JP2016120665A - Gas barrier laminate, and solar cell module and image display element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas barrier laminate which has sufficient barrier performance as applications of a packaging material, a solar cell and an image display element, and does not impair the barrier performance even when a foreign matter exists.SOLUTION: A gas barrier laminate 10 has a gas barrier layer 12 formed of an inorganic material and an organic layer 13 sequentially laminated on a resin substrate 11. The gas barrier layer 12 is formed by vapor-depositing a vapor deposition material containing metallic silicon and silicon dioxide. The organic layer 13 is formed of an organic silicon compound represented by chemical formula (1): (RO)Si-(CH)n-Si(OR)or its hydrolyzate and has a contact angle of pure water to the organic layer 13 of 100° or more. In the chemical formula (1), R is an alkyl group, and n is an integer of 1-8.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a gas barrier laminate, a solar cell module using the same, and an image display element.

  For packaging materials used for packaging foods, pharmaceuticals, etc., it is required to prevent the contents from being altered. For example, for food packaging materials, pharmaceutical packaging materials that are required to suppress oxidation and alteration of proteins, fats and oils, and to maintain flavor and freshness, and that require handling in aseptic conditions. Therefore, it is required to suppress the alteration of the active ingredient in the contents and to maintain its efficacy. In addition to packaging applications, materials having gas barrier properties are required for liquid crystal display elements, solar cells, EL substrates, and the like.

  Such alteration of the contents is mainly caused by oxygen or water vapor that permeates the packaging material or other gases that react with the contents. For this reason, packaging materials used for packaging foods and pharmaceuticals are required to have properties (gas barrier properties) that do not allow gas such as oxygen and water vapor to permeate.

  Here, as a material having gas barrier properties, it is known to form a metal oxide thin film on a film substrate to form a gas barrier film substrate. For example, Patent Document 1 was obtained by applying and drying a coating liquid containing an inorganic oxide vapor deposition layer formed by a vacuum vapor deposition method and a water-soluble polymer having a silane compound and a hydroxyl group on a substrate. A gas barrier laminated film in which a gas barrier coating layer is laminated is disclosed.

  However, the vacuum vapor deposition method for forming the inorganic oxide vapor deposition layer is a film formation method involving heat, so that the film is heated to cause partial deformation, and the subsequent formation of the gas barrier coating layer is not uniform. As a result, there was a problem that sufficient barrier ability could not be obtained. In addition, in the process of forming the inorganic oxide vapor deposition layer and the process of forming the gas barrier coating layer, there is a problem that the barrier performance is impaired when foreign matter is mixed.

International Publication No. 2004/048081

  An object of the present invention is to provide a gas barrier laminate that has sufficient barrier performance as a packaging material, a solar battery, and an image display element, and that does not impair the barrier performance even if foreign matter is present.

As a result of repeated examinations about the cause of the deterioration of the barrier performance of the conventional gas barrier film, it became clear that it was caused by the scratch of the barrier layer when the gas barrier film was formed into a roll form. . When the scratch is generated, the thin layer is destroyed and the barrier property is impaired. Based on such examination results, the present inventor suppresses the occurrence of scratches on the thin film formed on the plastic substrate and does not impair the barrier property if the gas barrier film of the present invention has the following configuration. I found that I can do it.

The invention according to claim 1 of the present invention is a gas barrier laminate in which an inorganic gas barrier layer and an organic layer are sequentially laminated on a resin substrate,
The gas barrier layer is formed by vacuum-depositing a deposition material containing metallic silicon and silicon dioxide,
The organic layer is composed of an organosilicon compound represented by the following chemical formula (1) or a hydrolyzate thereof,
A gas barrier laminate, wherein a contact angle of pure water with respect to the organic layer is 100 ° or more.
_{(RO) 3 Si- (CH 2} ) n-Si (OR) 3 (1)
[However, R is an alkyl group, and n is an integer of 1 to 8.]

  The invention according to claim 2 of the present invention is the gas barrier laminate according to claim 1, wherein an anchor coat layer is formed between the resin substrate and the gas barrier layer.

  The invention according to claim 3 of the present invention is a solar cell module comprising the gas barrier laminate according to claim 1 or 2.

  According to a fourth aspect of the present invention, there is provided an image display element comprising the gas barrier laminate according to the first or second aspect.

  The gas barrier film of the present invention does not generate scratches when formed into a roll form, and does not impair gas barrier properties, and can provide a gas barrier laminate that exhibits sufficient gas barrier properties even for solar cell and display device applications.

The schematic sectional drawing of 1st embodiment of the gas-barrier laminated body which concerns on this invention is shown. The schematic sectional drawing of 2nd embodiment of the gas-barrier laminated body which concerns on this invention is shown. The schematic sectional drawing of 3rd embodiment of the gas-barrier laminated body which concerns on this invention is shown.

  Hereinafter, the gas barrier laminate of the present invention will be described with reference to the drawings and embodiments. However, the present invention is not limited to the following embodiments.

<First embodiment>
As shown in FIG. 1, a gas barrier laminate 10 according to the first embodiment of the present invention has a gas barrier layer 12 made of an inorganic substance, an organic layer made of an organosilicon compound or a hydrolyzate thereof on one side of a resin substrate 11. 13 is sequentially laminated.

(Resin substrate 11)
It does not specifically limit as the resin base material 11, It can select suitably from a sheet-like base material (a film-like thing is included). For example, polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefin films such as polyethylene and polypropylene, polyether sulfone (PES), polystyrene film, polyamide film, polyvinyl chloride film, polycarbonate film, polyacrylic Examples include nitrile films, polyimide films, and biodegradable plastic films such as polylactic acid. The resin substrate 11 may contain known additives such as an antistatic agent, an ultraviolet absorber, a plasticizer, a lubricant, and a colorant.

  The thickness of the resin substrate 11 is not particularly limited, but is preferably 6 μm to 700 μm, more preferably 40 μm to 200 μm, and still more preferably 50 μm to 150 μm. Further, in any case, the haze is preferably 3% or less, more preferably 2% or less, further preferably 1% or less, and the total light transmittance is preferably 70% or more, more preferably 80% or more, and further preferably 90%. That's it.

  The resin substrate 11 may be subjected to physical treatment such as corona treatment, plasma treatment, and flame treatment for improving adhesion, and chemical treatment such as chemical treatment with acid or alkali.

(Gas barrier layer 12)
The gas barrier layer (deposition layer) 12 is formed by depositing an inorganic substance, and is not particularly limited. Conventionally, the gas barrier layer (deposition layer) 12 can be appropriately selected from inorganic compounds having gas barrier properties. For example, Si, Al, Zn, Sn, Fe And metals such as Mn and inorganic compounds containing one or more of these metals. Examples of the inorganic compound include metal oxides, nitrides, carbides and fluorides. Among these, at least one selected from metals and metal oxides is preferable.

As a vapor deposition method, a known method such as a physical vapor deposition (PVD) method such as a vacuum vapor deposition method or a sputtering method, or a chemical vapor deposition (PVD) method such as a plasma vapor deposition method may be appropriately used. Among these, vacuum deposition is preferable because high-speed film formation is possible and productivity is excellent. In order to increase the transparency of the vapor deposition layer 12, when vapor deposition material is vapor-deposited, reactive vapor deposition may be performed by reacting with evaporated particles and oxygen gas introduced into the atmosphere. By performing reactive vapor deposition with oxygen gas or argon gas, the metal component in the vapor deposition material is oxidized, and the transparency of the gas barrier layer 12 can be improved. When introducing the gas, it is desirable that the pressure in the film forming chamber be 2 × 10 ⁻¹ Pa or less. If the pressure in the film forming chamber is higher than 2 × 10 ⁻¹ Pa, the gas barrier layer 12 may not be neatly laminated, and the water vapor barrier property may be deteriorated.

  Since the gas barrier layer 12 is particularly excellent in transparency and barrier properties against oxygen gas and water vapor, it is preferable that a vapor deposition material containing metal silicon and silicon dioxide is vacuum-deposited. In the vapor deposition material, the ratio of the content of metal silicon and silicon dioxide is not particularly limited, but the element ratio O / Si between silicon and oxygen is preferably contained at a ratio of 1.0 to 1.8. / Si is more preferably contained at a ratio of 1.2 to 1.7. When O / Si is 1.0 or more, transparency is good, and when O / Si is 1.8 or less, barrier properties are good.

  It is preferable that the vapor deposition material containing metallic silicon and silicon dioxide further contains a metal selected from the group consisting of Al, Zn, Sn, Fe, and Mn (hereinafter, a specific metal) or an oxide thereof. Thereby, a vapor deposition layer having a higher film density can be formed than in the case where a mixture of metal silicon and silicon dioxide is used as a vapor deposition material, and high gas barrier properties are exhibited. Due to the synergistic effect of the vapor deposition layer and the organic layer 13, the gas barrier property of the entire laminate is further improved. The specific metal or oxide thereof contained in the vapor deposition material may be one type or two or more types.

  In the vapor deposition material, the content of the specific metal or its oxide is preferably 1% by mass or more and 50% by mass or less, more preferably 1% by mass or more and 40% by mass or less with respect to 100% by mass of the total of metal silicon and silicon dioxide. 5 mass% or more and 30 mass% or less are more preferable. If it is 1 mass% or more, the effect of improving the film density is sufficiently obtained. If it exceeds 50% by mass, the contents of metal silicon and silicon dioxide are relatively reduced, so that the transparency of the vapor-deposited layer, the barrier property in a moist heat resistant environment, and the like may be lowered. In the vapor deposition material, the remainder other than the specific metal or its oxide is preferably made of metal silicon and silicon dioxide. That is, the total of the specific metal or its oxide, metal silicon, and silicon dioxide is preferably 100% by mass.

  As described above, when a vapor deposition material containing metal silicon and silicon dioxide is vacuum-deposited, a gas barrier layer (deposition layer) made of an inorganic material containing silicon oxide (SiOx) is formed. In addition, when a vapor deposition material containing metal silicon, silicon dioxide, and a specific metal or oxide thereof is vacuum-deposited, a gas barrier layer (vapor deposition layer) made of silicon oxide and an inorganic material containing the specific metal or oxide thereof Is formed.

  The content of silicon oxide in the gas barrier layer 12 is preferably 15 atm% or more, and more preferably 25 atm% or more, as the abundance ratio of Si elements in all elements constituting the vapor deposition layer 12. If it is 25 atm% or more, it is excellent in transparency, barrier properties, and the like. In the gas barrier layer 12, the content of the specific metal or its oxide is preferably 1 atm% or more and 20 atm% or less, preferably 3 atm% or more and 15 atm% or less as the abundance ratio of the specific metal element in all elements constituting the vapor deposition layer 12. More preferred is 3 atm% or more and 10 atm% or less. If it is 1 atm% or more, a high gas barrier property will express. If it exceeds 20 atm%, the content of silicon oxide is relatively reduced, so that the transparency of the gas barrier layer, the barrier property in a moist heat resistant environment, and the like may be reduced.

  The vapor deposition layer in which the abundance ratio of the specific metal element is 1 atm% or more and 20 atm% or less is, for example, a ratio of 1% by mass or more and 50% by mass or less of the specific metal or its oxide with respect to 100% by mass in total of metal silicon and silicon dioxide. It can form by using the vapor deposition material mix | blended with. The kind and abundance ratio of the elements constituting the gas barrier layer (deposition layer) 12 can be measured by an X-ray photoelectron spectrometer (ESCA).

  The film thickness of the gas barrier layer (deposition layer) 12 is preferably 5 nm to 300 nm, and more preferably 10 nm to 150 nm. When the thickness is 5 nm or more, sufficient barrier properties are exhibited, and when the thickness is 300 nm or less, generation of cracks in the post-process and the like, and deterioration of the barrier properties are less likely to occur.

(Organic layer 13)
The organic layer 13 is a coating liquid containing at least one (A) (hereinafter referred to as the component (A)) selected from the group consisting of an organosilicon compound represented by the following chemical formula (1) and a hydrolyzate thereof. It is applied to a basgallia layer (deposition layer) 12 and heat-dried.
_{(RO) 3 Si- (CH 2} ) n-Si (OR) 3 ··· (1)
[However, R is an alkyl group, and n is an integer of 1 to 8.]

  In the chemical formula (1), the alkyl group of R is preferably an alkyl group having 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group.

  In addition, a fluorine-based leveling agent is added to the organic layer 13 which is the outermost layer of the gas barrier laminate of the present invention, and the contact angle with pure water is 100 ° or more. By adding a fluorine-based leveling agent and setting the contact angle with pure water to 100 ° or more, there is no generation of scratches due to friction when forming a roll, and gas barrier properties are not impaired.

  By laminating the organic layer 13 on the gas barrier layer 12, it is possible to obtain excellent gas barrier properties that cannot be achieved with a single gas barrier layer 12. The organic layer 13 also has a function of protecting the dense and fragile gas barrier layer 12, and can suppress the generation of cracks due to rubbing and bending.

In addition, in an organosilicon compound having a Si-OR structure, an OR group bonded to a silicon atom becomes an OH group (hydroxyl group) by a hydrolysis reaction, and a siloxane bond is formed by dehydration condensation of the OH group. By using the organic silicon compound represented by the chemical formula (1), a dense and strong network polymerization film can be formed. Moreover, by having (CH ₂ ) _n in the molecule, an organic-inorganic composite film having both toughness and flexibility is formed. Therefore, as described in Patent Documents 1 and 2, the organic layer sufficiently functions as an organic layer without complexing an organic silicon compound and a water-soluble polymer such as polyvinyl alcohol, and has heat resistance and water resistance. In addition, the moisture resistance and the like are excellent. By synergistically acting, these are considered to exhibit excellent gas barrier properties over a long period even in harsh environments such as outdoors.

  Conjugation with a water-soluble polymer as described in Patent Document 1 is considered to have contributed to a decrease in water resistance and moisture resistance. Therefore, the water resistance and the moisture resistance can be further improved by forming the organic layer 13 without using a water-soluble polymer, or by forming the organic layer 13 by reducing the amount of the organic layer 13 used compared to the conventional one.

  Examples of the organosilicon compound represented by the chemical formula (1) include bistrimethoxysilylmethane, bistrimethoxysilylethane, and bistrimethoxysilylhexane. Examples of the hydrolyzate of the organosilicon compound include those in which at least one of the six ORs in the formula is OH. The hydrolyzate can be prepared by a known method. For example, it can be prepared by dissolving an organosilicon compound in an alcohol such as methanol or isopropyl alcohol, and adding an aqueous solution of an acid such as hydrochloric acid to the solution to cause a hydrolysis reaction.

  (A) A component may be used individually by 1 type, or may use 2 or more types together. The blending amount of the component (A) in the coating liquid can be appropriately set in consideration of barrier properties, durability, suitability for post-processing, and the like, and is not particularly limited, but is preferably 1 to 100% by mass with respect to the total solid content. -90 mass% is more preferable. When it is 1% by mass or more, barrier properties and wet heat durability are good. When it is 90% by mass or less, durability is better.

In addition to the component (A), the coating liquid further includes an organosilicon compound represented by the following chemical formula (b1), an organosilicon compound represented by the following chemical formula (b2), and a hydrolyzate thereof. It is preferable to contain at least one selected from (B) (hereinafter referred to as component (B)).
Si (OR ₁ ) ₄ (b1)
R ₃ —Si (OR ₂ ) ₃ (b2)
[However, R ₁ and R ₂ are alkyl groups, and R ₃ is an organic group having one of an epoxy group and an NCO group. ]

  The component (B) functions as an auxiliary component for the component (A). By further containing the component (B), barrier properties, particularly wet heat resistance, are improved. Among the above, the organosilicon compound represented by the formula (b1) and the hydrolyzate thereof are particularly preferable in terms of barrier properties, and the organosilicon compound represented by the formula (b2) and the hydrolyzate thereof are particularly preferable. It is preferable in terms of wet heat resistance. (B) It is preferable that a component contains at least 1 sort (s) chosen from the organosilicon compound represented by Formula (b2) and its hydrolyzate among the above.

In formula (b1), examples of the alkyl group for R ₁ include the same alkyl groups as those for R. Examples of the organosilicon compound include tetraethoxysilane, tetramethoxysilane, and tetrapropoxysilane. These may be used alone or in combination of two or more. Further, as the hydrolyzate of the four OR ₁ in the formula, at least one include those became OH.

In the formula (b2), examples of the alkyl group for R ₂ include the same alkyl groups as those for R. As the _{R 3,} for example, groups represented by the following chemical formula (b3).
_{X- (CH 2) m- ··· (} b3)
(However, X is a glycidoxy group or an NCO group, and m is an integer of 1 to 8.)

Examples of the organosilicon compound represented by the formula (b2) include those having an epoxy group such as 3-glycidoxypropyltrimethoxysilane and those having an NCO group (isocyanate group) such as 3-isocyanatopropyltriethoxysilane. Etc. In addition, examples of the hydrolyzate include those in which at least one of the three OR _{2 in} the formula is OH.

  The hydrolyzate of the organosilicon compound represented by the formula (b1) or (b2) can be prepared by a known method. For example, it can be prepared by dissolving an organosilicon compound in an alcohol such as methanol or isopropyl alcohol, and adding an aqueous solution of an acid such as hydrochloric acid to the solution to cause a hydrolysis reaction.

  (B) A component may be used individually by 1 type, or may use 2 or more types together. The amount of component (B) in the coating solution is preferably such that the sum of component (A) is 1 to 100% by mass relative to the total solid content. Further, the ratio (B) / (A) of the component (B) to the component (A) in the coating solution is preferably 1/100 to 100/1, more preferably 1/10 to 10/1, in terms of mass ratio. The effect which mix | blends (B) component is fully acquired as it is 1/100 or more. If it exceeds 10/1, the proportion of the component (A) is relatively low, so that flexibility, barrier properties and the like may be lowered.

In addition to the component (A) or in addition to the component (A) and the component (B), the coating liquid further includes an acrylic polyol (C) having two or more OH groups (hereinafter referred to as the component (C). ) And an isocyanate compound (D) having at least two NCO groups in the molecule (hereinafter referred to as component (D)) or both. This
A homogeneous organic-inorganic composite can be formed, and resistance to long-term storage under high temperature and high humidity is further improved.

  Compared with the case where only the organosilicon compound is used, the effect of improving the gas barrier property due to the interaction with the vapor deposition layer 12 is further enhanced, and the swelling deterioration of the organic layer 13 in a high-temperature and high-humidity atmosphere or a hot water atmosphere is caused. It is suppressed. Furthermore, the deterioration of the protective function with respect to the vapor deposition layer 12 is suppressed, and excellent gas barrier properties can be maintained for a long time even in those atmospheres.

  For example, the component (C) is compatible with a polymer formed by polymerization of a hydrolyzate of an organosilicon compound represented by the formula (a), (b1) or (b2). The effect of improving gas barrier properties is exhibited by combining with coalescence.

  Moreover, (D) component reacts with the Si-OH group formed by hydrolysis of the organosilicon compound represented by the formula (a), (b1) or (b2) to form a urethane bond. Furthermore, when both (C) component and (D) component are used together, the OH group of (C) component reacts with the NCO group of (D) component to form a urethane bond. Therefore, a composite cross-linked structure is formed by a urethane bond in addition to the siloxane bond, and an excellent gas barrier property improving effect is obtained.

As component (C), a polymer compound obtained by polymerizing an (OH) group-containing (meth) acrylic acid derivative monomer, an OH group-containing (meth) acrylic acid derivative monomer and other monomers are copolymerized. And high molecular compounds that can be used. In the present specification, “(meth) acrylic acid derivative” includes (meth) acrylic acid in addition to those obtained by changing a part of the structure of (meth) acrylic acid (for example, (meth) acrylic acid ester). It is intended to include itself. Examples of the (meth) acrylic acid derivative monomer having an OH group include hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate and hydroxybutyl (meth) acrylate.

Moreover, as another monomer copolymerizable with the (meth) acrylic acid derivative monomer which has OH group, the (meth) acrylic acid derivative monomer which does not have OH group is preferable. Examples of (meth) acrylic acid derivative monomers having no OH group include (meth) acrylic acid derivative monomers having an alkyl group, (meth) acrylic acid derivative monomers having a carboxyl group, and (meth) acrylic having a ring structure. Examples include acid derivative monomers.
Examples of (meth) acrylic acid derivative monomers having an alkyl group include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and t-butyl (meth) acrylate. Is mentioned.
Examples of the (meth) acrylic acid derivative monomer having a carboxyl group include (meth) acrylic acid.
Examples of the (meth) acrylic acid derivative monomer having a ring structure include benzyl (meth) acrylate and cyclohexyl (meth) acrylate.
As other monomers, monomers other than (meth) acrylic acid derivative monomers may be used. Examples of the monomer include styrene monomer, cyclohexylmaleimide monomer, and phenylmaleimide monomer.
Monomers other than the (meth) acrylic acid derivative monomer may have an OH group.

  The component (C) preferably has an OH group value of 50 to 250 mgKOH / g. The hydrolyzate of the organosilicon compound represented by the general formula (a) and the hydrolyzate of the organosilicon compound represented by the general formula (b1) or (b2) are polymers having a high OH group content. Form. When the OH group value of the component (C) is within the above range, the compatibility with the polymer is excellent. The OH group value (mgKOH / g) is an index of the amount of OH groups in the acrylic polyol, and indicates the number of mg of potassium hydroxide necessary for acetylating the hydroxyl group in 1 g of the acrylic polyol.

  Although the weight average molecular weight of (C) component is not prescribed | regulated, 3000 or more and 200,000 or less are preferable, 5000 or more and 100,000 or less are more preferable, and 5000 or more and 40000 or less are more preferable. In addition, the weight average molecular weight of (C) component is measured by GPC (gel permeation chromatography) on the basis of polystyrene.

(C) A component may be used individually by 1 type, or may use 2 or more types together.
5-50 mass% is preferable with respect to the total solid, and, as for the compounding quantity of (C) component in a coating liquid, 10-25 mass% is more preferable. The effect which mix | blends (C) component is fully acquired as it is 5 mass% or more. If it exceeds 50% by mass, the barrier property may be lowered.

  As the component (D), any compound having at least two NCO groups in the molecule may be used. Fragrances such as aliphatic isocyanates such as methylene diisocyanate (HDI), bisisocyanate methylcyclohexane (H6XDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (H12MDI), xylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI) Aliphatic isocyanates and the like can be mentioned. Also, polymers or derivatives of these monomeric isocyanates can be used. Examples of the polymer or derivative include a trimer nurate type, an adduct type reacted with 1,1,1-trimethylolpropane and the like, a biuret type reacted with biuret, and the like.

  The component (D) may be arbitrarily selected from the above-mentioned monomeric isocyanates, polymers thereof, derivatives, and the like, and may be used alone or in combination of two or more. 5-50 mass% is preferable with respect to the total solid, and, as for the compounding quantity of (D) component in a coating liquid, 10-30 mass% is more preferable. The effect which mix | blends (D) component is fully acquired as it is 5 mass% or more. If it exceeds 50 mass%, the barrier property may be lowered.

  The coating liquid which forms the organic layer 13 can be prepared by mixing (A) component, arbitrary components ((B)-(D) component), and a solvent. Any solvent may be used as long as it can dissolve the compounding components, and examples thereof include water, alcohol, toluene, ethyl acetate, acetone, and methyl ethyl ketone. These solvents can be used alone or in combination of two or more. About (A) component and (B) component, when mix | blending a hydrolyzate, you may use the hydrolysis liquid obtained by hydrolyzing beforehand.

  The organic layer 13 can be formed by applying the coating solution on the vapor deposition layer 12 and drying by heating. As a coating method of the coating solution, a normal coating method can be used. For example, known methods such as a dipping method, a roll coating method, a gravure coating method, a reverse coating method, an air knife coating method, a comma coating method, a die coating method, a screen printing method, a spray coating method, and a gravure offset method can be used. Moreover, the drying method can use the method of applying heat, such as hot air drying, hot roll drying, high frequency irradiation, infrared irradiation, and UV irradiation, or one or a combination of two or more. The heating temperature is preferably 60 to 200 ° C, more preferably 100 to 150 ° C. When it is 60 ° C. or higher, desired barrier properties are exhibited, which is good. If it is 150 degreeC or less, if it is a vapor deposition short time, it will be suitable, without a deformation | transformation of a base material and a crack generating in a vapor deposition film.

  The film thickness of the organic layer 13 is preferably 0.1 to 2 μm, and more preferably 0.2 to 1.0 μm. When it is 0.1 μm or more, the barrier property is stably expressed, and when it is 1 μm or less, it is excellent in post-processing suitability such as printing or lamination of other films or bending.

<Second Embodiment>
Next, a second embodiment according to the present invention will be described with reference to FIG.
The gas barrier laminate 20 is a laminate having a configuration in which the anchor coat layer 24, the vapor deposition layer 12, and the organic layer 13 are sequentially laminated on one surface of the resin base material 11. The gas barrier laminate 20 has the same configuration as the gas barrier laminate 10 of the first embodiment except that an anchor coat layer 24 is provided between the resin base material 11 and the vapor deposition layer 12. In addition, the same code | symbol is attached | subjected to the component corresponding to 1st embodiment, and the detailed description is abbreviate | omitted.

(Anchor coat layer 24)
The anchor coat layer 24 enhances the adhesion between the resin base material 11 and the vapor deposition layer 12 on the resin base material 11, and various sterilization treatments such as boil sterilization and retort sterilization, and occurrence of peeling of the vapor deposition layer 12 by long-term outdoor installation. And provided to prevent the gas barrier property from deteriorating.
The anchor coat layer 24 has an acrylic polyol (1) having two or more OH groups and at least two NCO groups in the molecule from the viewpoint of improving the adhesion between the resin substrate 11 and the vapor deposition layer 12. It is preferably formed using an anchor coating agent containing an isocyanate compound (2).

As the acrylic polyol (1), a polymer compound obtained by polymerizing a (meth) acrylic acid derivative monomer having an OH group, a (meth) acrylic acid derivative monomer having an OH group and another monomer are copolymerized. Examples thereof include a polymer compound obtained.
Examples of the (meth) acrylic acid derivative monomer having an OH group include hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate and hydroxybutyl (meth) acrylate.

As the other monomer copolymerizable with the (meth) acrylic acid derivative monomer having an OH group, a (meth) acrylic acid derivative monomer having no OH group is preferable. Examples of (meth) acrylic acid derivative monomers having no OH group include (meth) acrylic acid derivative monomers having an alkyl group, (meth) acrylic acid derivative monomers having a carboxyl group, and (meth) acrylic having a ring structure. Examples include acid derivative monomers.
Examples of (meth) acrylic acid derivative monomers having an alkyl group include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and t-butyl (meth) acrylate. Is mentioned.
Examples of the (meth) acrylic acid derivative monomer having a carboxyl group include (meth) acrylic acid.
Examples of the (meth) acrylic acid derivative monomer having a ring structure include benzyl (meth) acrylate and cyclohexyl (meth) acrylate.
As other monomers, monomers other than (meth) acrylic acid derivative monomers may be used. Examples of the monomer include styrene monomer, cyclohexylmaleimide monomer, and phenylmaleimide monomer.
Monomers other than the (meth) acrylic acid derivative monomer may have an OH group.

  The acrylic polyol (1) preferably has an OH group value of 50 to 250 mgKOH / g. The OH group value (mgKOH / g) is an indicator of the amount of OH groups in the acrylic polyol as described above, and represents the number of mg of potassium hydroxide required for acetylating the hydroxyl group in 1 g of the acrylic polyol. Show.

  When the OH group value is less than 50 mgKOH / g, the reaction amount with the isocyanate compound (2) is small, and the effect of improving the adhesion between the resin substrate 11 and the vapor deposition layer 12 by the anchor coat layer 24 may not be sufficiently exhibited. There is. On the other hand, if the OH group value is larger than 250 mgKOH / g, the amount of reaction with the isocyanate compound (2) increases so that the shrinkage of the anchor coat layer 24 may increase. If the film shrinkage is large, the deposited layer 12 is not neatly laminated thereon, and there is a possibility that sufficient gas barrier properties are not exhibited.

  The weight average molecular weight of the acrylic polyol (1) is not particularly defined, but is preferably 3000 or more and 200000 or less, more preferably 5000 or more and 100000 or less, and further preferably 5000 or more and 40000 or less. The weight average molecular weight of the acrylic polyol (1) is measured in the same manner as the weight average molecular weight of the component (C). Acrylic polyol (1) may be used individually by 1 type, or may use 2 or more types together.

The isocyanate compound (2) may be any compound having at least two NCO groups in the molecule. Examples of the monomeric isocyanate include aromatic isocyanates such as tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI), Hexamethylene diisocyanate (HDI), bisisocyanate methylcyclohexane (H6XDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (H12MDI) and other aliphatic isocyanates, xylene diisocyanate (XDI), tetramethylxylylene diisocyanate (TMXDI), etc. Examples include aromatic aliphatic isocyanates. Also, polymers or derivatives of these monomeric isocyanates can be used. Examples of the polymer or derivative include a trimer nurate type, an adduct type reacted with 1,1,1-trimethylolpropane and the like, a biuret type reacted with biuret, and the like.
As an isocyanate compound (2), you may select arbitrarily from said monomeric isocyanate, its polymer, a derivative, etc., and can be used individually by 1 type or in combination of 2 or more types.

  In the anchor coating agent, the equivalent ratio (NCO / OH) of the NCO group of the isocyanate compound (2) to the OH group of the acrylic polyol (1) is preferably 0.15 to 0.75, preferably 0.25 to 0 .60 is more preferable. When NCO / OH is 0.15 or more, the adhesion to the substrate is improved, and when it is 0.75 or less, the adhesion after the wet heat resistance test is improved. The blending amount of the acrylic polyol (1) and the isocyanate compound (2) in the anchor coating agent is preferably blended based on the equivalent ratio, and the isocyanate compound (2) is generally based on 100 parts by mass of the acrylic polyol (1). It is preferably 10 to 90 parts by mass, and more preferably 20 to 80 parts by mass.

  The anchor coating agent may further contain a silane coupling agent in order to further improve the adhesion between the resin substrate 11 and the vapor deposition layer 12. For example, those having an epoxy group such as 3-glycidoxypropyltrimethoxysilane, those having an amino group such as 3-aminopropyltrimethoxysilane, those having a mercapto group such as 3-mercaptopropyltrimethoxysilane, -What has isocyanate groups, such as isocyanate propyl triethoxysilane, etc. are mentioned. As the silane coupling agent, one kind may be used alone, or two or more kinds may be used in combination.

  The anchor coating agent can be prepared by mixing an acrylic polyol (1), an isocyanate compound (2), an optional component (such as a silane coupling agent), and a solvent. Any solvent may be used as long as it can dissolve the acrylic polyol (1) and the isocyanate compound (2). Examples thereof include methyl acetate, ethyl acetate, butyl acetate, methyl ethyl ketone, dioxolane, tetrahydrofuran, cyclohexanone, and acetone. These solvents can be used alone or in combination of two or more.

  The anchor coat layer 24 can be formed by applying the anchor coat agent on the resin substrate 11 and drying it by heating. As a coating method, a normal coating method can be used. For example, known methods such as a dipping method, a roll coating method, a gravure coating method, a reverse coating method, an air knife coating method, a comma coating method, a die coating method, a screen printing method, a spray coating method, and a gravure offset method can be used. Moreover, as a drying method, the method of applying heat, such as hot air drying, hot roll drying, high frequency irradiation, infrared irradiation, and UV irradiation, can be used alone or in combination of two or more. The heating temperature is not particularly limited, but is preferably 60 to 140 ° C., and can be appropriately selected under such conditions that there is no residual solvent and there is no so-called blocking phenomenon in which the coated surface sticks to the back surface even after winding. You may perform an aging process at 40-60 degreeC as needed.

  The film thickness of the anchor coat layer 24 is preferably 0.02 μm or more and 1.0 μm or less, and more preferably 0.04 μm or more and 0.5 μm or less. Adhesiveness of the resin base material 11 and the vapor deposition layer 12 becomes fully favorable as it is 0.02 micrometer or more. If it is thicker than 0.5 μm, the influence of internal stress becomes large, and the vapor deposition layer 12 is not neatly laminated, and there is a risk that the expression of gas barrier properties will be insufficient.

<Third embodiment>
Next, a third embodiment according to the present invention will be described with reference to FIG.
The gas barrier laminate 30 has an anchor coat layer 24, a vapor deposition layer 12, an organic layer 13, an adhesive layer 31, and a laminate resin layer 32 sequentially laminated on one surface of the resin base material 11. This is a laminate having a configuration in which an adhesive layer 33 and a laminate resin layer 34 are sequentially laminated on the surface. The gas barrier laminate 30 has a configuration in which laminate resin layers 32 and 34 are laminated on both surfaces of the gas barrier laminate 20 of the second embodiment via adhesive layers 31 and 33, respectively. Constituent elements corresponding to the second embodiment are denoted by the same reference numerals, and detailed description thereof is omitted.

  The gas barrier laminate 30 can be highly practical by selecting the material of the laminate resin layers 32 and 34. For example, by using a sealant film made of a heat-sealable resin for both of the laminate resin layers 32 and 34, the gas barrier laminate 30 is used as an adhesive part when forming a bag-like package or the like. can do. Examples of the resin constituting the sealant film include polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-acrylic acid copolymer, ethylene- Examples thereof include acrylic acid ester copolymers and their metal cross-linked products. The thickness of the sealant film is determined according to the purpose, but is generally in the range of 15 μm to 200 μm.

  A sealant film may be used for either one of the laminate resin layers 32 and 34, and a resin film other than the sealant film may be used for the other. Alternatively, a laminate resin layer may be laminated only on one side of the gas barrier laminate 20 via an adhesive layer. In other words, any one of the adhesive layer 31, the laminate resin layer 32, the adhesive layer 33, and the laminate resin layer 34 may be omitted.

  Further, by using a polyethylene terephthalate film or a polyethylene naphthalate film as the laminate resin layers 32 and 34, the gas barrier laminate 30 can be used for a liquid crystal display element, a solar cell, an electromagnetic wave shield, a transparent conductive sheet used for a touch panel, or the like. It can also be used as a sealing material.

  The gas barrier laminate 30 can be produced by laminating laminate resin layers 32 and 34 on both surfaces of the gas barrier laminate 20 via adhesive layers 31 and 33, respectively. The lamination resin layers 32 and 34 can be laminated by a known laminating method, and examples thereof include dry lamination using an adhesive and extrusion molding using a heat-adhesive resin. In the case of dry lamination using an adhesive, the adhesive becomes the adhesive layers 31 and 33, and in the case of extrusion molding using a thermal adhesive resin, the thermal adhesive resin becomes the adhesive layers 31 and 33.

  The gas barrier laminate of the present invention has been described with reference to the embodiment. However, the specific configuration of the present invention is not limited to the contents of the above-described embodiment, and does not depart from the spirit of the present invention. Any changes in the design of the range are included in the present invention. The gas barrier laminate of the present invention may be plate-shaped or film-shaped. For example, it may be formed into a film shape by winding with a roll or the like.

  Hereinafter, the present invention will be described in more detail with reference to examples.

<Example 1>
Acrylic polyol (weight average molecular weight of about 10,000) was obtained by copolymerization using hydroxyethyl methacrylate (HEMA) and methyl methacrylate (MMA) so that the OH group value was 178 mgKOH / g.

  Next, as an anchor coating agent, the acrylic polyol obtained above is used as a main agent, and hexamethylene diisocyanate (HDI) as a curing agent is blended so as to be 0.5 equivalent to the amount of OH groups of the main agent, A methyl ethyl ketone solution having a solid content of 5% by mass was prepared.

  Next, the anchor coating agent is applied to the corona-treated surface of a 100 μm-thick PEN film (Dupont-Teijin Q65A) with one side corona-treated, and the thickness after drying is 0.15 μm using a gravure coater. After that, the film was stored in a thermostatic chamber at 50 ° C. for 48 hours and subjected to an aging treatment to form an anchor coat layer.

  Next, a metal tin powder is further added to the material obtained by mixing the metal silicon powder and the silicon dioxide powder so that the element ratio O / Si is 1.5 by using a vacuum vapor deposition machine on the anchor coat layer. The vapor deposition material (B) mixed by mass% was vapor-deposited to form a vapor deposition layer (SiOx-Sn composite vapor deposition film) having a thickness of 50 nm.

  As a coating solution for forming an organic layer, a hydrolyzed solution of bistrimethoxysilylethane (a 4-fold molar equivalent of bistrimethoxysilylethane as water using 0.001N hydrochloric acid) and glycidoxypropyltrimethoxysilane And bistrimethoxysilylethane: glycidoxypropyltrimethoxysilane = 80: 20 (molar ratio), and diluted with IPA to prepare a solution having a solid content of 5% by mass.

  Next, the coating liquid for forming the organic layer was applied on the vapor deposition layer, and heat drying was performed at 120 ° C. for 2 minutes to form an organic layer having a thickness of 1 μm.

  Furthermore, the process of forming the previous vapor deposition layer on the organic layer was repeated twice to produce a gas barrier laminate having three vapor deposition layers and three organic layers. In addition, a fluorine-based leveling agent (DIC Megafac RS-75) was added to the third layer (outermost layer) of the organic layer in a weight ratio of 0.02 with respect to the coating solution for forming the organic layer.

<Comparative Example 1>
A gas barrier laminate was produced in the same manner as in Example 1 except that the leveling agent was not added to the coating solution for forming the organic layer for forming the third layer (outermost layer) of the organic layer.

<Comparative example 2>
Gas barrier properties in the same manner as in Example 1 except that a silicon-based leveling agent (Big Chemy BYK3570) was added as a leveling agent to the coating solution for forming the organic layer for forming the third layer (outermost layer) of the organic layer. A laminate was produced.

<Comparative Example 3>
Gas barrier properties in the same manner as in Example 1 except that a silicon-based leveling agent (Big Chemy BYK3530) was added as a leveling agent to the coating solution for forming the organic layer for forming the third layer (outermost layer) of the organic layer. A laminate was produced.

<Evaluation method>
About the gas-barrier laminated body obtained by the Example and the comparative example, the contact angle, the abrasion, and the water vapor transmission rate were evaluated by the method described below. The results are shown in Table 1 below.

(Contact angle measurement)
Measurement was performed according to JIS R3257. The previous JIS was a method for measuring the contact angle with respect to the substrate glass surface, and the contact angle between pure water and the outermost layer of the barrier film was determined by replacing the base material with the barrier film of this example.

(Existence of scratches)
The roll shape was unwound and the presence or absence was visually determined.

(Measurement of water vapor permeability)
Water vapor permeability meter (MOCON PERMATRAN-W manufactured by Modern Control)
3/31), water vapor permeability [g / m ² · day] in an atmosphere of 40 ° C.-90% RH was measured.

From Example 1, the contact angle between the outermost organic layer and pure water was 100 ° or more by adding a fluorine-based leveling agent to the outermost organic layer. Moreover, there was no abrasion and the water vapor permeability was 0.03 g / m ² · day.

From Comparative Example 1, in the system in which the leveling agent was not added to the outermost organic layer, the contact angle between the outermost organic layer and pure water was less than 90 °. As a result, scratches were confirmed in the organic layer, and the water vapor permeability was 0.3 g / m ² · day.

From Comparative Examples 2 and 3, in the system in which a silicon leveling agent was added to the outermost organic layer, the contact angle between the outermost organic layer and pure water was less than 100 °. As a result, scratches were confirmed in the organic layer, and the water vapor permeability was 0.3 g / m ² · day.

  From the evaluation results of Example 1 and Comparative Examples 1 to 3, the contact angle between the outermost organic layer and pure water is set to 100 ° or more, thereby reducing the friction between the base material and the organic layer and suppressing the generation of scratches. Further, it is presumed that the water vapor permeability maintains a low value.

  ADVANTAGE OF THE INVENTION According to this invention, the gas barrier laminated body which does not generate | occur | produce the abrasion at the time of making it a roll form, does not impair gas barrier property, and exhibits sufficient gas barrier property also in a solar cell or a display element use can be provided.

10 Gas barrier laminate 11 Resin substrate 12 Gas barrier layer (deposition layer)
13 Organic layer 20 Gas barrier laminate 24 Anchor coat layer 30 Gas barrier laminate 31 Adhesive layer 32 Laminate resin layer 33 Adhesive layer 34 Laminate resin layer

Claims (4)

A gas barrier laminate in which a gas barrier layer made of an inorganic material and an organic layer are sequentially laminated on a resin substrate,
The gas barrier layer is formed by vacuum-depositing a deposition material containing metallic silicon and silicon dioxide,
The organic layer is composed of an organosilicon compound represented by the following chemical formula (1) or a hydrolyzate thereof,
A gas barrier laminate, wherein a contact angle of pure water with respect to the organic layer is 100 ° or more.
_{(RO) 3 Si- (CH 2} ) n-Si (OR) 3 (1)
[However, R is an alkyl group, and n is an integer of 1 to 8.]   The gas barrier laminate according to claim 1, wherein an anchor coat layer is formed between the resin substrate and the gas barrier layer.   A solar cell module comprising the gas barrier laminate according to claim 1.   An image display element comprising the gas barrier laminate according to claim 1.