the total amount of the reaction composition, a photopolymerization initiator (2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, manufactured by Ciba Specialty Chemicals, Inc., trade name “ After adding 0.1 part by weight of Irgacure 907 ”), the reaction composition was irradiated with ultraviolet rays for 15 minutes using an ultraviolet lamp (9 W) at an irradiation amount of 1000 mJ / cm ² , so that vinyltrimethoxysilane (A2 The radical polymerization of the vinyl group contained in the hydrolyzate of vinyltrimethoxysilane (A2) was carried out until the polymerization conversion of the hydrolyzate of 5) reached 5%.

3. Main Polymerization Step The reaction composition irradiated with ultraviolet rays was applied to one surface of a polyethylene terephthalate (PET) film (thickness 50 μm) with a gravure coater. Next, the reaction composition applied to one surface of the PET film is irradiated with an electron beam under the conditions of an acceleration voltage of 175 kV and an irradiation dose of 150 kGy using an electron beam irradiation apparatus (product name EC300 / 165/800 manufactured by ESI). By carrying out radical polymerization of the vinyl group of the hydrolyzate of vinyltrimethoxysilane (A2) until the polymerization conversion rate of the hydrolyzate of vinyltrimethoxysilane (A2) reaches 98%. As a result, a radical polymer was obtained. Then, the silanol derived from the hydrolyzate of vinyltrimethoxysilane (A2) in the radical polymer by heating the PET film coated with the reaction composition in an oven at a temperature of 120 ° C. for 0.2 hours. The silanol groups possessed by the hydrolyzate of tetraethoxysilane (B) were dehydrated and condensed to form siloxane bonds that cross-link between the radical polymers. Thereby, a gas barrier resin layer (thickness 8 μm) was formed on one surface of the PET film.

4). Inorganic compound film forming step Inorganic compound consisting of silicon oxide on one side of gas barrier resin layer by RF magnetron sputtering using a target made of silicon oxide while maintaining the temperature of PET film and gas barrier resin layer at 60 ° C A film (thickness 80 nm) was formed directly. As a result, a gas barrier film in which a gas barrier resin layer and an inorganic compound film were laminated and integrated in this order on one surface of the PET film was obtained.

[Comparative Example 1]
1. Hydrolysis step: Adding 54 parts by weight of water and 0.002 parts by weight of nitric acid to a raw material composition containing 100 parts by weight of 3-methacryloxypropyltrimethoxysilane (A1) and 94 parts by weight of tetraethoxysilane (B). Gave a mixture. By stirring the mixture at 35 ° C. for 1 hour, the methoxy group of 3-methacryloxypropyltrimethoxysilane (A1) and the ethoxy group of tetraethoxysilane (B) are each hydrolyzed to produce silanol groups. Formed. Thereby, the reaction composition containing the hydrolyzate of 3-methacryloxypropyl trimethoxysilane (A1) and the hydrolyzate of tetraethoxysilane (B) was obtained.

2. Main polymerization step The reaction composition was applied to one surface of a polyethylene terephthalate (PET) film (thickness 50 μm) by a gravure coater. Next, the reaction composition applied to one surface of the PET film is irradiated with an electron beam under the conditions of an acceleration voltage of 175 kV and an irradiation dose of 150 kGy using an electron beam irradiation apparatus (product name EC300 / 165/800 manufactured by ESI). Thus, the hydrolyzate of 3-methacryloxypropyltrimethoxysilane (A1) has until the polymerization conversion rate of the hydrolyzate of 3-methacryloxypropyltrimethoxysilane (A1) reaches 95%. A radical polymer was obtained by performing radical polymerization of a 3-methacryloxypropyl group. Then, the hydrolyzate of 3-methacryloxypropyltrimethoxysilane (A1) in the radical polymer by heating the PET film coated with the reaction composition in an oven at a temperature of 120 ° C. for 0.2 hours. The silanol group derived from the above and the silanol group contained in the hydrolyzate of tetraethoxysilane (B) were subjected to dehydration condensation to form a siloxane bond that cross-links between the radical polymers. Thereby, a gas barrier resin layer (thickness 8 μm) was formed on one surface of the PET film.

3. Inorganic compound film forming step Inorganic compound consisting of silicon oxide on one side of gas barrier resin layer by RF magnetron sputtering using a target made of silicon oxide while maintaining the temperature of PET film and gas barrier resin layer at 60 ° C A film (thickness 80 nm) was formed directly. As a result, a gas barrier film in which a gas barrier resin layer and an inorganic compound film were laminated and integrated in this order on one surface of the PET film was obtained.

[Comparative Examples 2-3]
A gas barrier film was produced in the same manner as in Comparative Example 1, except that the amounts of tetraethoxysilane (B), water, and nitric acid in the production of the reaction composition were changed as shown in Table 1, respectively.

[Comparative Example 4]
1. Hydrolysis step A mixture is obtained by adding 32 parts by weight of water and 0.001 part by weight of nitric acid to a raw material composition containing 100 parts by weight of vinyltrimethoxysilane (A2) and 70 parts by weight of tetraethoxysilane (B). It was. By stirring the mixture at 20 ° C. for 10 hours, the methoxy group of vinyltrimethoxysilane (A2) and the ethoxy group of tetraethoxysilane (B) were each hydrolyzed to form silanol groups. . Thereby, the reaction composition containing the hydrolyzate of vinyltrimethoxysilane (A2) and the hydrolyzate of tetraethoxysilane (B) was obtained.

2. Main polymerization step The reaction composition was applied to one surface of a polyethylene terephthalate (PET) film (thickness 50 μm) by a gravure coater. Next, the reaction composition applied to one surface of the PET film is irradiated with an electron beam under the conditions of an acceleration voltage of 175 kV and an irradiation dose of 150 kGy using an electron beam irradiation apparatus (product name EC300 / 165/800 manufactured by ESI). By performing radical polymerization of the vinyl group of the hydrolyzate of vinyltrimethoxysilane (A2) until the polymerization conversion rate of the hydrolyzate of vinyltrimethoxysilane (A2) reaches 99%. As a result, a radical polymer was obtained. Then, the silanol derived from the hydrolyzate of vinyltrimethoxysilane (A2) in the radical polymer by heating the PET film coated with the reaction composition in an oven at a temperature of 120 ° C. for 0.2 hours. The silanol groups possessed by the hydrolyzate of tetraethoxysilane (B) were dehydrated and condensed to form siloxane bonds that cross-link between the radical polymers. Thereby, a gas barrier resin layer (thickness 8 μm) was formed on one surface of the PET film.

3. Inorganic compound film forming step Inorganic compound consisting of silicon oxide on one side of gas barrier resin layer by RF magnetron sputtering using a target made of silicon oxide while maintaining the temperature of PET film and gas barrier resin layer at 60 ° C A film (thickness 80 nm) was formed directly. As a result, a gas barrier film in which a gas barrier resin layer and an inorganic compound film were laminated and integrated in this order on one surface of the PET film was obtained.

[Comparative Example 5]
1. Hydrolysis step: Adding 43 parts by weight of water and 0.002 parts by weight of nitric acid to a raw material composition containing 100 parts by weight of 3-methacryloxypropyltrimethoxysilane (A1) and 63 parts by weight of tetraethoxysilane (B). Gave a mixture. By stirring the mixture at 25 ° C. for 3 hours, the methoxy group of 3-methacryloxypropyltrimethoxysilane (A1) and the ethoxy group of tetraethoxysilane (B) are each hydrolyzed to produce silanol groups. Formed. Thereby, the reaction composition containing the hydrolyzate of 3-methacryloxypropyl trimethoxysilane (A1) and the hydrolyzate of tetraethoxysilane (B) was obtained.

2. Prepolymerization step To the total amount of the reaction composition, a photopolymerization initiator (2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, manufactured by Ciba Specialty Chemicals, Inc., trade name “ After adding 2 parts by weight of Irgacure 907 "), the reaction composition was irradiated with ultraviolet rays at an irradiation dose of 4000 mJ / cm ² for 45 minutes using an ultraviolet lamp (9 W), thereby producing 3-methacryloxypropyltrimethoxysilane. Until the polymerization conversion of the hydrolyzate of (A1) reached 78%, radical polymerization of the 3-methacryloxypropyl group of the hydrolyzate of 3-methacryloxypropyltrimethoxysilane (A1) was performed. .

3. Gas barrier resin layer forming step Since the viscosity of the reaction composition irradiated with ultraviolet rays increased excessively, 15 parts by weight of ethyl acetate was added to 100 parts by weight of the reaction composition to the reaction composition irradiated with ultraviolet rays. By mixing, the viscosity of the reaction composition was reduced. The reaction composition with reduced viscosity was applied to one surface of a polyethylene terephthalate (PET) film (thickness 50 μm) by a gravure coater. Then, the hydrolyzate of 3-methacryloxypropyltrimethoxysilane (A1) in the radical polymer by heating the PET film coated with the reaction composition in an oven at a temperature of 120 ° C. for 0.2 hours. The silanol group derived from the above and the silanol group contained in the hydrolyzate of tetraethoxysilane (B) were subjected to dehydration condensation to form a siloxane bond that cross-links between the radical polymers. Thereby, a gas barrier resin layer (thickness 8 μm) was formed on one surface of the PET film.

4). Inorganic compound film forming step Inorganic compound consisting of silicon oxide on one side of gas barrier resin layer by RF magnetron sputtering using a target made of silicon oxide while maintaining the temperature of PET film and gas barrier resin layer at 60 ° C A film (thickness 80 nm) was formed directly. As a result, a gas barrier film in which a gas barrier resin layer and an inorganic compound film were laminated and integrated in this order on one surface of the PET film was obtained.

[Comparative Example 6]
1. Hydrolysis step 3-methacryloxypropyltrimethoxysilane (A1) 100 parts by weight, tetraethoxysilane (B) 14.7 parts by weight, tripropylene glycol diacrylate 85.3 parts by weight, and 2-ethylhexyl acrylate 91.1 parts by weight A mixture was obtained by adding 2.9 parts by weight of water and 0.001 part by weight of nitric acid to the raw material composition containing parts. By stirring the mixture at 20 ° C. for 24 hours, the methoxy group of 3-methacryloxypropyltrimethoxysilane (A1) and the ethoxy group of tetraethoxysilane (B) are each hydrolyzed to produce silanol groups. Formed. Thereby, the reaction composition containing the hydrolyzate of 3-methacryloxypropyl trimethoxysilane (A1) and the hydrolyzate of tetraethoxysilane (B) was obtained.

2. Main polymerization step The reaction composition was applied to one surface of a polyethylene terephthalate (PET) film (thickness 50 μm) by a gravure coater. Next, the reaction composition applied to one surface of the PET film is irradiated with an electron beam under the conditions of an acceleration voltage of 175 kV and an irradiation dose of 150 kGy using an electron beam irradiation apparatus (product name EC300 / 165/800 manufactured by ESI). Thus, the hydrolyzate of 3-methacryloxypropyltrimethoxysilane (A1) has until the polymerization conversion rate of the hydrolyzate of 3-methacryloxypropyltrimethoxysilane (A1) reaches 95%. A radical polymer was obtained by radical polymerization of a 3-methacryloxypropyl group, an acryloxy group possessed by tripropylene glycol diacrylate, and an acryloxy group possessed by 2-ethylhexyl acrylate. Then, the hydrolyzate of 3-methacryloxypropyltrimethoxysilane (A1) in the radical polymer by heating the PET film coated with the reaction composition in an oven at a temperature of 120 ° C. for 0.2 hours. The silanol group derived from the above and the silanol group contained in the hydrolyzate of tetraethoxysilane (B) were subjected to dehydration condensation to form a siloxane bond that cross-links between the radical polymers. Thereby, a gas barrier resin layer (thickness 8 μm) was formed on one surface of the PET film.

3. Inorganic compound film forming step Inorganic compound consisting of silicon oxide on one side of gas barrier resin layer by RF magnetron sputtering using a target made of silicon oxide while maintaining the temperature of PET film and gas barrier resin layer at 60 ° C A film (thickness 80 nm) was formed directly. As a result, a gas barrier film in which a gas barrier resin layer and an inorganic compound film were laminated and integrated in this order on one surface of the PET film was obtained.

[Comparative Example 7]
1. Hydrolysis Step 3- Raw material composition containing 100 parts by weight of 3-methacryloxypropyltrimethoxysilane (A1), 20 parts by weight of tetraethoxysilane (B) and 100 parts by weight of tripropylene glycol diacrylate, 2.2 parts by weight of water And 0.001 weight part of nitric acid was added, and the mixture was obtained. By stirring the mixture at 20 ° C. for 24 hours, the methoxy group of 3-methacryloxypropyltrimethoxysilane (A1) and the ethoxy group of tetraethoxysilane (B) are each hydrolyzed to produce silanol groups. Formed. Thereby, the reaction composition containing the hydrolyzate of 3-methacryloxypropyl trimethoxysilane (A1) and the hydrolyzate of tetraethoxysilane (B) was obtained.

2. Main polymerization step The reaction composition was applied to one surface of a polyethylene terephthalate (PET) film (thickness 50 μm) by a gravure coater. Next, the reaction composition applied to one surface of the PET film is irradiated with an electron beam under the conditions of an acceleration voltage of 175 kV and an irradiation dose of 150 kGy using an electron beam irradiation apparatus (product name EC300 / 165/800 manufactured by ESI). Thus, the hydrolyzate of 3-methacryloxypropyltrimethoxysilane (A1) has until the polymerization conversion rate of the hydrolyzate of 3-methacryloxypropyltrimethoxysilane (A1) reaches 95%. A radical polymer was obtained by performing radical polymerization of a 3-methacryloxypropyl group and an acryloxy group possessed by tripropylene glycol diacrylate. Then, the hydrolyzate of 3-methacryloxypropyltrimethoxysilane (A1) in the radical polymer by heating the PET film coated with the reaction composition in an oven at a temperature of 120 ° C. for 0.2 hours. The silanol group derived from the above and the silanol group contained in the hydrolyzate of tetraethoxysilane (B) were subjected to dehydration condensation to form a siloxane bond that cross-links between the radical polymers. Thereby, a gas barrier resin layer (thickness 8 μm) was formed on one surface of the PET film.

3. Inorganic compound film forming step Inorganic compound consisting of silicon oxide on one side of gas barrier resin layer by RF magnetron sputtering using a target made of silicon oxide while maintaining the temperature of PET film and gas barrier resin layer at 60 ° C A film (thickness 80 nm) was formed directly. As a result, a gas barrier film in which a gas barrier resin layer and an inorganic compound film were laminated and integrated in this order on one surface of the PET film was obtained.

[Comparative Example 8]
1. Hydrolysis step 2.9 parts by weight of water and 0.001 part by weight of nitric acid are added to a raw material composition containing 100 parts by weight of 3-methacryloxypropyltrimethoxysilane (A1) and 250 parts by weight of tripropylene glycol diacrylate. This gave a mixture. By stirring the mixture at 20 ° C. for 24 hours, the methoxy group of 3-methacryloxypropyltrimethoxysilane (A1) and the ethoxy group of tetraethoxysilane (B) are each hydrolyzed to produce silanol groups. Formed. Thereby, the reaction composition containing the hydrolyzate of 3-methacryloxypropyl trimethoxysilane (A1) and the hydrolyzate of tetraethoxysilane (B) was obtained.

2. Main polymerization step The reaction composition was applied to one surface of a polyethylene terephthalate (PET) film (thickness 50 μm) by a gravure coater. Next, the reaction composition applied to one surface of the PET film is irradiated with an electron beam under the conditions of an acceleration voltage of 175 kV and an irradiation dose of 150 kGy using an electron beam irradiation apparatus (product name EC300 / 165/800 manufactured by ESI). Thus, the hydrolyzate of 3-methacryloxypropyltrimethoxysilane (A1) has until the polymerization conversion rate of the hydrolyzate of 3-methacryloxypropyltrimethoxysilane (A1) reaches 95%. A radical polymer was obtained by performing radical polymerization of a 3-methacryloxypropyl group and an acryloxy group possessed by tripropylene glycol diacrylate. Then, the hydrolyzate of 3-methacryloxypropyltrimethoxysilane (A1) in the radical polymer by heating the PET film coated with the reaction composition in an oven at a temperature of 120 ° C. for 0.2 hours. Silanol groups derived from were dehydrated and condensed to form siloxane bonds. Thereby, a gas barrier resin layer (thickness 8 μm) was formed on one surface of the PET film.

3. Inorganic compound film forming step Inorganic compound consisting of silicon oxide on one side of gas barrier resin layer by RF magnetron sputtering using a target made of silicon oxide while maintaining the temperature of PET film and gas barrier resin layer at 60 ° C A film (thickness 80 nm) was formed directly. As a result, a gas barrier film in which a gas barrier resin layer and an inorganic compound film were laminated and integrated in this order on one surface of the PET film was obtained.

[Comparative Example 9]
1. Hydrolysis step 2.9 parts by weight of water and nitric acid were added to a raw material composition containing 100 parts by weight of 3-methacryloxypropyltrimethoxysilane (A1), 20 parts by weight of tripropylene glycol diacrylate, and 100 parts by weight of 2-ethylhexyl acrylate. A mixture was obtained by adding 0.001 part by weight. The mixture was stirred at 20 ° C. for 24 hours to hydrolyze the methoxy group of 3-methacryloxypropyltrimethoxysilane (A1) to form a silanol group. Thereby, the reaction composition containing the hydrolyzate of 3-methacryloxypropyl trimethoxysilane (A1) was obtained.

2. Main polymerization step The reaction composition was applied to one surface of a polyethylene terephthalate (PET) film (thickness 50 μm) by a gravure coater. Next, the reaction composition applied to one surface of the PET film is irradiated with an electron beam under the conditions of an acceleration voltage of 175 kV and an irradiation dose of 150 kGy using an electron beam irradiation apparatus (product name EC300 / 165/800 manufactured by ESI). Thus, the hydrolyzate of 3-methacryloxypropyltrimethoxysilane (A1) has until the polymerization conversion rate of the hydrolyzate of 3-methacryloxypropyltrimethoxysilane (A1) reaches 95%. A radical polymer was obtained by radical polymerization of a 3-methacryloxypropyl group, an acryloxy group possessed by tripropylene glycol diacrylate, and an acryloxy group possessed by 2-ethylhexyl acrylate. Then, the hydrolyzate of 3-methacryloxypropyltrimethoxysilane (A1) in the radical polymer by heating the PET film coated with the reaction composition in an oven at a temperature of 120 ° C. for 0.2 hours. Silanol groups derived from the above were dehydrated and condensed to form siloxane bonds that cross-link between the radical polymers. Thereby, a gas barrier resin layer (thickness 8 μm) was formed on one surface of the PET film.

3. Inorganic compound film forming step Inorganic compound consisting of silicon oxide on one side of gas barrier resin layer by RF magnetron sputtering using a target made of silicon oxide while maintaining the temperature of PET film and gas barrier resin layer at 60 ° C A film (thickness 80 nm) was formed directly. As a result, a gas barrier film in which a gas barrier resin layer and an inorganic compound film were laminated and integrated in this order on one surface of the PET film was obtained.

(Evaluation)
The gas barrier film was subjected to a bending resistance test according to the following procedure, and the water vapor transmission rate before and after the bending resistance test was measured. The results are shown in Table 1.

(Bend resistance test)
The gas barrier film was subjected to a bending resistance test based on JIS C5016. The bending resistance test is performed between a fixed plate and a movable plate of a bending resistance tester in a state where the gas barrier film is bent in a U shape so that the inorganic compound film forming surface is formed as a convex surface. After being attached, the movable plate was repeatedly moved back and forth repeatedly at a predetermined stroke. The bending radius of the gas barrier film was 10 mm, the stroke was 60 mm, and the number of reciprocating motions of the movable plate was 50.

(Water vapor transmission rate)
The water vapor transmission rate (g / m ² · day) of the gas barrier film was determined by a gas / vapor transmission rate measuring device (GTR-Tech., Product name: GTR- 300XASC), measurement was performed for 2 hours under the conditions of a temperature of 40 ° C. and a relative humidity of 90%.

10 Synthetic resin film 20 Inorganic compound film 30 Gas barrier resin layer

Claims (6)

100 parts by weight of alkoxysilane (A) having two or more alkoxy groups and one or more radical polymerizable groups in the molecule, and two or more alkoxy groups in the molecule and having radical polymerizable groups The raw material composition containing 25 to 200 parts by weight of alkoxysilane (B) is added with 10 to 100 parts by weight of water to hydrolyze the alkoxy group of the alkoxysilane (A) and the alkoxy group of the alkoxysilane (B). A hydrolysis step of obtaining a reaction composition containing a hydrolyzate of the alkoxysilane (A) and a hydrolyzate of the alkoxysilane (B) by decomposing,
Radiation polymerization of the hydrolyzate of the alkoxysilane (A) until the reaction composition is irradiated with active energy rays and the polymerization conversion rate of the hydrolyzate of the alkoxysilane (A) becomes 1 to 60%. A prepolymerization step of performing
The reaction composition irradiated with active energy rays is applied onto a substrate, and the reaction composition is further irradiated with active energy rays, whereby the polymerization conversion rate of the hydrolyzate of alkoxysilane (A) is 80. % Of the alkoxysilane (A) hydrolyzate to obtain a radical polymer of the alkoxysilane (A), and then the radical polymer and the alkoxysilane (B A main polymerization step of forming a gas barrier resin layer by dehydration condensation with the hydrolyzate of
An inorganic compound film forming step of forming an inorganic compound film on the gas barrier resin layer;
A method for producing a gas barrier film, comprising: The method for producing a gas barrier film according to claim 1, wherein the alkoxysilane (A) contains an alkoxysilane represented by the following general formula (1).

(In the formula, R ¹ represents a (meth) acryloxyalkyl group having 4 to 9 carbon atoms or a vinyl group, R ² represents an alkyl group having 1 to 8 carbon atoms, and R ³ represents an alkyl having 1 to 4 carbon atoms. Represents a group, and n is 0 or 1.)   The method for producing a gas barrier film according to claim 1 or 2, wherein the alkoxysilane (A) contains 3- (meth) acryloxypropyltrimethoxysilane and / or vinyltrimethoxysilane. The method for producing a gas barrier film according to any one of claims 1 to 3, wherein the alkoxysilane (B) contains an alkoxysilane represented by the following general formula (II).

(In the formula, R ⁴ and R ⁵ each represent an alkyl group having 1 to 8 carbon atoms, and m is an integer of 0 to 2.)   The inorganic compound film includes at least one metal oxide selected from the group consisting of silicon oxide, aluminum oxide, calcium oxide, magnesium oxide, zirconium oxide, and titanium oxide. A method for producing a gas barrier film according to claim 1.   The method for producing a gas barrier film according to any one of claims 1 to 5, wherein the inorganic compound film is formed by a sputtering method.

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