TW201514018A - Electronic device - Google Patents

Abstract

This electronic device is provided with an electronic device body, and a protective sheet that protects the surface of the electronic device body. The protective sheet comprises a multilayer structure having at least one of each of a substrate (X), a layer (Y) and a layer (Z). The layer (Y) contains aluminum atoms. The layer (Z) contains a polymer (E) containing monomeric units having phosphorus atoms. In at least one set of the layer (Y) and the layer (Z), said layers are laminated adjacent to one another. The electronic device is suitable for maintaining gas barrier properties of the protective sheet at a high level even when subjected to physical stress.

Description

Electronic device

The present invention relates to an electronic device having a protective sheet.

The protective member disposed on the surface of the electronic device is required to be detrimental to the characteristics of the electronic device. With the advent of electronic devices that can meet the requirements for thinning and light weight, a thin protective sheet using a multilayer structure has been developed as a substitute for a thicker protective member represented by a glass plate. One of the characteristics required for the protective sheet is a gas barrier. When a gas barrier property is required, the constituent material of the protective sheet is a multilayered structure in which gas barrier properties are improved.

A multilayer structure having a gas barrier property, for example, a multilayered structure including a transparent gas barrier film containing a reaction product of an alumina particle and a phosphorus compound (Patent Document 1: International Publication No. 2011-) is known. No. 122036). This transparent gas barrier film is formed by applying a coating liquid containing alumina particles and a phosphorus compound onto a substrate.

Patent Document 1: International Publication No. 2011-122036

However, the above-mentioned conventional multilayer structure is excellent in gas barrier properties in the initial stage, but when subjected to physical stress such as deformation or punching, the gas barrier film may have defects such as cracks and pinholes. There is no way to ensure gas barriers for a long time. Sexual situation. The multilayer structure for the protective sheet of an electronic device is subjected to various physical stresses not only in the manufacturing stage and the distribution stage of the electronic device, but also in a long period of use. Therefore, an electronic device is required to maintain the gas barrier property of the multilayered structure at a high level even under physical pressure.

SUMMARY OF THE INVENTION An object of the present invention is to provide an electronic device which is suitable for maintaining a gas barrier property of a multilayered structure at a high level even under physical pressure.

An electronic device according to the present invention includes an electronic device body and a protective sheet for protecting a surface of the electronic device body, wherein the protective sheet includes a plurality of layers each having a base material (X), a layer (Y), and a layer (Z) In the structure, the layer (Y) contains an aluminum atom, and the layer (Z) contains a polymer (E), and at least one of the layers (Y) and the layer (Z) are laminated adjacent to each other, and the polymer (E) Contains monomer units with phosphorus atoms.

In the electronic device of the present invention, the substrate (X), the layer (Y), and the layer (Z) may be at least one set of the substrate (X) / the layer (Y) / The layers (Z) are sequentially laminated.

In the electronic device of the present invention, the polymer (E) may be a single polymer or copolymer of a (meth) acrylate having a phosphate group at the terminal of the side chain.

In the electronic device of the present invention, the polymer (E) may be a single polymer of acid phosphoxy ethyl (meth) acrylate.

In the electronic device of the present invention, the polymer (E) may have a repeating unit represented by the following formula (I).

[In the formula (I), n represents a natural number].

In the electronic device of the present invention, the layer (Y) may be a layer (YA) containing a reaction product (R). The reaction product (R) is a reaction product obtained by reacting an aluminum-containing metal oxide (A) with a phosphorus compound (B), and the infrared absorption spectrum of the layer (YA) is in the range of 800 to 1400 cm ^-1 . The maximum wave number (n ¹ ) of infrared absorption can be in the range of 1080 to 1130 cm ^-1 .

In the electronic device of the present invention, the layer (Y) may be an aluminum vapor deposited layer (YB) or an aluminum oxide deposited layer (YC).

In the electronic device of the present invention, the substrate (X) may include at least one selected from the group consisting of a thermoplastic resin film layer, a paper layer, and an inorganic vapor deposition layer.

In the electronic device of the present invention, the protective sheet may have an oxygen permeability of 2 ml/(m ² ‧day‧atm) or less at 20 ° C and 85% RH.

In the electronic device of the present invention, the protective sheet is held in a state of 5% stretching in a state of 5% at 23 ° C and 50% RH for 5 minutes, and then the multilayer structure is at 20 ° C, 85% RH. The oxygen permeability measured under the conditions may be 4 ml/(m ² ‧day‧atm) or less.

The electronic device of the present invention may be a photoelectric conversion device, an information display device, or a lighting device.

In the electronic device of the present invention, the protective sheet may have flexibility. In the present specification, the term "having flexibility" means that the outer peripheral side surface of the cylindrical core material having an outer diameter of 30 cm can be wound to form a wound body, and the object to be wound is not caused by the winding. (eg protective sheet) broken damage.

The present invention can obtain an electronic device which is suitable for maintaining the gas barrier properties of a multilayered structure at a high level even under physical pressure.

1‧‧‧Electronic device body

2‧‧‧ Sealing material

3‧‧‧Protection film

10‧‧‧Electronic devices

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing a state of an electronic device of the present invention.

Hereinafter, an embodiment of the present invention will be described. Further, in the following description, although a material exhibiting a specific function is exemplified as a specific material (a compound or the like), the present invention is not limited to the use of the material. In addition, the exemplified materials are used singly or in combination of two or more kinds, unless otherwise specified.

[electronic device]

The electronic device is provided with an electronic device body and a protective sheet for protecting the surface of the electronic device body.

One form of the electronic device of the present invention is shown in FIG. The electronic device 10 includes an electronic device body 1 and a sealing material 2 for sealing the electronic device body 1 and a protective sheet 3 for protecting the surface of the electronic device body 1. The sealing material 2 is covered with the entire surface of the electronic device body 1. The protective sheet 3 is disposed on one surface of the electronic device body 1 by the sealing member 2. Although not shown in the drawings, a protective sheet may be disposed on the surface opposite to the surface on which the protective sheet 3 is disposed. However, the surface on the opposite side may be provided with other protective members different from the protective sheet 3.

The electronic device body 1 is not particularly limited, and is, for example, a photoelectric conversion device such as a solar cell, an organic EL display, an information display device such as a liquid crystal display or an electronic paper, or an illumination device such as an organic EL light-emitting device. The sealing material 2 is adapted to the type and use of the electronic device body 1 When attaching any component. As the sealing material 2, EVA (ethylene-vinyl acetate resin), PVB (polyvinyl butyral), or the like is used. The protective sheet 3 may be disposed so as to be able to protect the surface of the electronic device body 1 and may be disposed directly on the surface of the electronic device body 1 or may be disposed on the surface of the electronic device body 1 by other members such as the sealing member 2 .

The electronic device body 1, typically a solar cell. Examples of solar cells include lanthanide solar cells, compound semiconductor solar cells, organic solar cells, and the like. Examples of the tantalum solar cell include a single crystal germanium solar cell, a polycrystalline germanium solar cell, an amorphous germanium solar cell, and the like. Examples of the compound semiconductor solar cell include a III-V compound semiconductor solar cell, a II-VI compound semiconductor solar cell, an I-III-VI compound semiconductor solar cell, and the like. Further, the solar cell may be an integrated solar cell in which a plurality of unit cells are connected in series, or may be a non-integrated solar cell.

The electronic device body 1 can be manufactured by a so-called roll to roll method depending on the type thereof. In the roll-to-roll method, a flexible substrate (for example, a stainless steel substrate or a resin substrate) that is wound into a feed roller is fed out, and an element is formed on the substrate to form an electronic device body 1. The electronic device body 1 is wound by a roll. take. In this case, the shape of the long sheet in which the protective sheet 3 is also flexible (having flexibility) may be prepared in advance, and more specifically, the shape of the wound body of the long sheet. The protective sheet 3 fed from the delivery roller is laminated on the electronic device body 1 which is taken up before the take-up roller, and is taken up together with the electronic device body 1. Alternatively, the electronic device body 1 that has been taken up by the take-up roll may be additionally taken out from the roll and laminated with the protective sheet 3. A preferred embodiment of the invention is that the electronic device itself has flexibility.

The protective sheet 3 contains a multilayer structure which will be described below. The protective sheet 3 may be composed only of a multilayered structure, and may be further laminated with members other than the multilayered structure. Protective sheet 3 If it is suitable for protecting a layered laminate of the surface of an electronic device and contains the following multilayer structure, the thickness and material thereof are not particularly limited.

[multilayer structure]

The multilayer structure system has a multilayer structure of one or more layers of a substrate (X), a layer (Y) and a layer (Z), the layer (Y) contains an aluminum atom, and the layer (Z) contains a polymer (E), at least one group The layer (Y) is laminated adjacent to the layer (Z), and the polymer (E) contains a monomer unit having a phosphorus atom. This multilayered structure is excellent in suppressing the property of the gas barrier property of the film due to physical stress (hereinafter sometimes referred to as "bending resistance").

[layer (Y)]

The layer (Y) of the multilayered structure may also be a layer (YA) containing a reaction product obtained by reacting at least an aluminum-containing metal oxide (A) with a phosphorus compound (B) ( R). Alternatively, the layer (Y) may be a layer of a vapor deposited layer of aluminum (hereinafter sometimes referred to as "layer (YB)") or a vapor deposited layer of alumina (hereinafter sometimes referred to as "layer (YC)"). The following is explained in order.

[layer (YA)]

When the layer (Y) of the multilayer structure is the above layer (YA), in the infrared absorption spectrum of the layer (YA), the maximum absorption of infrared rays (n ¹ ) in the range of 800 to 1400 cm ^-1 is in 1080. ~1130cm ^-1 range.

Hereinafter, the wave number (n ¹ ) is referred to as a "maximum absorption wave number (n ¹ )". The metal oxide (A) is usually reacted with the phosphorus compound (B) in the form of metal oxide (A) particles.

Typically, the layer (YA) of the multilayer structure has a structure in which metal oxide (A) particles are bonded to each other via a phosphorus atom derived from the phosphorus compound (B). via The type of phosphorus atom bonding includes a type bonded via an atomic group containing a phosphorus atom, and includes a type bonded, for example, via a group containing a phosphorus atom and containing no metal atom.

In the layer (YA) of the multilayered structure, the number of moles of the metal atom to which the metal oxide (A) particles are bonded to each other and the metal atom not derived from the metal oxide (A) is to cause the metal oxide ( A) The range of 0 to 1 times the molar number of the phosphorus atoms to which the particles are bonded to each other (for example, in the range of 0 to 0.9 times) is preferably, for example, 0.3 times or less, 0.05 times or less, 0.01 times or less, or 0 times.

The layer (YA) which the multilayer structure has may also partially contain the metal oxide (A) and/or the phosphorus compound (B) which do not participate in the reaction.

In general, when a metal compound reacts with a phosphorus compound to form a bond represented by MOP, a characteristic peak is generated in an infrared absorption spectrum, and the bond represented by MOP constitutes a metal atom (M) of a metal compound and is derived from phosphorus. The phosphorus atom (P) of the compound is bonded via an oxygen atom (O). Here, the characteristic peak exhibits an absorption peak at a specific wave number depending on the environment, structure, and the like around the bond. As a result of review by the present inventors, it was found that when the absorption peak based on the MOP bond is in the range of 1080 to 1130 cm ^-1 , the obtained multilayer structure exhibits excellent gas barrier properties. And it is understood that, especially when the absorption peak exhibits an absorption peak of the maximum absorption wave number in a region of 800 to 1400 cm ^{-1 which} usually sees absorption of various atoms and oxygen atoms, the obtained multilayer structure exhibits More excellent gas barrier properties.

Further, although the invention is not limited in any way, it is inferred that when the metal oxide (A) particles are bonded to each other via a phosphorus atom derived from the phosphorus compound (B) and not via a metal atom not derived from the metal oxide (A), And a bond represented by MOP is formed (the bond represented by the MOP is formed by bonding a metal atom (M) constituting the metal oxide (A) and a phosphorus atom (P) via an oxygen atom (O)). Because of the relatively fixed environment on the surface of the metal oxide (A) particles, in the infrared absorption spectrum of the layer (YA), the absorption peak based on the MOP bond will be maximally absorbed in the region of 800 to 1400 cm ^-1 . absorption peak form appeared in the wave number range of 1080 ~ 1130cm ^-1.

On the other hand, when a metal compound in which a metal oxide such as a metal alkoxide or a metal salt is not formed and a phosphorus compound (B) are previously mixed and then hydrolyzed and condensed, it is obtained from A composite in which a metal atom of a metal compound is substantially uniformly mixed with a phosphorus atom derived from a phosphorus compound (B), and the maximum absorption wave number (n ¹ ) in the range of 800 to 1400 cm ^-1 is not in the infrared absorption spectrum. ~1130cm ^-1 range.

Becomes more excellent in terms of aspects of the multilayer structure of gas barrier property, the maximum number (n ¹⁾ is preferably in the range of absorption wavelength 1085 ~ 1120cm ^-1, the preferable range of 1090 ~ 1110cm ^-1.

In the infrared absorption spectrum of the layer (YA) of the multilayered structure, in the range of 2,500 to 4,000 cm ^-1 , absorption of the stretching vibration of the hydroxyl group bonded to various atoms is observed. Examples of the hydroxyl group to be absorbed are seen in this range, and examples thereof include a hydroxyl group which is present on the surface of the metal oxide (A) and has an M-OH type, and a phosphorus atom derived from the phosphorus compound (B). And a hydroxyl group having a P-OH form, and a hydroxyl group having a C-OH form derived from the polymer (C), which will be described later. The amount of the hydroxyl group present in the layer (YA) may be related to the absorbance (α ² ) of the wave number (n ² ) based on the maximum absorption of the hydroxyl stretching vibration in the range of 2500 to 4000 cm ^-1 . Here, in the infrared absorption spectrum of the wave number (n ² ) layer (YA), the infrared absorption based on the stretching vibration of the hydroxyl group in the range of 2500 to 4000 cm ^-1 has the largest wave number. Hereinafter, the wave number (n ² ) may be referred to as "maximum absorption wave number (n ² )".

The more the amount of the hydroxyl group present in the layer (YA), the lower the density of the layer (YA), and as a result, the gas barrier property tends to decrease. Further, infrared inference multilayer structure has the layer (YA) of the absorption spectrum, the maximum wavenumber absorption (n ¹⁾ of the absorbance (α ¹⁾ and the above absorbance (α ²⁾ of the ratio of [the absorbance (α ²⁾ / The smaller the absorbance (α ¹ )], the more the metal oxide (A) particles are effectively bonded to each other via the phosphorus atom derived from the phosphorus compound (B). Therefore, the ratio [absorbance (α ² ) / absorbance (α ¹ )) is preferably 0.2 or less, and more preferably 0.1 or less from the viewpoint that the gas barrier properties of the obtained multilayer structure can be highly exhibited. The multilayer structure in which the layer (YA) has the above ratio [absorbance (α ² ) / absorbance (α ¹ )] can be adjusted by adjusting the number of moles (N _M ) of the metal atom constituting the metal oxide (A) described later, and The ratio of the molar number (N _P ) of the phosphorus atom derived from the phosphorus compound (B), heat treatment conditions, and the like are obtained. Further, although not particularly limited, but the layer described later (YA) of the precursor layer, which is an infrared absorption spectrum, 800 ~ 1400cm ^-1 in the range of maximum absorbance (α ¹ ') and the range of 2500 ~ 4000cm ^-1 based The maximum absorbance (α ² ') of the hydroxyl stretching vibration sometimes satisfies the relationship of the absorbance (α ² ') / the absorbance (α ¹ ') > 0.2.

In the infrared absorption spectrum of the layer (YA) of the multilayer structure, the maximum absorption wave number (n ¹ ) has a maximum half value width of the absorption peak, and from the viewpoint of the gas barrier property of the obtained multilayer structure, It is preferably 200 cm ^-1 or less, more preferably 150 cm ^-1 or less, still more preferably 130 cm ^-1 or less, still more preferably 110 cm ^-1 or less, still more preferably 100 cm ^-1 or less, and particularly preferably 50 cm ^-1 or less. . Although the invention is not limited in any way, it is inferred that when the particles of the metal oxide (A) are bonded to each other via a phosphorus atom, when the particles of the metal oxide (A) pass each other via the phosphorus atom from the phosphorus compound (B) and are not The metal atom not derived from the metal oxide (A) is bonded to form a bond represented by MOP (the bond represented by the MOP, which constitutes the metal atom (M) of the metal oxide (A) and the phosphorus atom (P) ), which is bonded via an oxygen atom (O), causes a half value of the maximum absorption peak at the maximum absorption wave number (n ¹ ) due to such a relatively fixed environment on the surface of the metal oxide (A) particle. The width will become the above range. Further, in the present specification, the absorption peak maximum absorption wave number (n ¹⁾ of the half-value width can be obtained by the following way: the requirements for having an absorption peak absorbance (α ¹⁾ half (absorbance (α ¹⁾ /2) The wave number of 2 points and calculate the difference.

The infrared absorption spectrum of the above layer (YA) can be measured by the ATR method (total reflection measurement method), or can be obtained by scraping the layer (YA) from the multilayer structure and measuring the infrared absorption spectrum thereof by the KBr method. .

In the layer (YA) of the multilayered structure, the shape of each particle of the metal oxide (A) is not particularly limited, and examples thereof include a spherical shape, a flat shape, a polyhedral shape, a fiber shape, and a needle shape. In terms of a multilayer structure having more excellent gas barrier properties, it is preferably in the form of a fiber or a needle. The layer (YA) may have only particles having a single shape, or particles having two or more different shapes. In addition, the particle size of the metal oxide (A) is not particularly limited, and examples thereof include a nanostructure to a submicron size, and a metal oxide (A) in terms of a multilayer structure having more excellent gas barrier properties. The size of the particles is preferably in the range of an average particle diameter of from 1 to 100 nm.

Further, the above-described fine structure in the layer (YA) of the multilayered structure can be confirmed by observing the cross section of the layer (YA) by a transmission electron microscope (TEM). Further, the particle diameter of each of the metal oxides (A) in the layer (YA) can be observed by a layer (YA) cross section obtained by a transmission electron microscope (TEM), and the maximum length of the longest axis of each particle, And the average value of the maximum length of the particle with the axis perpendicular to it, and the arbitrarily selected 10 of the cross-sectional observation image The particle diameters of the individual particles are averaged, whereby the above average particle diameter can be obtained.

As an example of the layer (YA) of the multilayered structure, the structure has the following structure: the particles of the metal oxide (A) pass each other through the phosphorus atom from the phosphorus compound (B) and do not pass through the non-metal oxide ( A) The structure in which the metal atoms are bonded. That is, in one example, the particles having the metal oxide (A) may be bonded to each other via a metal atom derived from the metal oxide (A), but may not be bonded via a metal atom other than the metal atom (A). Here, the "structure through which a phosphorus atom derived from the phosphorus compound (B) is bonded without a metal atom other than the metal oxide (A)" means a bonded metal oxide (A) particle. The inter-bonded main chain has a structure derived from a phosphorus atom of the phosphorus compound (B) and does not have a metal atom other than the metal oxide (A), and also includes a structure in which a side chain of the bond has a metal atom. The layer (YA) of the multilayered structure may have a structure in which the particles of the metal oxide (A) are bonded to each other via a phosphorus atom and a metal atom derived from the phosphorus compound (B). Structure (main chain of particles bonded between the bonded metal oxides (A) having a structure of both a phosphorus atom and a metal atom derived from the phosphorus compound (B)).

In the layer (YA) of the multilayered structure, the bonding form of each particle of the metal oxide (A) and the phosphorus atom may, for example, be a metal atom (M) constituting the metal oxide (A) and a phosphorus atom. (P), a type formed by bonding oxygen atoms (O). The particles of the metal oxide (A) may be bonded to each other via a phosphorus atom (P) derived from one molecule of the phosphorus compound (B), or may be bonded via a phosphorus atom (P) derived from two or more molecules of the phosphorus compound (B). Knot. The specific bonding type between the particles of the two metal oxides (A) bonded, if one of the bonds is represented by (M α), the metal atom of the metal oxide (A) particle is formed by (M) β)) represents a metal atom constituting the metal oxide (A) particle, and may, for example, be a bonding type of (M α)-OPO-(M β); (M α)-OP-[ OP] _n -O-(M β) bonding type; (M α)-OPZPO-(M β) bonding type; (M α)-OPZP-[OPZP] _n -O-(M β ) Bond type and so on. In the above example of the bonding type, n represents an integer of 1 or more, and Z represents a constituent atomic group existing between two phosphorus atoms when the phosphorus compound (B) has two or more phosphorus atoms in the molecule, and is bonded. The description of the other substituents of the phosphorus atom is omitted here. From the viewpoint of gas barrier properties of the obtained multilayered structure, it is preferred that in the layer (YA) of the multilayered structure, one metal oxide (A) particle and a plurality of other metal oxides (A) Particle bonding.

The metal oxide (A) may also be a hydrolysis condensate of the compound (L) containing a metal atom (M) to which a hydrolyzable characteristic group is bonded. Examples of the characteristic base include X ¹ of the formula (I) to be described later.

Further, the hydrolysis condensate of the compound (L) can be substantially regarded as a metal oxide. Therefore, in this specification, the hydrolysis condensate of the compound (L) may be referred to as "metal oxide (A)". In other words, in this specification, "metal oxide (A)" can be interpreted as "hydrolysis condensate of compound (L)", and "hydrolysis condensate of compound (L)" can be interpreted as "metal oxide (A)" .

[Metal Oxide (A)]

The metal atom constituting the metal oxide (A) (sometimes referred to as "metal atom (M)") may be a metal having a valence of 2 or more (for example, 2 to 4, 3 to 4). Specific examples of the atom include a metal of Group 2 of the periodic table such as magnesium or calcium; a metal of Group 12 of the periodic table such as zinc; a metal of Group 13 of the periodic table such as aluminum; and a metal of Group 14 of the periodic table. , transition metals such as titanium and zirconium. Furthermore, 矽 is sometimes classified as a semi-metal, but 矽 is included in the metal in this specification. The metal atom (M) constituting the metal oxide (A) may be one type or two or more types, but it is necessary Must contain at least aluminum. The metal atom (M) which can be used together with aluminum is preferably selected from the group consisting of titanium and zirconium in terms of ease of handling for producing the metal oxide (A), and the gas barrier property of the obtained multilayered structure is excellent. At least one of the groups.

The total ratio of aluminum, titanium, and zirconium in the metal atom (M) may be 60% by mole or more, 70% by mole or more, 80% by mole or more, 90% by mole or more, 95% by mole or more, or 100% by mole. Further, the proportion of aluminum in the metal atom (M) may be 60 mol% or more, 70 mol% or more, 80 mol% or more, 90 mol% or more, 95 mol% or more, or 100 mol%. .

The metal oxide (A) can be obtained by a liquid phase synthesis method, a gas phase synthesis method, a solid pulverization method, or the like, but considering the shape and size of the obtained metal oxide (A), the control efficiency and the production efficiency. Etc., preferably prepared by liquid phase synthesis.

In the liquid phase synthesis method, a compound (L) in which a hydrolyzable characteristic group is bonded to a metal atom (M) is used as a raw material, and is hydrolyzed and condensed, whereby a metal oxide (A) can be synthesized into a compound ( A hydrolysis condensate of L). Among them, the metal atom (M) of the compound (L) must contain at least aluminum. Further, when the hydrolysis condensate of the compound (L) is produced by a liquid phase synthesis method, a compound (L) obtained by partially hydrolyzing the compound (L) may be used in addition to the method of using the compound (L) itself as a raw material. a partial hydrolyzate, a complete hydrolyzate of the compound (L) obtained by completely hydrolyzing the compound (L), a partial hydrolysis condensate of the compound (L) obtained by partial hydrolysis condensation of the compound (L), and a compound (L) The metal oxide (A) is produced by partially condensing a complete hydrolyzate or by mixing two or more of these as a raw material, and condensing or hydrolyzing the mixture. The metal oxide (A) obtained in this manner is also referred to as "the hydrolysis condensate of the compound (L)" in the present specification. Hydrolyzable characteristic base The type of the energy group is not particularly limited, and examples thereof include a halogen atom (F, Cl, Br, I, etc.), an alkoxy group, a decyloxy group, a dimercaptomethyl group, a nitro group, etc., and the controllability of the reaction. In an excellent aspect, a halogen atom or an alkoxy group is preferred, and an alkoxy group is more preferred.

The compound (L) is preferably at least one compound (L ¹ ) represented by the following formula (II), in that the reaction control is easy and the gas barrier property of the obtained multilayered structure is excellent.

AlX ¹ _m R ¹ _(3-m) (II) In the formula (II), X ^{1 is} selected from the group consisting of F, Cl, Br, I, R ² O-, R ³ C(=O)O-, (R ⁴ C(=O)) ₂ CH- and NO ₃ group. R ¹ , R ² , R ³ and R ⁴ are each selected from the group consisting of an alkyl group, an aralkyl group, an aryl group and an alkenyl group. In the formula (II), when a plurality of X ¹ is present, the X ¹ may be the same or different. In the formula (II), when plural R ¹ is present, the R ^{1 's} may be the same or different. In the formula (II), when plural R ² is present, the R ^{2 's} may be the same or different. In the formula (II), when plural R ³ is present, the R ^{3 's} may be the same or different. In the formula (II), when plural R ⁴ is present, the R ^{4 's} may be the same or different. m represents an integer from 1 to 3. 〕

The alkyl group represented by R ¹ , R ² , R ³ and R ⁴ may, for example, be methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, t-butyl or 2- Ethylhexyl and the like. Examples of the aralkyl group represented by R ¹ , R ² , R ³ and R ⁴ include a benzyl group, a phenethyl group, a trityl group and the like. Examples of the aromatic group represented by R ¹ , R ² , R ³ and R ⁴ include a phenyl group, a naphthyl group, a tolyl group, a xylyl group, and a 2,4,6-trimethylphenyl group (mesityl). )Wait. Examples of the alkenyl group represented by R ¹ , R ² , R ³ and R ⁴ include a vinyl group, an allyl group and the like. R ^{1 is} preferably, for example, an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. X ^{1 is} preferably F, Cl, Br, I, R ² O-. Compound (L ¹⁾ of the preferred embodiment tie X ¹ is a halogen atom (F, Cl, Br, I ) , or an alkoxy group having a carbon number of 1 ~ 4 (R ² O -), m is 3. In one example of the compound (L ¹ ), X ¹ is a halogen atom (F, Cl, Br, I) or an alkoxy group (R ² O-) having a carbon number of 1 to 4, and m is 3.

Further, the compound (L) may contain at least one compound represented by the following formula in addition to the compound (L ¹ ).

M ¹ X ¹ _m R ¹ _(nm) (III) wherein M ¹ represents Ti or Zr. X ¹ and R ¹ are each as illustrated in the formula (II). Wherein, in the formula (III), n is equal to the valence of M ¹ , and m is an integer of 1 to n. 〕

Specific examples of the compound (L ¹ ) include aluminum chloride, aluminum triethoxide, aluminum tri-n-propoxide, aluminum triisopropoxide, aluminum tri-n-butoxide, and aluminum tri-butoxide. An aluminum compound such as aluminum trisodium butoxide, aluminum triacetate, aluminum acetonate or aluminum nitrate. Among these, the compound (L ¹ ) is preferably at least one compound selected from the group consisting of aluminum triisopropoxide and aluminum tri-butoxide. The compound (L ¹ ) may be used alone or in combination of two or more.

The proportion of the compound (L ¹ ) in the compound (L) is not particularly limited. The ratio of the compound other than the compound (L ¹ ) to the compound (L) is, for example, 20 mol% or less, 10 mol% or less, 5 mol% or less, and 0 mol%. In one example, the compound (L) is composed only of the compound (L ¹ ).

Further, as the compound other than ⁽¹ L) (L) compound can be obtained as long as the effects of the present invention is not particularly limited, and examples thereof include titanium, zirconium, magnesium, calcium, zinc, silicon and other metal atoms is bonded, A compound obtained by the above hydrolyzable property group or the like. Furthermore, there are cases where bismuth is classified as a semimetal, but 矽 is included in the metal in this specification. Among these, it is excellent in terms of gas barrier properties of the obtained multilayered structure, other than the compound ⁽¹ L) (L) preferably as a titanium or zirconium atom of the metal compound. Specific examples of the compound (L) other than the compound (L ¹ ) include, for example, titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetrakis(2-ethylhexanol), titanium tetraethoxide, A titanium compound such as titanium tetraethoxide or titanium acetonate; a zirconium compound such as zirconium tetra-n-propoxide, zirconium tetrabutoxide or zirconium tetraethoxide.

At least a part of the hydrolyzable characteristic group possessed by the compound (L) can be substituted with a hydroxyl group by hydrolyzing the compound (L). Further, the hydrolyzate thereof is condensed to form a compound in which a metal atom (M) is bonded via an oxygen atom (O). When this condensation is repeated, a compound which is substantially regarded as a metal oxide is formed. Further, a surface of the metal oxide (A) formed in this manner usually has a hydroxyl group.

Like the oxygen atom (O) in the structure represented by MOM, only the oxygen atom bonded to the metal atom (M) (for example, the oxygen atom (O) in the structure represented by MOH is bonded to the metal atom (M) and The ratio of the number of moles of the hydrogen atom (except for the oxygen atom of the hydrogen atom) to the number of moles of the metal atom (M) ([the number of moles of the oxygen atom (O) bonded only to the metal atom (M)] / [Molecular Number of Metal Atom (M)] is a compound of 0.8 or more, and such a compound is contained in the metal oxide (A) in the present specification. The above ratio of the metal oxide (A) is preferably 0.9 or more, more preferably 1.0 or more, still more preferably 1.1 or more. The upper limit of the above ratio is not particularly limited, and when the atomic value of the metal atom (M) is n, it is usually represented by n/2.

In order for the above hydrolysis condensation to occur, it is important that the compound (L) has a hydrolyzable characteristic group (functional group). When such a group is not bonded, it is difficult to prepare a desired metal oxide (A) because the hydrolysis condensation reaction does not occur or is extremely slow.

The hydrolysis condensate can be produced from a specific raw material by a method such as a conventional sol-gel method. The raw material may be selected from the group consisting of a compound (L), a partial hydrolyzate of the compound (L), a complete hydrolyzate of the compound (L), a partial hydrolysis condensate of the compound (L), and a partial hydrolyzate of the compound (L). At least one of the groups consisting of condensers (below Sometimes referred to as "compound (L) component"). These raw materials can be produced by a known method, and can also be used by a commercial person. It is not particularly limited, and for example, a condensate obtained by hydrolysis and condensation of about 2 to 10 compounds (L) can be used as a raw material. Specifically, for example, a condensate in which aluminum triisopropoxide is hydrolyzed and condensed into a 2 to 10-weight body can be used as a part of the raw material.

The number of molecules condensed in the hydrolysis condensate of the compound (L) can be controlled depending on the conditions at the time of condensation or hydrolytic condensation of the compound (L) component. For example, the number of molecules to be condensed can be controlled depending on the amount of water, the type of catalyst, the concentration, the temperature at the time of condensation or hydrolytic condensation, the time, and the like.

As described above, the layer (YA) of the multilayered structure contains the reaction product (R), and the reaction product (R) is formed by reacting at least the aluminum-containing metal oxide (A) with the phosphorus compound (B). Reaction product. Such a reaction product can be formed by reacting a metal oxide (A) with a phosphorus compound (B). Is supplied to the metal oxide (A) mixed with the phosphorus compound (B) (before being mixed), which may be the metal oxide (A) itself or a composition containing the metal oxide (A) Type. Preferably, the metal oxide (A) and the phosphorus compound (B) are mixed in a liquid (solution or dispersion) form obtained by dissolving or dispersing the metal oxide (A) in a solvent.

Preferred methods for producing a solution or dispersion of the metal oxide (A) are described below. Here, the case where the metal oxide (A) does not contain a metal atom other than the aluminum atom, that is, the case where the metal oxide (A) is alumina is taken as an example, the dispersion for producing the same is described. The method, but a similar manufacturing method can be employed in the production of a solution or dispersion containing other metal atoms. A preferred dispersion of alumina can be obtained by hydrolytically condensing aluminum alkoxide in an aqueous solution after adjusting the pH with an acid catalyst as needed to form a slurry of alumina. It is degummed in the presence of an amount of acid.

The temperature of the reaction system when the alkane alumina is hydrolyzed and condensed is not limited. The temperature of the reaction system is usually in the range of 2 to 100 °C. When the water is in contact with the alkane alumina, the temperature of the liquid rises. When the hydrolysis proceeds, the alcohol is formed as a by-product. When the boiling point of the alcohol is lower than that of the water, the alcohol will volatilize, causing the temperature of the reaction system to not rise to The case where the boiling point of the alcohol is higher than the above. In this case, since the growth of alumina is slowed down, it is effective to heat to around 95 ° C and remove the alcohol. The reaction time will differ depending on the reaction conditions (the presence, amount, type, etc. of the acid catalyst). The reaction time is usually in the range of 0.01 to 60 hours, preferably in the range of 0.1 to 12 hours, more preferably in the range of 0.5 to 6 hours. Further, the reaction can be carried out in various gas atmospheres such as air, carbon dioxide, nitrogen, and argon.

The amount of water used in the hydrolysis condensation is preferably from 1 to 200 moles, more preferably from 10 to 100 moles, relative to the alkane oxide. When the amount of water is less than 1 mole, the hydrolysis does not proceed sufficiently, which is not preferable. On the other hand, in the case of more than 200 moles, the manufacturing efficiency is lowered or the viscosity is high, which is not preferable. When a component containing water (for example, hydrochloric acid, nitric acid, or the like) is used, it is preferable to determine the amount of water to be used in consideration of the amount of water introduced by the component.

As the acid catalyst used for the hydrolysis condensation, hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, benzoic acid, acetic acid, lactic acid, butyric acid, carbonic acid, oxalic acid, maleic acid or the like can be used. Among these, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, lactic acid, and butyric acid are preferred, and nitric acid and acetic acid are more preferred. In the case where an acid catalyst is used in the hydrolysis condensation, it is preferred to use an appropriate amount depending on the kind of the acid so that the pH before the hydrolysis condensation is in the range of 2.0 to 4.0.

The alumina slurry obtained by hydrolysis condensation can also be used as an alumina dispersion directly, and the obtained alumina slurry can be heated and degummed in the presence of a specific amount of acid to obtain transparency and viscosity stability. Excellent alumina dispersion.

As the acid to be used for the degumming, a monovalent inorganic acid or an organic acid such as nitric acid, hydrochloric acid, perchloric acid, formic acid, acetic acid or propionic acid can be used. Among these, nitric acid, hydrochloric acid, and acetic acid are preferred, and nitric acid and acetic acid are more preferred.

When the acid used in the degumming is nitric acid or hydrochloric acid, the amount thereof is preferably 0.001 to 0.4 mol times, more preferably 0.005 to 0.3 mol times, relative to the aluminum atom. When it is less than 0.001 moles, there are cases where the degumming does not proceed sufficiently or it takes a very long time. Further, when it exceeds 0.4 mol, the obtained alumina dispersion tends to have a low stability over time.

On the other hand, when the acid used in the degumming uses acetic acid, the amount thereof is preferably 0.01 to 1.0 mol times, more preferably 0.05 to 0.5 mol times, relative to the aluminum atom. When it is less than 0.01 moles, there are cases where the degumming does not proceed sufficiently or it takes a very long time. Further, when it exceeds 1.0 mol, the obtained alumina dispersion tends to have a reduced stability over time.

The acid which is present during the degumming may be added during the hydrolysis and condensation. However, when the acid is also removed when the alcohol formed by the hydrolysis is removed during the hydrolysis condensation, it is preferably added in an amount of the above range.

The degumming is carried out in the range of 40 to 200 ° C, whereby the gel is degreased in a short period of time with an appropriate acid amount, and a dispersion of alumina having a specific particle size and excellent viscosity stability can be produced. If the temperature at the time of degumming is less than 40 ° C, the degumming takes a long time. If it exceeds 200 ° C, the increase in the dissolving speed due to the increase in temperature is only a little. On the other hand, it is necessary to have a high withstand voltage. Containers and the like are therefore economically disadvantageous and therefore not good.

After the completion of the degumming, the solvent may be diluted as needed, and concentrated by heating to obtain a dispersion having a specific concentration of alumina. In the case where heating and concentration are carried out in order to suppress adhesion and gelation, it is preferably carried out at 60 ° C or lower under reduced pressure.

The metal oxide (A) to be mixed with the phosphorus compound (B) (the composition of the phosphorus-containing compound (B) when used as a composition) preferably contains substantially no phosphorus atom. However, for example, due to the influence of impurities in the preparation of the metal oxide (A), etc., it may be sometimes supplied to be mixed with the phosphorus compound (B) (the composition of the phosphorus-containing compound (B) when used as a composition) A small amount of phosphorus atoms are mixed in the metal oxide (A). Therefore, the metal oxide (A) to be mixed with the phosphorus compound (B) (the composition of the phosphorus-containing compound (B) when used as a composition) may be added to the extent that the effects of the present invention are not impaired. Contains a small amount of phosphorus atoms. In the aspect of obtaining a multilayer structure having more excellent gas barrier properties, it is supplied to a metal oxide mixed with a phosphorus compound (B) (a composition containing a phosphorus compound (B) when used as a composition) The content of the phosphorus atom contained in the substance (A) is based on the number of moles of all the metal atoms (M) contained in the metal oxide (A) (100 mol%), preferably 30 mol. % or less, more preferably 10 mol% or less, still more preferably 5 mol% or less, particularly preferably 1 mol% or less, and may be 0 mol%.

a layer (YA) having a multilayer structure having a specific structure in which particles of a metal oxide (A) are bonded to each other via a phosphorus atom derived from a phosphorus compound (B), and a metal oxide in the layer (YA) The shape and size of the particles of (A) and the shape of the particles of the metal oxide (A) to be mixed with the phosphorus compound (B) (the composition of the phosphorus-containing compound (B) when used as a composition) The sizes may be the same or different. That is, the particles of the metal oxide (A) used as the raw material of the layer (YA) may vary in shape and size in the process of forming the layer (YA). In particular, when the layer (YA) is formed using the coating liquid (U) described later, in the coating liquid (U), or in the liquid (S) which will be described later, or the coating liquid (U) The shape and size may vary in each step after application to the substrate (X).

[Phosphorus compound (B)]

The phosphorus compound (B) contains a site reactive with the metal oxide (A), and typically contains a plurality of such sites. In a preferred embodiment, the phosphorus compound (B) contains 2 to 20 such sites (atoms or functional groups). Examples of such a site include a site reactive with a functional group (for example, a hydroxyl group) present on the surface of the metal oxide (A). For example, examples of such a site include a halogen atom directly bonded to a phosphorus atom and an oxygen atom directly bonded to a phosphorus atom. These halogen atoms and oxygen atoms may initiate a condensation reaction (hydrolysis condensation reaction) with a hydroxyl group present on the surface of the metal oxide (A). The functional group (for example, a hydroxyl group) present on the surface of the metal oxide (A) is usually bonded to the metal atom (M) constituting the metal oxide (A).

The phosphorus compound (B) can be a structure having a structure in which a halogen atom or an oxygen atom is directly bonded to a phosphorus atom, and by using such a phosphorus compound (B), a hydroxyl group present on the surface of the metal oxide (A) can be used. The (hydrolysis) condensation is carried out while the bonding is carried out. The phosphorus compound (B) may be one having one phosphorus atom or one having two or more phosphorus atoms.

The phosphorus compound (B) may be at least one compound selected from the group consisting of phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid, and derivatives thereof. Specific examples of the polyphosphoric acid include pyrophosphoric acid, triphosphoric acid, and polyphosphoric acid obtained by condensing four or more phosphoric acids. Examples of the above derivatives include phosphoric acid, polyphosphoric acid, phosphorous acid, phosphonic acid salts, (partial) ester compounds, halides (chlorides, etc.), and dehydrates (phosphorus pentoxide). Further, examples of the derivative of the phosphonic acid also include a compound in which a hydrogen atom directly bonded to a phosphonic acid (HP(=O)(OH) ₂ ) phosphorus atom is substituted with an alkyl group which may have various functional groups (for example, Nitrilotris (methylene phosphonate), N, N, N', N'-ethylenediamine tetra (methylene phosphonic acid), etc., salts thereof, (partial) ester compounds , halides and dehydrates. Further, an organic polymer having a phosphorus atom such as a phosphorylated starch or a polymer (E) to be described later can also be used as the phosphorus compound (B). These phosphorus compounds (B) may be used alone or in combination of two or more. Among these phosphorus compounds (B), the coating liquid (U) having a layer (YA) to be formed by using the coating liquid (U) described later is more excellent in gas barrier properties of the obtained multilayer structure. In particular, it is preferred to use phosphoric acid alone or in combination with phosphoric acid other than phosphoric acid.

As described above, the layer (YA) of the multilayered structure contains the reaction product (R), and the reaction product (R) is a reaction in which at least the metal oxide (A) and the phosphorus compound (B) are reacted. Product. Such a reaction product can be formed by mixing and reacting the metal oxide (A) with the phosphorus compound (B). The phosphorus compound (B) supplied to the metal oxide (A) (before mixing) may be the phosphorus compound (B) itself or the form of the composition of the phosphorus-containing compound (B). The form of the composition of the phosphorus-containing compound (B) is preferred. One preferred embodiment is a mixture of a phosphorus compound (B) and a metal oxide (A) in a form of a solution obtained by dissolving a phosphorus compound (B) in a solvent. Any solvent may be used as the solvent at this time, and a preferred solvent is water or a mixed solvent of water.

In the aspect of obtaining a multilayer structure having more excellent gas barrier properties, it is preferably supplied to the composition of the phosphorus compound (B) or the phosphorus-containing compound (B) mixed with the metal oxide (A). The content of the metal atom is low. The content ratio of the metal atom contained in the composition of the phosphorus compound (B) or the phosphorus-containing compound (B) to be mixed with the metal oxide (A), when the phosphorus compound (B) or the phosphorus-containing compound is used When the number of moles of all the phosphorus atoms contained in the composition of (B) is based on (100 mol%), it is preferably 100 mol% or less, more preferably 30 mol% or less, still more preferably 5 or less. The molar percentage is 5% or less, particularly preferably 1% by mole or less, and may be 0% by mole.

[Reaction product (R)]

The reaction product (R) contains a reaction product produced by reacting only the metal oxide (A) and the phosphorus compound (B). Further, the reaction product (R) also contains a reaction product formed by reacting the metal oxide (A) with the phosphorus compound (B) and further compounds. The reaction product (R) can be formed by the method described in the production method described later.

[ratio of metal oxide (A) to phosphorus compound (B)]

In the layer (YA), the molar number N _M of the metal atom constituting the metal oxide (A) and the molar number N _P of the phosphorus atom derived from the phosphorus compound (B) satisfy 1.0 ≦ (mole number N _M ) / ( The relationship between the molar number N _P ) ≦ 3.6 is better, and the relationship of 1.1 ≦ (mole number N _M ) / (mole number N _P ) ≦ 3.0 is better. If the value of (molar number N _M ) / (mole number N _P ) exceeds 3.6, the metal oxide (A) is excessive with respect to the phosphorus compound (B), and the particles of the metal oxide (A) are bonded to each other. In addition, the amount of the hydroxyl group present on the surface of the metal oxide (A) is increased, and the gas barrier property and the stability thereof tend to be lowered. On the other hand, if the value of (molar number N _M ) / (mole number N _P ) is less than 1.0, the phosphorus compound (B) is excessive with respect to the metal oxide (A) and does not participate in metal oxides. The amount of the phosphorus compound (B) remaining in the (A) bond is increased, and the amount of the hydroxyl group derived from the phosphorus compound (B) tends to increase, and the gas barrier property and the stability thereof tend to be lowered.

Further, the above ratio can be adjusted by the ratio of the amount of the metal oxide (A) to the amount of the phosphorus compound (B) in the coating liquid for forming the layer (YA). The ratio of the molar number N _M to the molar number N _P in the layer (YA) is usually the ratio in the coating liquid, and the molar number of the metal atom constituting the metal oxide (A) and the phosphorus compound ( The ratio of the molar numbers of the phosphorus atoms of B) is the same.

[Polymer (C)]

The layer (YA) of the multilayer structure may further contain a specific polymer (C). polymerization The substance (C) is a polymer having at least one functional group (f) selected from the group consisting of a hydroxyl group, a carboxyl group, a carboxylic anhydride group, and a salt of a carboxyl group. The polymer (C) in the layer (YA) of the multilayer structure may also be bonded to the particles of the metal oxide (A) and the phosphorus atom derived from the phosphorus compound (B) via the functional group (f) One or both are directly or indirectly bonded. Further, the reaction product (R) in the layer (YA) of the multilayered structure may have a polymer (C) produced by reacting the polymer (C) with the metal oxide (A) or the phosphorus compound (B). )section. Further, in the present specification, a polymer which satisfies the polymer of the phosphorus compound (B) and contains the functional group (f) is not contained in the polymer (C) but is treated as the phosphorus compound (B).

As the polymer (C), a polymer containing a constituent unit having a functional group (f) can be used. Specific examples of such a constituent unit include a functional group such as a vinyl alcohol unit, an acrylic acid unit, a methacrylic acid unit, a maleic acid unit, an itaconic acid unit, a maleic anhydride unit, or a phthalic anhydride unit. (f) One or more constituent units. The polymer (C) may contain only one constituent unit having a functional group (f), or may contain two constituent units having a functional group (f).

In order to obtain a multilayer structure having more excellent gas barrier properties and stability thereof, the total constituent unit of the polymer (C) has a constituent unit ratio of the functional group (f), preferably 10 mol% or more. More preferably, it is 20 mol% or more, more preferably 40 mol% or more, and particularly preferably 70 mol% or more, and may be 100 mol%.

When the polymer (C) is composed of a constituent unit having a functional group (f) and other constituent units other than the constituent unit, the type of the other constituent unit is not limited. Examples of the other constituent unit include: methyl acrylate unit, methyl methacrylate unit, ethyl acrylate unit, ethyl methacrylate unit, butyl acrylate unit, and butyl methacrylate unit, etc. (methyl) a constituent unit derived from acrylate; a vinyl formate unit and vinyl acetate a constituent unit derived from a vinyl ester such as an ester unit; a constituent unit derived from an aromatic ethylene such as a styrene unit and a p-styrenesulfonic acid unit; a constituent unit derived from an olefin such as an ethylene unit, a propylene unit, and an isobutylene unit; Wait. When the polymer (C) contains two or more constituent units, the polymer (C) may be any of an alternating copolymer, a random copolymer, a block copolymer, and a tapered copolymer. .

Specific examples of the polymer (C) having a hydroxyl group include polyvinyl alcohol, a partial saponified product of polyvinyl acetate, polyethylene glycol, polyhydroxyethyl (meth) acrylate, and polysaccharides such as starch. A polysaccharide derivative derived from a polysaccharide or the like. Specific examples of the polymer (C) having a salt of a carboxyl group, a carboxylic anhydride group or a carboxyl group include polyacrylic acid, polymethacrylic acid, poly(acrylic acid/methacrylic acid), and the like. Further, specific examples of the polymer (C) containing a constituent unit containing no functional group (f) include an ethylene-vinyl alcohol copolymer, an ethylene-maleic anhydride copolymer, and a styrene-maleic anhydride. Copolymer, isobutylene-maleic anhydride alternating copolymer, ethylene-acrylic acid copolymer, styrene of ethylene-ethyl acrylate copolymer, and the like. In order to obtain a multilayer structure having more excellent gas barrier properties and stability thereof, the polymer (C) is preferably selected from the group consisting of polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polysaccharide, polyacrylic acid, and polyacrylic acid. At least one polymer of a group consisting of polymethacrylic acid and a salt of polymethacrylic acid.

The molecular weight of the polymer (C) is not particularly limited. In order to obtain a multilayered structure having more excellent gas barrier properties and mechanical properties (falling strength, etc.), the number average molecular weight of the polymer (C) is preferably 5,000 or more, more preferably 8,000 or more, still more preferably 10,000. the above. The upper limit of the number average molecular weight of the polymer (C) is not particularly limited and is, for example, 1,500,000 or less.

In order to improve the gas barrier properties, the polymer (C) in the layer (YA) When the content is based on the mass of the layer (YA) (100% by mass), it is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, and may be 20% by mass. %the following. The polymer (C) may or may not react with other components in the layer (YA). Further, in the present specification, when the polymer (C) is reacted with other components, it also appears as a polymer (C). For example, when the polymer (C) is bonded to the metal oxide (A), and/or the phosphorus atom derived from the phosphorus compound (B), it also appears as the polymer (C). In this case, the content of the polymer (C) is calculated by dividing the mass of the polymer (C) before the metal oxide (A) and/or the phosphorus atom is bonded by the mass of the layer (YA).

The layer (YA) of the multilayered structure may be a reaction product (R) obtained by reacting only at least an aluminum-containing metal oxide (A) with a phosphorus compound (B) (which contains a polymer (C) portion The composition may be composed only of the reaction product (R) and the unreacted polymer (C), and may further contain other components.

Examples of the other components mentioned above include inorganic acid metal salts such as carbonates, hydrochlorides, nitrates, hydrogencarbonates, sulfates, hydrogen sulfates, borates, and aluminates; oxalates, acetates, and tartrates. An organic acid metal salt such as stearate; an ethylene acetone metal complex (such as aluminum acetonate, etc.), a cyclopentadienyl metal complex (titanocene, etc.), and a cyano metal a metal complex such as a substance; a layered clay compound; a crosslinking agent; a polymer compound other than the polymer (C); a plasticizer; an antioxidant; a UV absorber; a flame retardant.

The content of the other component in the layer (YA) in the multilayer structure is preferably 50% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, and particularly preferably 5% by mass or less. It is 0% by mass (excluding other ingredients).

[Thickness of layer (YA)]

The thickness of the layer (YA) of the multilayered structure (the total thickness of each layer (YA) when the multilayer structure has two or more layers (YA)) is preferably 4.0 μm or less, more preferably 2.0 μm or less. More preferably, it is 1.0 μm or less, and may be 0.9 μm or less. By thinning the layer (YA), it is possible to suppress the dimensional change of the multilayer structure during processing such as printing, lamination, etc., and the flexibility of the multilayer structure is increased, and the mechanical properties thereof can be made close to the substrate. Its own mechanical properties.

In the multilayer structure, when the total thickness of the layer (YA) is 1.0 μm or less (for example, 0.5 μm or less), the oxygen permeability at 20 ° C and 85% RH may be 2 ml / (m ² ‧ day) ‧atm) below. Further, the thickness of the layer (YA) (the total thickness of each layer (YA) when the multilayer structure has two or more layers (YA)) is preferably 0.1 μm or more (for example, 0.2 μm or more). Further, the thickness of each layer (YA) is preferably 0.05 μm or more (for example, 0.15 μm or more) from the viewpoint of further improving the gas barrier properties of the multilayer structure. The thickness of the layer (YA) can be controlled by the concentration of the coating liquid (U) to be used for forming the layer (YA), and the coating method thereof.

[layer (YB) and layer (YC)]

The layer (Y) of the multilayered structure may be a layer (YB) which is an evaporated layer of aluminum or a layer (YC) which is an evaporated layer of alumina. These vapor deposition layers can be produced by the same method as the inorganic vapor deposition layer described later.

[layer (Z)]

The layer (Z) of the multilayer structure contains a polymer (E) containing a monomer unit having a phosphorus atom. The layer (Z) is formed in such a manner that the layer (Z) is adjacent to the layer (Y), whereby the bending resistance of the multilayer structure can be greatly improved.

[Polymer (E)]

The polymer (E) has a plurality of phosphorus atoms in its molecule. For example, the phosphorus atom is contained in an acidic group or a derivative thereof. Examples of the acidic group containing a phosphorus atom include a phosphate group, a polyphosphoric acid group, a phosphite group, and a phosphonic acid group. Among the plurality of phosphorus atoms of the polymer (E), at least one of the phosphorus atoms contains a site reactive with the metal oxide (A). In a preferred embodiment, the polymer (E) contains about 10 to 1000 such phosphorus atoms. Examples of the site of the phosphorus atom reactive with the metal oxide (A) include the structural moiety described for the phosphorus compound (B).

The polymer (E) is not particularly limited as long as it satisfies the above conditions, and a preferred example thereof is a single polymer or copolymer of a (meth) acrylate containing a phosphate group at the side of the side chain. These polymers can be synthesized by a monomer having a (meth) acrylate group having a phosphate group at the terminal of the side chain, and these are separately polymerized or copolymerized with other vinyl group-containing monomers. .

The (meth) acrylate which has a phosphate group at the terminal side of the side chain used in the present invention may be at least one compound represented by the following formula (IV).

[In the formula (IV), R ⁵ and R ⁶ are a hydrogen atom or an alkyl group selected from methyl, ethyl, n-propyl or isopropyl, and a hydrogen atom of a part of the alkyl group may pass through other atoms. Replaced by functional groups. Further, n is a natural number, and is typically an integer from 1 to 6. 〕

In a typical example, R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is a hydrogen atom or a methyl group.

Among the monomers represented by the formula (IV), examples of the monomer which can be suitably used in the present invention include acryloyloxyethyl acrylate, phosphatidyl methacrylate, and acrylic acid. Acidic phosphorusoxypolyoxyethylene glycol ester, acid phosphatoxy polyoxyethylene glycol methacrylate, acid oxyphosphoryl polyoxypropylene glycol acrylate, acid phosphatoxy polyoxypropylene glycol methacrylate And 3-chloro-2-acid type phosphorus propyl acrylate and 3-chloro-2-acid phosphorus propyl methacrylate. Among them, the individual polymer of the phosphatidyl methacrylate is preferable from the viewpoint of obtaining a multilayer structure excellent in bending resistance. However, the monomer which can be used in the present invention is not limited to these. A portion of such monomers can be suitably purchased from the uni-chemical company under the trade name Phosmer type.

The polymer (E) may be a single polymer of a monomer represented by the formula (IV), or a copolymer of two or more monomers represented by the formula (IV), or at least A copolymer of a monomer represented by the formula (IV) and another vinyl monomer.

The other vinyl monomer copolymerizable with the monomer represented by the formula (IV) is not particularly limited as long as it can be copolymerized with the monomer represented by the formula (IV), and a conventional one can be used. Examples of such a vinyl monomer include acrylic acid, acrylate, methacrylic acid, methacrylic acid ester, acrylonitrile, methacrylonitrile, styrene, nuclear-substituted styrene, alkyl vinyl ether, and alkane. Vinyl esters, perfluoroalkylvinylethers, perfluoro-alkyl vinyl esters, maleic acid, maleic anhydride, fumaric acid, itaconic acid, cis-butane Ethylidene imine or phenyl maleimide or the like. Among these vinyl monomers, those which are preferably used are methacrylates, acrylonitrile, styrenes, maleimide, and phenylmaleimide.

In order to obtain a multilayered structure having more excellent bending resistance, the ratio of the constituent units derived from the monomer represented by the general formula (IV) in the total constituent unit of the polymer (E) is preferably 10 mol% or more. More preferably, it is more than 20% by mole, and even more preferably 40% by mole or more. It is particularly preferably 70 mol% or more, and may be 100 mol%.

The polymer (E) is not particularly limited as long as it satisfies the above conditions, and preferred examples thereof include individual polymers or copolymers of a vinylphosphonic acid group containing a phosphoric acid group. Here, the term "vinylphosphonic acid" means the following requirements.

(a) a phosphonic acid having a substituent, a phosphinic acid having a substituent, or an ester thereof.

(b) a phosphorus atom (phosphonic acid group, phosphinic acid group or phosphorus atom in the ester) in which a carbon chain of a substituent is bonded to a molecule via a phosphorus-carbon bond. There are carbon-carbon double bonds in the carbon chain. A part of the carbon chain may also constitute a carbon ring.

(c) at least one hydroxyl group is bonded to a phosphorus atom (phosphonic acid group, phosphinic acid group or phosphorus atom in the ester) in the molecule.

An example of the vinylphosphonic acid is a phosphonic acid having a substituent and/or a phosphinic acid, and satisfies the above requirement (b). For example, an example of a phosphonic acid is a phosphonic acid having a substituent and satisfies the above requirement (b).

The carbon chain which is bonded to the substituent of the phosphorus atom may have a carbon number in the range of 2 to 30 (for example, in the range of 2 to 10). Examples of the substituent include a hydrocarbon chain having a carbon-carbon double bond (e.g., vinyl, allyl, 1-propenyl, isopropenyl, 2-methyl-1-propenyl, 2-methyl-2- Propylene, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 1-hexenyl, 1,3-hexadienyl, 1,5-hexadienyl Wait). A hydrocarbon chain having a carbon-carbon double bond may also contain one or more oxycarbonyl groups in the molecular chain. Examples of the carbocyclic ring include a benzene ring, a naphthalene ring, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclopropene ring, a cyclobutene ring, a cyclopentene ring, and the like. Further, in addition to the hydrocarbon chain having a carbon-carbon double bond on the carbocyclic ring, one or more of the bonds may be bonded. Hydrocarbon chain (eg methyl, ethyl, propyl, etc.). Examples of the substituent bonded to the phosphorus atom include a hydrocarbon chain having a carbon-carbon double bond such as a vinyl group, a 4-vinylbenzyl group, or the like, and the above hydrocarbon chain is bonded to the above hydrocarbon chain. The carbon ring.

The structure constituting the ester group of the ester is a structure in which a hydrogen atom bonded to a hydroxyl group of a phosphorus atom of a phosphinic acid or a phosphonic acid is substituted with an alkyl group, and examples of the alkyl group include a methyl group, an ethyl group, and a propyl group. , butyl, pentyl, hexyl and the like.

The polymer (E) can also be obtained by polymerizing a monomer of a vinylphosphonic acid or copolymerizing with another vinyl-containing monomer. Further, the polymer (E) can also be obtained by subjecting a vinylphosphonic acid derivative such as a phosphonic acid halide or an ester to hydrolysis by acylation or copolymerization.

Examples of suitable vinylphosphonic acid monomers include alkenylphosphonic acids such as vinylphosphonic acid and 2-propene-1-phosphonic acid; 4-vinylbenzylphosphonic acid and 4-vinylphenylphosphine. Alkenyl aromatic phosphonic acid such as acid; 6-[(2-phosphonoacetyl)oxy]hexylacrylate, phosphonomethylmethacrylate, Phosphine (meth) acrylates such as 11-phosphinyl methacrylate and 1,1-diphosphine ethyl methacrylate; vinyl phosphinic acid, 4-vinylbenzylphosphinic acid, etc. Phosphonic acids and the like. Among them, poly(vinylphosphonic acid), which is a single polymer of vinylphosphonic acid, is preferred from the viewpoint of obtaining a multilayer structure excellent in bending resistance. However, the monomers that can be used are not limited to these.

The polymer (E) may be a single polymer of a vinylphosphonic acid monomer, or a copolymer of two or more kinds of monomers using a vinylphosphonic acid, or at least one vinylphosphonic acid. a copolymer of a monomer and another vinyl monomer.

Other vinyl monomers copolymerizable with vinylphosphonic acid monomers, as long as The copolymerizable with the vinylphosphonic acid monomer is not particularly limited, and a conventional one can be used. Examples of such a vinyl monomer include acrylic acid, acrylates, methacrylic acid, methacrylic acid esters, acrylonitrile, methacrylonitrile, styrene, nuclear-substituted styrenes, and alkyl vinyl ethers. Alkyl vinyl esters, perfluoro-alkyl vinyl ethers, perfluoro-alkyl vinyl esters, maleic acid, maleic anhydride, fumaric acid, itaconic acid, cis Butylene diimide or phenyl maleimide or the like. Among these vinyl monomers, those which are preferably used are methacrylates, acrylonitrile, styrenes, maleimide, and phenyl maleimide.

In order to obtain a multilayer structure having more excellent bending resistance, in the total constituent unit of the polymer (E), the proportion of constituent units derived from the vinylphosphonic acid monomer is preferably 10 mol% or more, more preferably 20 mol% or more, more preferably 40 mol% or more, particularly preferably 70 mol% or more, or 100 mol%.

The polymer (E) may also be a polymer having a repeating unit represented by the following formula (I), and more specifically, a poly(vinylphosphonic acid).

[In the formula (I), n represents a natural number].

n is not particularly limited. n is, for example, a number that satisfies the number average molecular weight as described below.

The molecular weight of the polymer (E) is not particularly limited, and typically, the number average molecular weight of the polymer (E) is in the range of 1,000 to 100,000. If the number average molecular weight is within this range, then The improvement effect of the bending resistance by the layer (Z) laminate and the viscosity stability of the coating liquid (V) containing the polymer (E) described later can be achieved at a high level. Further, when the molecular weight of the polymer (E) per phosphorus atom is in the range of from 150 to 500, the effect of improving the bending resistance by the layer (Z) laminate may be further improved.

The layer (Z) of the multilayered structure may be composed only of the polymer (E) containing a monomer unit having a phosphorus atom, and may further contain other components.

Examples of the other components include inorganic acid metal salts such as carbonates, hydrochlorides, nitrates, hydrogencarbonates, sulfates, hydrogen sulfates, and borates; oxalates, acetates, tartrates, and stearates. a metal complex such as an organic acid metal salt; an ethyl acetonide metal complex (such as acetoacetate or the like), a cyclopentadienyl metal complex (titanocene or the like), or a cyano metal complex; Layered clay compound; cross-linking agent; polymer compound other than polymer (E); plasticizer; antioxidant; ultraviolet absorber; flame retardant.

In the layer (Z) in the multilayer structure, the content of the other component is preferably 50% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less, and particularly preferably 5% by mass or less. It can also be 0% by mass (excluding other ingredients).

The polymerization reaction for forming the polymer (E) can be carried out by using a polymerization initiator in a solvent which is a monomer component of the raw material and a polymer which is formed. Examples of the polymerization initiator include 2,2-azobisisobutyronitrile and 2,2-azobis(2,4-dimethylvaleronitrile). , 2,2-azobis(2-methylpropionate), dimethyl 2,2-azobisisobutyrate, etc. a peroxide-based initiator such as a starter, lauroyl peroxide, benzoyl peroxide, or 2-ethyl-tert-butyl peroctoate . when In the case of copolymerization with other vinyl monomers, a suitable solvent can be selected depending on the combination of comonomers with each other. Two or more kinds of mixed solvents may be used as needed.

One example of the polymerization reaction is carried out at a polymerization temperature of 50 to 100 ° C while dropping a mixed solution of a monomer, a polymerization initiator, and a solvent, and maintaining the polymerization temperature for about 1 to 24 hours after the completion of the dropwise addition or At the above temperature, stirring is continued to complete the polymerization.

When the monomer component is 1, the solvent is preferably used in a weight ratio of about 1.0 to 3.0, and the polymerization initiator is preferably used in a weight ratio of about 0.005 to 0.05. More preferably, the weight ratio is from 1.5 to 2.5, and the polymerization initiator is about 0.01. When the amount of the solvent or the polymerization initiator to be used is not within the above range, gelation of the polymer may be caused to be insoluble in various solvents, and problems such as application by solution may not be performed.

The layer (Z) of the multilayer structure can be formed by coating a solution of the polymer (E). Any solvent may be used at this time, and preferred solvents include water, alcohols, or a mixed solvent thereof.

[thickness of layer (Z)]

The thickness of each layer (Z) is 0.005 μm or more, preferably 0.03 μm or more, and more preferably 0.05 μm or more (for example, 0.15 μm or more) from the viewpoint of better bending resistance of the multilayer structure. The upper limit of the thickness of the layer (Z) is not particularly limited. When the thickness is 1.0 μm or more, the effect of improving the bending resistance is saturated. Therefore, it is preferable to limit the thickness of the layer (Z) to 1.0 μm on the economical level. The thickness of the layer (Z) can be controlled by the concentration of the coating liquid (V) to be used later for forming the layer (Z), and the coating method thereof.

[Substrate (X)]

The material of the substrate (X) which the multilayer structure has is not particularly limited, and a substrate made of various materials can be used. The material of the substrate (X) may, for example, be a resin such as a thermoplastic resin or a thermosetting resin; a metal; a metal oxide or the like. Further, the substrate may be a composite structure or a multilayer structure composed of a plurality of materials.

The form of the substrate (X) is not particularly limited, and may be a layered substrate such as a film or a sheet.

The layered substrate may, for example, be a single layer or a plurality of layers including at least one selected from the group consisting of a thermoplastic resin film layer, a thermosetting resin film layer, an inorganic vapor deposition layer, a metal oxide layer, and a metal foil layer. The substrate. Among these, a substrate containing a thermoplastic resin film layer is preferable, and in this case, the substrate may be a single layer or a plurality of layers. The use of a multilayer structure (laminated structure) having such a substrate is excellent in properties required for use as a protective sheet.

The thermoplastic resin film forming the thermoplastic resin film layer may, for example, be a polyolefin resin such as polyethylene or polypropylene; polyethylene terephthalate or polyethylene-2,6-naphthalate (polyethylene-2) , 6-naphthalate), polybutylene terephthalate, polyester resins such as these copolymers; polyamine-based resins such as nylon-6, nylon-66, nylon-12; polyvinyl alcohol, ethylene- Hydroxy-containing polymer such as ethylene-vinyl alcohol copolymer; polystyrene; poly(meth)acrylate; polyacrylonitrile; polyvinyl acetate; polycarbonate; polyarylate (Polyarylate); regenerated cellulose; polyimine; polyether quinone; polyfluorene; polyether oxime; polyetheretherketone; ionic polymer resin and other thermoplastic resin obtained by forming a film.

When a transparent protective sheet is sought, it is preferable to use a light-transmitting thermoplastic resin as the material of the substrate (X). Examples of the translucent thermoplastic resin include polyethylene terephthalate, polycarbonate, polymethyl methacrylate, polystyrene, polymethyl Methyl acrylate/styrene copolymer, syndiotactic polystyrene, cyclic polyolefin, cyclic olefin copolymer, cellulose acetate, polyimine, polypropylene, polyethylene, polynaphthalene Ethylene glycolate, polyvinyl acetal, polyvinyl butyral, polyvinyl alcohol, polyvinyl chloride, polymethylpentene, and the like. Among these, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), and cyclic olefin copolymer (COC) have high transparency at the same time. It is preferable from the viewpoint of excellent heat resistance.

The thermoplastic resin film layer may be composed of a plurality of resins.

The thermoplastic resin film may be a stretched film or a non-stretched film. Since the obtained multilayer structure is excellent in processing suitability (printing, lamination, etc.), it is preferably a stretched film, and particularly preferably a biaxially stretched film. The biaxially stretched film may be a biaxially stretched film produced by any of the simultaneous biaxial stretching method, the sequential biaxial stretching method, and the tubular stretching method.

The inorganic deposited layer is preferably one which has barrier properties against oxygen and water vapor. The inorganic vapor-deposited layer can be suitably used as a metal vapor-deposited layer such as aluminum, and has transparency. The inorganic vapor-deposited layer can be formed by vapor-depositing an inorganic material on the substrate for vapor deposition, and the entire laminate in which the inorganic vapor-deposited layer is formed on the vapor deposition substrate can be used as the substrate (X) having a multilayer structure. The inorganic vapor-deposited layer having transparency may, for example, be a layer formed of an inorganic oxide such as alumina, cerium oxide, cerium oxynitride, magnesium oxide, tin oxide, or a mixture thereof; cerium nitride or cerium carbonitride a layer formed of an inorganic nitride such as (silicon carbonitride); a layer formed of an inorganic carbide such as ruthenium carbide or the like. Among these, a layer formed of alumina, cerium oxide, magnesium oxide, or cerium nitride is preferred from the viewpoint of excellent oxygen barrier properties and water vapor barrier properties.

The preferred thickness of the inorganic deposited layer varies depending on the type of the components constituting the inorganic deposited layer, and is usually in the range of 2 to 500 nm. Selecting the barrier property of the multilayer structure in this range, the machine The thickness of the mechanical properties is good. When the thickness of the inorganic vapor-deposited layer is less than 2 nm, the reproducibility of the barrier property of the inorganic vapor-deposited layer of oxygen or water vapor tends to be lowered, and the inorganic vapor-deposited layer may not exhibit sufficient barrier properties. When the thickness of the inorganic deposited layer exceeds 500 nm, when the multilayered structure is stretched or bent, the barrier property of the inorganic deposited layer tends to be lowered. The thickness of the inorganic deposited layer is preferably in the range of 5 to 200 nm, and more preferably in the range of 10 to 100 nm.

Examples of the method for forming the inorganic deposited layer include a vacuum deposition method, a sputtering method, an ion plating method, and a chemical vapor deposition method (CVD). Among these, from the viewpoint of productivity, a vacuum deposition method is preferred. The heating method for performing vacuum vapor deposition is preferably any one of an electron beam heating method, a resistance heating method, and an induction heating method. Further, in order to improve the adhesion to the vapor deposition substrate on which the inorganic vapor deposition layer is formed and the denseness of the inorganic vapor deposition layer, plasma assisted method or ion beam assisted method may be used for vapor deposition. . Moreover, in order to improve the transparency of the inorganic vapor deposition layer, a vapor deposition method in which a reaction is formed by blowing oxygen or the like may be employed during vapor deposition.

The thickness of the base material (X) in the form of a layer is preferably in the range of 1 to 1000 μm, more preferably in the range of 5 to 500 μm, from the viewpoint of satisfactory mechanical strength and workability of the obtained multilayer structure. More preferably, it is in the range of 9 to 200 μm.

[Next layer (H)]

In the multilayer structure, the layer (Y) and/or the layer (Z) may be laminated in direct contact with the substrate (X), and the layer (Y) and/or the layer (Z) may also be disposed on the substrate (X). An adhesive layer (H) between the layer (Y) and/or the layer (Z) is laminated on the substrate (X). According to this configuration, the adhesion between the substrate (X) and the layer (Y) and/or the layer (Z) may be improved. Then layer (H) can also It is formed by a resin. The adhesive layer (H) composed of an adhesive resin can be formed by treating the surface of the substrate (X) with a conventional anchor coating agent or applying a conventional adhesive to the surface of the substrate (X). The binder is preferably a two-liquid reaction type polyurethane-based adhesive which is obtained by mixing and reacting a polyisocyanate component and a polyol component. Further, by adding an additive such as a conventional decane coupling agent to the anchor coating agent or the adhesive, the adhesion can be further improved. Preferable examples of the decane coupling agent include a decane coupling agent having a reactive group such as an isocyanate group, an epoxy group, an amine group, a ureido group or a thiol group. By strongly bonding the substrate (X) and the layer (Y) and/or the layer (Z) by the adhesive layer (H), it is possible to more effectively suppress the multilayer structure by performing processing such as printing or lamination. Gas barrier properties and deterioration of appearance.

The strength of the multilayer structure can be increased by thickening the adhesive layer (H). However, if the layer (H) is excessively thickened, the appearance tends to deteriorate. The thickness of the layer (H) is preferably in the range of 0.03 to 0.18 μm. According to this configuration, when the multilayer structure is subjected to processing such as printing or lamination, the gas barrier property and the deterioration of the appearance can be more effectively suppressed, and the drop strength of the protective sheet using the multilayer structure can be improved. The thickness of the layer (H) is preferably in the range of 0.04 to 0.14 μm, more preferably in the range of 0.05 to 0.10 μm.

[Composition of multilayer structure]

The multilayer structure (layered body) may be composed only of the substrate (X), the layer (Y), and the layer (Z), or may be composed only of the substrate (X), the layer (Y), the layer (Z), and the subsequent layer ( H) Composition. The multilayer structure may comprise a plurality of layers (Y) and/or a plurality of layers (Z). Further, the multilayer structure may further contain other members than the substrate (X), the layer (Y), the layer (Z), and the subsequent layer (H) (for example, a thermoplastic resin film layer or another layer such as an inorganic vapor deposition layer). A multilayer structure having such other members (other layers, etc.) can be manufactured by, for example, directly or via a layer (H) And laminating the layer (Z) after the substrate (X), further directly or via the subsequent layer, and then forming or forming the other member (other layers, etc.). Such other members (other layers, etc.) are contained in the multilayer structure, whereby the characteristics of the multilayer structure or the imparting of new characteristics can be improved. For example, it is possible to impart heat sealability to the multilayer structure or to further improve barrier properties and mechanical properties.

In particular, by making the outermost layer of the multilayered structure a polyolefin layer, it is possible to impart heat sealability to the multilayered structure or to improve mechanical properties of the multilayered structure. The polyolefin is preferably polypropylene or polyethylene from the viewpoints of heat sealability, improvement of mechanical properties, and the like. Further, in order to improve the mechanical properties of the multilayered structure, it is preferable that the other layer is at least one selected from the group consisting of a film made of a polyester, a film made of polyamine, and A film composed of a polymer containing a hydroxyl group. From the viewpoint of improvement in mechanical properties, the polyester is preferably polyethylene terephthalate (PET), the polyamine is preferably nylon-6, and the hydroxyl group-containing polymer is preferably ethylene-ethylene. Alcohol copolymer. Further, a layer composed of an anchor coating layer and an adhesive may be provided between the layers as needed.

The multilayer structure can be formed by laminating at least one set of layers (Y) and (Z) and at least one other layer (including a substrate). Examples of the other layer include a polyester layer, a polyamide layer, a polyolefin layer (which may be a pigment-containing polyolefin layer, a heat-resistant polyolefin layer, or a biaxially stretched heat-resistant polyolefin layer), and a hydroxyl group-containing layer. A polymer layer (for example, an ethylene-vinyl alcohol copolymer layer), an inorganic deposited film layer, a thermoplastic elastomer layer, and an adhesive layer. As long as the multilayer structure contains the substrate, the layer (Y), and the layer (Z), and at least one of the layers (Y) and the layer (Z) are adjacent to each other and laminated, the other layers and the layers (Y) and layers ( The number of Z) and the order of lamination are not particularly limited. Further, a preferred example is a structure in which at least one set of the substrate (X), the layer (Y), and the layer (Z) are laminated in the order of the substrate (X) / layer (Y) / layer (Z). Multi-layer structure.

[protective sheet for electronic devices]

According to a preferred embodiment of the present invention, the protective sheet can achieve one or both of the following properties. The thickness of one of the preferred layers (Y) (the total thickness of each layer (Y) when the multilayer structure has two or more layers (Y)) is a multilayer of 1.0 μm or less (for example, 0.5 μm or more and 1.0 μm or less). The structure can achieve the following performance. Further, the measurement conditions of the oxygen permeability will be described in detail by way of examples.

(Performance 1) The oxygen permeability of the protective sheet under conditions of 20 ° C and 85% RH is 2 ml / (m ² ‧ day ‧ atm) or less, preferably 1.5 ml / (m ² ‧ day ‧ atm) or less.

(Performance 2) The oxygen permeability of the protective sheet under the conditions of 20 ° C and 85% RH after the protective sheet was held in a state of uniaxially stretching 5% under conditions of 23 ° C and 50% RH for 5 minutes. It is 4 ml/(m ² ‧day‧atm) or less, preferably 2.5 ml/(m ² ‧day‧atm) or less.

Since the protective sheet in the electronic device of the present invention has the above-described multilayer structure, it has excellent gas barrier properties, and can maintain gas barrier properties at a high level even when subjected to physical stress such as deformation or punching. The protective sheet in the electronic device of the present invention may have a barrier property against water vapor in addition to gas barrier properties. In this case, the water vapor barrier property can be maintained at a high level even when subjected to physical stress such as deformation or punching.

The protective sheet in the electronic device of the present invention can also be used as a film of a substrate film such as a substrate film for an LCD, a substrate film for an organic EL, or a substrate film for an electronic paper. Further, the electronic device to be protected is not limited to the above-described ones, and may be, for example, an IC tag (IC tag), an optical communication device, a fuel cell, or the like.

The protective sheet may also include a surface protective layer disposed on one surface or both surfaces of the multilayer structure. The surface protective layer is preferably a layer composed of a resin which is less likely to cause scratches. Again, such as A surface protective layer which is sometimes used for an outdoor device like a solar battery is preferably made of a resin having high weather resistance (for example, light resistance). Further, when it is desired to protect a surface through which light must be transmitted, a surface protective layer having high light transmittance is preferred. Examples of materials for the surface protective layer (surface protective film) include acrylic resin, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, ethylene-tetrafluoroethylene copolymer, and polytetrafluoroethylene. , 4-fluorinated ethylene-perchloroalkoxy copolymer, 4-fluorinated ethylene-6-fluorinated propylene copolymer, 2-ethylene-4-fluorinated ethylene copolymer, poly-3-fluorinated vinyl chloride, polyfluorinated Ethylene and polyvinyl fluoride. An example of the protective sheet includes an acrylic resin layer disposed on a surface. Further, in order to improve the durability of the surface protective layer, various additives (for example, ultraviolet absorbers) may be added to the surface protective layer. A preferred example of the surface protective layer having high weather resistance is an acrylic resin layer to which an ultraviolet absorber is added. Examples of the ultraviolet absorber include conventional ultraviolet absorbers, and examples thereof include ultraviolet absorbers including a benzotriazole system, a diphenylketone system, a salicylate system, a cyanoacrylate system, a nickel system, and a triazine system. Further, other stabilizers, light stabilizers, antioxidants, and the like may be used in combination.

When the protective sheet is bonded to the sealing material of the sealed electronic device body, the protective sheet preferably contains a bonding resin layer which can improve the adhesion to the sealing material. The bonding resin layer may, for example, be a polyethylene terephthalate (EVA easy-adhesion PET film) which can improve the adhesion to EVA.

The respective layers constituting the protective sheet can be joined using, for example, a conventional adhesive and the above-mentioned adhesive layer.

[Manufacturing method of multilayer structure]

The method of manufacturing the multilayer structure will be described below.

The method for producing a multilayer structure preferably comprises forming by coating a coating liquid (V) In step (IV) of layer (Z), the coating liquid (V) contains a polymer (E) containing a monomer unit having a phosphorus atom.

Further, when the layer (Y) of the multilayered structure is a layer (YB) of an aluminum vapor deposited layer or a vapor deposited layer (YC) of alumina, the layer (YB) and the layer (YC) can be generally Since the vapor deposition method is formed, detailed description is omitted. In the following, the case where the layer (Y) of the multilayered structure is the layer (YA) containing the reaction product (R), which is a metal oxide containing at least aluminum ( A) is formed by reacting with a phosphorus compound (B). Further, the formation method of the layer (Z) (step (IV) described later) can be the same in any of the layers (Y), the layers (YA), the layers (YB), and the layers (YC). method.

When the layer (Y) of the multilayer structure is a layer (YA) containing a reaction product (R), the reaction product (R) is a metal oxide (A) containing at least aluminum and a phosphorus compound (B). When the reaction is obtained, the method for producing the multilayered structure preferably comprises the steps (I), (II), (III) and (IV). In the step (I), a metal oxide (A) containing at least aluminum, a compound containing at least one compound capable of reacting with the metal oxide (A), and a solvent are mixed, whereby the metal oxide is contained ( A), at least one of the compounds and a coating liquid (U) of the solvent. In the step (II), a coating liquid (U) is applied onto the substrate (X) to form a layer (YA) precursor layer on the substrate (X). In the step (III), the precursor layer is heat-treated at a temperature of 140 ° C or higher to form a layer (YA) on the substrate (X). Then, in the step (IV), the coating liquid (V) containing the polymer (E) is applied to form a layer (Z) containing a monomer unit having a phosphorus atom. Further, typically, the above steps are carried out in the order of (I), (II), (III), (IV), when the layer (Z) is formed on the substrate (X) and the layer (YA). In the meantime, step (IV) can be carried out before step (II). Further, as will be described later, the step may be carried out after the step (IV). Step (III).

[Step (I)]

At least one compound containing a site reactive with the metal oxide (A) used in the step (I) may be referred to as "at least one compound (Z)" hereinafter. In the step (I), at least a metal oxide (A) and at least one compound (Z) are mixed with a solvent. In one aspect, in the step (I), a raw material containing a metal oxide (A) and at least one compound (Z) is reacted in a solvent. The raw material may contain other compounds in addition to the metal oxide (A) and at least one compound (Z). Typically, the metal oxide (A) is mixed in a particle form.

The coating liquid (U), the molar number N _M of the metal atom (M) constituting the metal oxide (A) and the molar number N _P of the phosphorus atom contained in the phosphorus compound (B) satisfy 1.0 ≦ ( The relationship between the molar number N _M ) / (mole number N _P ) ≦ 3.6. The preferred range of values of (molar number N _M ) / (mole number N _P ) is as described above, and thus the overlapping description will be omitted.

At least one compound (Z) contains a phosphorus compound (B). The number of moles of the metal atom contained in at least one of the compounds (Z) is preferably in the range of from 0 to 1 times the number of moles of the phosphorus atom contained in the phosphorus compound (B). Typically, at least one compound (Z) is a compound containing a plurality of sites reactive with the metal oxide (A), and the molar number of the metal atom contained in at least one compound (Z) is phosphorus. The range of 0 to 1 times the number of moles of the phosphorus atom contained in the compound (B).

The ratio of (the number of moles of the metal atom contained in at least one compound (Z)) / (the number of moles of the phosphorus atom contained in the phosphorus compound (B)) is in the range of 0 to 1 (for example, 0 to 0.9) The range), whereby a multilayer structure having more excellent gas barrier properties can be obtained. In order to enter one The step of increasing the gas barrier property of the multilayer structure is preferably 0.3 or less, more preferably 0.05 or less, still more preferably 0.01 or less, and may be 0. Typically, at least one compound (Z) is composed only of the phosphorus compound (B). In the step (I), the above ratio can be easily lowered.

Step (I) preferably comprises the following steps (a) to (c).

Step (a): a step of preparing a liquid (S) containing a metal oxide (A).

Step (b): a step of preparing a solution (T) containing the phosphorus compound (B).

Step (c): a step of mixing the liquid (S) obtained in the above steps (a) and (b) with the solution (T).

Step (b) may also be carried out before step (a), or simultaneously with step (a), or after step (a). The following is more specifically described for each step.

In the step (a), the liquid (S) containing the metal oxide (A) is prepared. The liquid (S) is a solution or dispersion. The liquid (S) can be prepared by a method such as that employed in a conventional sol-gel method. For example, the above compound (L) component, water, and an optional acid catalyst or an organic solvent may be mixed, and the compound (L) component may be condensed by a conventional method using a sol-gel method. Or hydrolytic condensation to prepare. The dispersion of the metal oxide (A) obtained by condensation or hydrolysis condensation of the compound (L) component can be directly used as the liquid (S) containing the metal oxide (A). However, the dispersion may be subjected to a specific treatment as needed (the above-mentioned degumming, addition or subtraction of a solvent for controlling the concentration, etc.).

The step (a) may further comprise a step of condensing (for example, hydrolytic condensation) at least one selected from the group consisting of the compound (L) and the hydrolyzate of the compound (L). Specifically, the step (a) may further comprise a step of condensing or hydrolytically condensing at least one selected from the group consisting of a partial condensation of the materials described below, the materials being the compound (L), Compound (L) a partial hydrolyzate, a complete hydrolyzate of the compound (L), a partial hydrolysis condensate of the compound (L), and a complete hydrolyzate of the compound (L).

Further, another example of the method for preparing the liquid (S) is a method comprising the following steps. First, the metal is vaporized into a metal atom by heat, and the metal atom is brought into contact with a reaction gas (oxygen), whereby molecules and clusters of the metal oxide are generated. Thereafter, the particles are instantaneously cooled to thereby produce particles of the metal oxide (A) having a small particle diameter. Next, the particles are dispersed in water or an organic solvent, whereby a liquid (S) (a dispersion containing a metal oxide (A)) is obtained. In order to improve the dispersibility to water or an organic solvent, the particles of the metal oxide (A) may be subjected to surface treatment or a stabilizer such as a surfactant may be added. Further, the dispersibility of the metal oxide (A) can also be improved by controlling the pH.

Still another example of the method for preparing the liquid (S) is to pulverize the bulk metal oxide (A) using a pulverizer such as a ball mill or a jet mill to disperse it in water or organic. A solvent is used to form a liquid (S) (a dispersion containing a metal oxide (A)). However, in this case, it may be difficult to control the distribution of the shape and size of the particles of the metal oxide (A).

The kind of the organic solvent which can be used in the step (a) is not particularly limited, and for example, an alcohol such as methanol, ethanol, isopropanol or n-propanol can be preferably used.

The content of the metal oxide (A) in the liquid (S) is preferably in the range of 0.1 to 40% by mass, more preferably in the range of 1 to 30% by mass, still more preferably in the range of 2 to 20% by mass. Inside.

The solution (T) of the phosphorus-containing compound (B) is prepared in the step (b). The solution (T) can be prepared by dissolving the phosphorus compound (B) in a solvent. When the phosphorus compound (B) has low solubility At the time, the dissolution can be promoted by heat treatment and ultrasonic treatment.

The solvent used for the preparation of the solution (T) can be appropriately selected depending on the kind of the phosphorus compound (B), but the water content is preferred. The solvent may also contain an alcohol such as methanol or ethanol as long as it does not interfere with the dissolution of the phosphorus compound (B); tetrahydrofuran, Alkane, three An ether such as trioxane or dimethoxyethane; a ketone such as acetone or methyl ethyl ketone; a glycol such as ethylene glycol or propylene glycol; methyl acesulfame or ethyl acesulfame; a diol derivative such as n-butyl cyanidin; glycerin; acetonitrile; guanamine such as dimethylformamide; dimethylsulfoxide; sulfolane.

The content of the phosphorus compound (B) in the solution (T) is preferably in the range of 0.1 to 99% by mass, more preferably in the range of 0.1 to 95% by mass, still more preferably in the range of 0.1 to 90% by mass. . Further, the content of the phosphorus compound (B) in the solution (T) may be in the range of 0.1 to 50% by mass, may be in the range of 1 to 40% by mass, or may be in the range of 2 to 30% by mass. Inside.

In the step (c), the liquid (S) and the solution (T) are mixed. When the liquid (S) and the solution (T) are mixed, in order to suppress the local reaction, it is preferred to carry out the mixing while suppressing the addition rate and vigorously stirring. At this time, the solution (T) may be added to the liquid (S) during stirring, or the liquid (S) may be added to the stirred solution (T). The temperature of the liquid (S) and the temperature of the solution (T) in the step (c) are preferably 50 ° C or less, more preferably 30 ° C or less, and even more preferably 20 ° C or less. Since the temperature at the time of mixing is set to 50 ° C or lower, the metal oxide (A) and the phosphorus compound (B) can be uniformly mixed, and the gas barrier properties of the obtained multilayered structure can be improved. Further, the stirring is continued for about 30 minutes from the end of the mixing, whereby the coating liquid (U) having excellent storage stability can be obtained.

Further, the coating liquid (U) may contain the polymer (C). The coating liquid (U) is contained The method of the polymer (C) is not particularly limited. It is also possible to dissolve the polymer (C) in the form of a powder or a pellet, for example, in a liquid (S), a solution (T), or a mixture of a liquid (S) and a solution (T). Further, a solution of the polymer (C) may be added to the liquid (S), the solution (T), or a mixture of the liquid (S) and the solution (T) to be mixed. Further, a liquid (S), a solution (T), or a mixture of the liquid (S) and the solution (T) may be added to the solution of the polymer (C) to be mixed. By mixing the liquid (S) with the solution (T) in step (c) by allowing the liquid (S) or the solution (T) to contain the polymer (C) before the step (c), the metal The reaction rate of the oxide (A) and the phosphorus compound (B) is moderated, and as a result, the coating liquid (U) excellent in stability over time can be obtained.

The layer (YA)-containing multilayer structure can be easily produced by allowing the coating liquid (U) to contain the polymer (C), and the layer (YA) contains the polymer (C).

The coating liquid (U) may contain at least one acid compound (D) selected from the group consisting of acetic acid, hydrochloric acid, nitric acid, trifluoroacetic acid, and trichloroacetic acid, as needed. Hereinafter, the at least one acid compound (D) may be simply referred to as "acid compound (D)". The method of causing the coating liquid (U) to contain the acid compound (D) is not particularly limited. For example, the acid compound (D) may be directly added to the liquid (S), the solution (T), or the mixture of the liquid (S) and the solution (T) to be mixed. Further, a solution of the acid compound (D) may be added to the liquid (S), the solution (T), or a mixture of the liquid (S) and the solution (T) to be mixed. Further, a liquid (S), a solution (T), or a mixture of the liquid (S) and the solution (T) may be added to the solution of the acid compound (D) to be mixed. By mixing the liquid (S) with the solution (T) in step (c) by causing any one of the liquid (S) or the solution (T) to contain the acid compound (D) before the step (c), the metal The reaction rate of the oxide (A) and the phosphorus compound (B) is moderated, and as a result, the coating liquid (U) excellent in stability over time can be obtained.

In the coating liquid (U) containing the acid compound (D), the reaction between the metal oxide (A) and the phosphorus compound (B) is suppressed, and precipitation and aggregation of the reactant in the coating liquid (U) can be suppressed. Therefore, the appearance of the obtained multilayered structure is improved by using the coating liquid (U) containing the acid compound (D). In addition, since the boiling point of the acid compound (D) is 200 ° C or lower, the acid compound (D) can be easily removed from the layer (YA) by volatilizing the acid compound (D) or the like during the production of the multilayer structure.

The content of the acid compound (D) in the coating liquid (U) is preferably in the range of 0.1 to 5.0% by mass, more preferably 0.5 to 2.0% by mass. Among these ranges, the effect of the addition of the acid compound (D) can be obtained, and the removal of the acid compound (D) is easy. When the acid component remains in the liquid (S), the amount of the acid compound (D) to be added may be determined in consideration of the residual amount thereof.

The liquid obtained by mixing in the step (c) can be used as the coating liquid (U) as it is. In this case, the solvent contained in the liquid (S) and the solution (T) is usually a solvent of the coating liquid (U). Further, the liquid obtained by mixing in the step (c) may be treated to prepare a coating liquid (U). For example, treatment such as adding an organic solvent, adjusting the pH, adjusting the viscosity, and adding an additive may be performed.

The liquid obtained by mixing in the step (c) may be added to the organic solvent in a range that does not impede the stability of the obtained coating liquid (U). It is possible to apply the coating liquid (U) to the substrate (X) in the step (II) by the addition of an organic solvent. The organic solvent is preferably one which can be uniformly mixed in the obtained coating liquid (U). Preferred examples of the organic solvent include alcohols such as methanol, ethanol, n-propanol, and isopropanol; tetrahydrofuran, and Alkane, three Ethers such as alkane and dimethoxyethane; ketones such as acetone, methyl ethyl ketone, methyl vinylketone, methyl isopropanone; glycols such as ethylene glycol and propylene glycol; methyl acesulfame, B Glycerin derivatives such as acesulfame, n-butyl cyanidin; glycerin; acetonitrile; guanamine such as dimethylformamide or dimethylacetamide; dimethyl hydrazine; Wait.

The solid content concentration of the coating liquid (U) is preferably in the range of 1 to 20% by mass from the viewpoint of the storage stability of the coating liquid (U) and the coating property of the coating liquid (U) on the substrate. More preferably, it is in the range of 2 to 15% by mass, and more preferably in the range of 3 to 10% by mass. The solid content concentration of the coating liquid (U) can be calculated by, for example, adding a predetermined amount of the coating liquid (U) to the culture dish, and separately removing the volatile component such as a solvent at a temperature of 100 ° C from the culture dish. The mass of the residual solid component was calculated by dividing the mass of the coating liquid (U) initially added. In this case, it is preferred to measure the amount of the solid component remaining after drying for a certain period of time so as to obtain the solid component concentration as the mass of the residual solid component when the mass difference of two consecutive times is negligible.

The pH of the coating liquid (U) is preferably in the range of 0.1 to 6.0, more preferably in the range of 0.2 to 5.0, from the viewpoints of storage stability of the coating liquid (U) and gas barrier properties of the multilayer structure. More preferably, it is in the range of 0.5 to 4.0.

The pH of the coating liquid (U) can be adjusted by a known method, and can be adjusted by adding, for example, an acidic compound or a basic compound. Examples of the acidic compound include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, butyric acid, and ammonium sulfate. Examples of the basic compound include sodium hydroxide, potassium hydroxide, ammonia, trimethylamine, pyridine, sodium carbonate, and sodium acetate.

The coating liquid (U) changes its state over time, and eventually becomes a gel-like composition or tends to cause precipitation. The time until the change to such a state depends on the composition of the coating liquid (U). In order to stably apply the coating liquid (U) to the coated substrate (X), it is preferred that the coating liquid (U) is stable in viscosity over a long period of time. The solution (U) is preferably prepared such that when the viscosity at the end of step (I) is used as the reference viscosity and is allowed to stand at 25 ° C for 2 days, by Brookfield The viscosity measured by a viscometer (B type viscometer: 60 rpm) was within 5 times of the reference viscosity. When the viscosity of the coating liquid (U) is in the above range, a multilayer structure having excellent storage stability and more excellent gas barrier properties can be obtained.

For the method of adjusting the viscosity of the coating liquid (U) to the above range, for example, a method of adjusting the concentration of the solid component, adjusting the pH, and adding a viscosity modifier may be employed. Examples of the viscosity modifier include carboxymethylcellulose, starch, bentonite, tragacanth gum, stearate, alginate, methanol, ethanol, n-propanol, and isopropanol.

The coating liquid (U) may contain other substances than the above substances as long as the effects of the present invention can be obtained. For example, the coating liquid (U) may also contain an inorganic metal salt such as a carbonate, a hydrochloride, a nitrate, a hydrogencarbonate, a sulfate, a hydrogen sulfate, a borate or an aluminate; an oxalate, an acetate, or a tartaric acid. Organic acid metal salts such as salts and stearates; acetonitrile and acetone metal complexes (such as aluminum acetonate), cyclopentadienyl metal complexes (titanocene, etc.), cyano metal complexes, etc. Metal complex; layered clay compound; crosslinking agent; polymer compound other than polymer (C); plasticizer; antioxidant; ultraviolet absorber; flame retardant.

[Step (II)]

In the step (II), a layer (YA) precursor layer is formed on the substrate (X) by applying a coating liquid (U) onto the substrate (X). The coating liquid (U) may also be applied directly to at least one side of the substrate (X). Further, before applying the coating liquid (U), the surface of the substrate (X) may be treated with a conventional anchor coating agent, or a known adhesive may be applied to the surface of the substrate (X). The adhesive layer (H) is formed in advance on the surface of the substrate (X). Further, the coating liquid (U) may be applied to the layer (Z) previously formed on the substrate (X) by the step (IV) described later, whereby the layer (YA) is formed on the layer (Z). Layer of matter.

Further, the coating liquid (U) may be subjected to deaeration and/or defoaming treatment as needed. The method of degassing and/or defoaming treatment is, for example, a method using vacuuming, heating, centrifugation, ultrasonication, or the like, and a method including evacuation is preferably used.

The viscosity of the coating liquid (U) at the time of coating in the step (II), that is, the viscosity measured by a Brookfieid type rotational viscometer (SB type viscometer: rotor No. 3, rotation speed: 60 rpm), was applied. The temperature at the time is preferably 3,000 mPa ‧ or less, more preferably 2,000 mPa ‧ s or less. By the viscosity of 3,000 mPa ‧ s or less, a multilayer structure in which the flatness of the coating liquid (U) is improved and the appearance is further improved can be obtained. The viscosity of the coating liquid (U) at the time of coating in the step (II) can be adjusted according to the concentration, the temperature, the stirring time after mixing in the step (c), and the stirring strength. For example, by stirring the mixing after the mixing of the step (c), the viscosity may be lowered.

The method of applying the coating liquid (U) to the substrate (X) is not particularly limited, and a conventional method can be employed. Preferred methods include casting, dipping, roll coating, gravur coating, screen coating, reverse coating, and spray coating. (spray coating), kiss coating, die coating, metaling bar coating, sealing doctor coating, chamber doctor coating, curtain coating Curtain coating, etc.

Usually, in the step (II), the layer (YA) precursor layer is formed by removing the solvent in the coating liquid (U). The method of removing the solvent is not particularly limited, and a conventional drying method can be used. Specifically, a drying method such as a hot air drying method, a hot roll contact method, an infrared heating method, or a microwave heating method may be used singly or in combination. The drying temperature is preferably lower than the flow starting temperature of the substrate (X) by 0 to 15 ° C or more. When the coating liquid (U) contains the polymer (C), the drying temperature is preferably 15 to 20 ° C or more lower than the thermal decomposition starting temperature of the polymer (C). The drying temperature is preferably 70 The range of ~200 ° C, more preferably in the range of 80 to 180 ° C, and even more preferably in the range of 90 to 160 ° C. The removal of the solvent can be carried out under either a normal pressure or a reduced pressure. Further, the solvent may be removed by heat treatment in the step (III) described later.

In the case of a two-layer layer (YA) of a layered substrate (X), the solvent can be removed after the coating liquid (U) is applied to one side of the substrate (X), thereby forming the first layer ( The first layer (YA) (the precursor layer), and then the coating liquid (U) is applied to the other side of the substrate (X), and then the solvent is removed, thereby forming the second layer (the second layer (YA) ) before the drive layer). The composition of the coating liquid (U) applied to each surface may be the same or different.

When a plurality of area layer layers (YA) having a three-dimensional shape of the substrate (X) are used, a layer (layer (YA) precursor layer) may be formed on each side by the above method. Alternatively, the coating liquid (U) is simultaneously applied to a plurality of faces of the substrate (X) and dried, whereby a plurality of layers (layer (YA) precursor layer) are simultaneously formed.

[Step (III)]

In the step (III), the precursor layer (layer (YA) precursor layer) formed in the step (II) is heat-treated at a temperature of 140 ° C or higher, thereby forming a layer (YA).

In the step (III), a reaction in which particles of the metal oxide (A) are bonded to each other via a phosphorus atom (phosphorus atom derived from the phosphorus compound (B)) is carried out. From another viewpoint, in the step (III), a reaction for forming the reaction product (R) is carried out. In order to sufficiently carry out the reaction, the temperature of the heat treatment is 140 ° C or higher, more preferably 170 ° C or higher, and still more preferably 190 ° C or higher. When the heat treatment temperature is low, the time required for obtaining a sufficient degree of reaction is long, which may cause a decrease in productivity. The preferred upper limit of the temperature of the heat treatment differs depending on the type of the substrate (X) and the like. For example, when a thermoplastic resin film composed of a polyamide resin is used as a substrate (X), the temperature of the heat treatment It is preferably 190 ° C or lower. Further, when a thermoplastic resin film composed of a polyester resin is used as the substrate (X), the temperature of the heat treatment is preferably 220 ° C or lower. The heat treatment can be carried out in air, under a nitrogen atmosphere, or under an argon atmosphere.

The heat treatment time is preferably in the range of 0.1 second to 1 hour, more preferably in the range of 1 second to 15 minutes, and even more preferably in the range of 5 to 300 seconds. One example of the heat treatment is carried out in the range of 140 to 220 ° C for 0.1 second to 1 hour. Further, another example of the heat treatment is performed in the range of 170 to 200 ° C for 5 to 300 seconds (for example, 10 to 300 seconds).

The method of the present invention for producing a multilayer structure may also comprise the step of irradiating the layer (YA) of the precursor layer or layer (YA) with ultraviolet rays. The ultraviolet irradiation can be carried out at any stage after the step (II) (for example, after the solvent removal of the applied coating liquid (U) is substantially completed). This method is not particularly limited, and a conventional method can be used. The wavelength of the ultraviolet ray to be irradiated is preferably in the range of 170 to 250 nm, more preferably in the range of 170 to 190 nm and/or in the range of 230 to 250 nm. Further, instead of ultraviolet irradiation, irradiation with radiation such as an electron beam or a γ-ray may be performed. By performing ultraviolet irradiation, there is a case where the gas barrier properties of the multilayer structure can be exhibited at a higher level.

In order to arrange the adhesive layer (H) between the substrate (X) and the layer (YA), the surface of the substrate (X) is treated with a conventional anchor coating agent before the coating liquid (U) is applied. When a conventional adhesive is applied to the surface of the substrate (X), it is preferred to carry out the ripening treatment. Specifically, it is preferred to place the substrate (X) coated with the coating liquid (U) at a relatively low temperature for a long time after applying the coating liquid (U) and before the heat treatment step of the step (III). . The temperature of the ripening treatment is preferably less than 110 ° C, more preferably 100 ° C or less, still more preferably 90 ° C or less. Further, the temperature of the ripening treatment is preferably 10 ° C or higher, more preferably 20 ° C or higher, and still more preferably 30 ° C or higher. Mature treatment The time is preferably in the range of 0.5 to 10 days, more preferably in the range of 1 to 7 days, and even more preferably in the range of 1 to 5 days. By performing such a ripening treatment, the adhesion between the substrate (X) and the layer (YA) becomes stronger.

[Step (IV)]

In the step (IV), a layer (Z) is formed on the substrate (X) (or on the layer (Y)) by coating the coating liquid (V), and the coating liquid (V) contains a polymer (E). ), which contains monomer units having a phosphorus atom. Usually, the coating liquid (V) is a solution in which the polymer (E) is dissolved in a solvent.

The coating liquid (V) can be prepared by dissolving the polymer (E) in a solvent, or a solution obtained by forming the polymer (E) can be used as it is. When the solubility of the polymer (E) is low, dissolution can be promoted by applying heat treatment or ultrasonic treatment.

The solvent to be used for the coating liquid (V) may be appropriately selected depending on the type of the polymer (E), and is preferably water, an alcohol or a mixed solvent of these. The solvent may also contain tetrahydrofuran, as long as it does not interfere with the dissolution of the polymer (E). Alkane, three Ethers such as alkane and dimethoxyethane; ketones such as acetone and methyl ethyl ketone; diols such as ethylene glycol and propylene glycol; and diols such as methyl cyproterone, ethyl cyanidin, n-butyl cyanidin Derivatives; glycerin; acetonitrile; decylamine such as dimethylformamide; dimethyl hydrazine;

The solid content concentration of the polymer (E) in the coating liquid (V) is preferably in the range of 0.1 to 60% by mass, more preferably 0.5 to 50, from the viewpoint of solution storage stability and coatability. Within the range of % by mass, more preferably in the range of 1.0 to 40% by mass. The solid content concentration can be determined by the same method as described for the coating liquid (U).

The pH of the solution of the polymer (E) is preferably in the range of 0.1 to 6.0, more preferably 0.2, from the viewpoints of storage stability of the coating liquid (V) and gas barrier properties of the multilayer structure. The range of ~5.0 is more preferably in the range of 0.5 to 4.0.

The pH of the coating liquid (V) can be adjusted by a conventional method, and can be adjusted by adding, for example, an acidic compound or a basic compound. Examples of the acidic compound include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, butyric acid, and ammonium sulfate. Examples of the basic compound include sodium hydroxide, potassium hydroxide, ammonia, trimethylamine, pyridine, sodium carbonate, and sodium acetate.

Further, when it is necessary to control the viscosity of the coating liquid (V), for example, a method of adjusting the concentration of the solid component, adjusting the pH, and adding a viscosity modifier may be employed. Examples of the viscosity modifier include carboxymethylcellulose, starch, bentonite, tragacanth, stearate, alginate, methanol, ethanol, n-propanol, and isopropanol.

Further, the coating liquid (V) may be subjected to deaeration and/or defoaming treatment as needed. The method of degassing and/or defoaming treatment is, for example, a method using vacuuming, heating, centrifugation, ultrasonication, etc., and a method including evacuation is preferably used.

The viscosity of the coating liquid (V) at the time of coating in the step (IV), that is, the viscosity measured by a Brookfield type rotary viscometer (SB type viscometer: rotor No. 3, rotation speed: 60 rpm), in coating The temperature is preferably 1000 mPa ‧ or less, more preferably 500 mPa ‧ or less. By the viscosity of 1000 mPa·s or less, a multilayer structure in which the flatness of the coating liquid (V) is improved and the appearance is further improved can be obtained. The viscosity of the coating liquid (V) at the time of coating in the step (IV) can be adjusted by the concentration and temperature.

The method of applying the solution of the coating liquid (V) to the substrate (X) or the layer (Y) is not particularly limited, and a conventional method can be employed. Preferred methods include casting, dipping, roll coating, gravure coating, screen printing, reverse coating, spray coating, conformal coating, die coating, and metal. Bar coating method, sealed scraper and coating method, curtain coating Law and so on.

Usually, in the step (IV), the layer (Z) is formed by removing the solvent in the coating liquid (V). The method of removing the solvent is not particularly limited, and a conventional drying method can be used. Specifically, a drying method such as a hot air drying method, a hot roll contact method, an infrared heating method, or a microwave heating method may be used singly or in combination. The drying temperature is preferably lower than the flow starting temperature of the substrate (X) by 0 to 15 ° C or more. The drying temperature is preferably in the range of 70 to 200 ° C, more preferably in the range of 80 to 180 ° C, and even more preferably in the range of 90 to 160 ° C. The removal of the solvent can be carried out under either a normal pressure or a reduced pressure. Further, the solvent may be removed by heat treatment in the step (III) described later.

When the layer (Z) is laminated on both sides of the layered substrate (X) with or without the layer (Y), the coating liquid (V) can be applied to one surface and the solvent can be removed, thereby forming the first Layer 1 (Z), and then the coating liquid (V) is applied to the other side, and the solvent is removed, thereby forming the second layer (Z). The composition of the coating liquid (V) applied to each surface may be the same or different.

When a plurality of faces of the substrate (X) having a three-dimensional shape are laminated (Z) with or without the layer (Y), the layer (Z) can be formed separately on each face by the above method. Alternatively, the coating liquid (V) is simultaneously applied to a plurality of faces and dried, whereby a plurality of layers (Z) are simultaneously formed.

As described above, the steps are typically carried out in the order of (I), (II), (III), (IV), but when the layer (Z) is formed on the substrate (X) and the layer (Y) Step (IV) may be carried out before step (II), and step (III) may also be carried out after step (IV). From the viewpoint of obtaining a multilayer structure excellent in appearance, it is preferred to carry out the step (IV) after the step (III).

The multilayer structure obtained in this way can be directly used to constitute a container wall structure Multi-layer structure of pieces. However, the multilayer structure may be further formed or formed into other layers (other layers or the like) as described above to form a multilayer structure. This component can then be carried out using conventional methods.

In one aspect, the method for producing a multilayer structure may further comprise the steps of: forming a layer (W) containing an aluminum atom (Y), and forming a coating liquid (V) containing the polymer (E) to form In the step (IV) of the above layer (Z), the polymer (E) contains a monomer unit having a phosphorus atom. As described above, when layer (Y) is layer (YA), step (W) may also include steps (I), (II), and (III). Further, when the layer (Y) is a layer (YB) or a layer (YC), the step (W) may also include a step of forming the layers by a vapor deposition method.

[Examples]

The present invention will be more specifically described by the following examples, but the present invention is not limited by the following examples. Further, each measurement and evaluation of the examples and comparative examples was carried out by the following method.

(1) Infrared absorption spectrum of layer (Y)

The infrared absorption spectrum of the layer (YA) was measured by the following method.

First, an infrared absorption spectrum was measured for a layer (YA) laminated on a substrate (X) using a Fourier-Transform Infrared Spectrometer ("Spectrum One" manufactured by Perkin Elmer Co., Ltd.). The infrared absorption spectrum is measured in the ATR (Total Reflection Measurement) mode, and the absorbance is measured in the range of 700 to 4000 cm ^-1 . When the thickness of the layer (YA) is 1 μm or less, the absorption peak derived from the substrate (X) is detected in the infrared absorption spectrum by the ATR method, and the absorption intensity derived only from the layer (YA) cannot be obtained correctly. Happening. In this case, only the infrared absorption spectrum of the substrate (X) is additionally measured and subtracted, whereby only the peak from the layer (X) is removed. The same method can be employed when the layer (YA) is laminated on the layer (Z). Furthermore, when the layer (YA) is formed inside the multilayer structure (for example, when the substrate (X) / layer (YA) / layer (Z) is laminated), the infrared absorption spectrum of the layer (YA) can be Before the formation of the layer (Z), or after the formation of the layer (Z), it is peeled off at the interface of the layer (YA), and the infrared absorption spectrum of the exposed layer (YA) is measured.

Based on the infrared absorption spectrum of the layer (YA) obtained in this manner, the maximum absorption wave number (n ¹ ) in the range of 800 to 1400 cm ^-1 and the absorbance of the maximum absorption wave number (n ¹ ) (α) are obtained. ¹ ). And determine the range of 2500 ~ 4000cm ^-1 based on the maximum in the stretching vibration of hydroxyl group absorption wave number (n ^2), and the absorbance (α ²⁾ Maximum wave number (n ²⁾ of the absorbent. Further, the half value width of the absorption peak of the maximum absorption wave number (n ¹ ) is obtained by obtaining the absorbance (absorbance (α ¹ )/2) having one half of the absorbance (α ¹ ) in the absorption peak. The wave number of the two points is obtained by calculating the difference between the wave numbers. Further, when the absorption peak of the maximum absorption wave number (n ¹ ) overlaps with the absorption peaks from other components, the maximum absorption is obtained in the same manner as described above by using the Gaussian function to separate the absorption peaks from the respective components by the least square method. The half value of the absorption peak of the wave number (n ¹ ) is wide.

(2) Appearance of the multilayer structure

The appearance of the obtained multilayered structure and the protective sheet was evaluated by visual observation in the following manner.

A: Colorless, transparent and uniform, very good appearance.

B: I saw some cloudiness or unevenness, but it was a good appearance.

(3) Method of manufacturing protective sheet

A two-component adhesive (manufactured by Mitsui Chemicals, Inc., A-520 (trade name) and A-50 (trade name)) was applied to an acrylic resin single-layer film (thickness: 50 μm) and dried. This is laminated with the obtained multilayer structure to obtain a laminate. Then The above-mentioned two-component type adhesive is applied to the multilayer structure of the laminate and dried, and this is combined with a polyethylene terephthalate film (Toyo Textile Co., Ltd. SHINEBEAM (product) Name) Q1A15. Hereinafter, EVA is easily followed by PET film (thickness 50 μm), and the polyethylene terephthalate film is improved and the ethylene-vinyl acetate copolymer (hereinafter referred to as EVA) is attached. By. In this manner, a protective sheet having the (outer) acrylic resin layer/adhesive layer/multilayer structure/adhesive layer/EVA easily followed by the PET film (inner side) was obtained. Furthermore, the side of the multilayer structure having the layer (Y) (the layered structure having no layer (Y) is the side having the layer (Z) or the layer (Y')), which is based on the substrate (X) It is made up of layers on the outside.

(4) Oxygen permeability (Om) of the protective sheet

A sample for oxygen permeability measurement was cut out from the obtained protective sheet. The oxygen permeability was measured using an oxygen permeation amount measuring device ("MOCON OX-TRAN 2/20" manufactured by Modern Control Co., Ltd.). Specifically, the acrylic resin layer constituting the laminate of the protective sheet faces the oxygen supply side, and the EVA of the laminate tends to be placed on the apparatus so that the PET layer faces the carrier gas side. The oxygen permeability is measured at a temperature of 20 ° C, a humidity of 85% RH on the oxygen supply side, a humidity of 100% RH on the carrier gas side, an oxygen pressure of 1 atmosphere, and a carrier gas pressure of 1 atmosphere (unit: ml/). (m ² ‧day‧atm)).

(5) Oxygen permeability (Of) of 5% stretched and maintained protective sheet

The protective sheet obtained was allowed to stand at 23 ° C and 50% RH for 24 hours or more, and then stretched by 5% in the long axis direction under the same conditions, and kept in a stretched state for 5 minutes, thereby obtaining protection after stretching. sheet. The oxygen permeability was measured using an oxygen permeation amount measuring device ("MOCON OX-TRAN 2/20" manufactured by Modern Control Co., Ltd.). Specifically, a protective sheet is provided such that the layer (Y) or the layer (Y') faces the oxygen supply side and the substrate (X) faces the carrier gas side at a temperature of 20 ° C and a humidity of 85% RH on the oxygen supply side. The oxygen permeability (unit: ml/(m ² ‧day‧atm)) was measured under the conditions that the humidity on the carrier gas side was 85% RH, the oxygen pressure was 1 atm, and the carrier gas pressure was 1 atm. The carrier gas system used nitrogen gas containing 2% by volume of hydrogen.

[Production Example of Coating Liquid (U)]

A manufacturing example of the coating liquid (U) for producing the layer (YA) is shown.

The temperature was raised to 70 ° C while stirring 230 parts by mass of distilled water. 88 parts by mass of aluminum isopropoxide was added dropwise to the distilled water over 1 hour, and the liquid temperature was gradually raised to 95 ° C to distill off the produced isopropanol, thereby performing hydrolysis condensation. 4.0 parts by mass of a 60% by mass aqueous solution of nitric acid was added to the obtained liquid, and the mixture was stirred at 95 ° C for 3 hours to deagglomerate the aggregate of the particles of the hydrolyzed condensate, and then concentrated to a solid content concentration of 10% by mass in terms of alumina. . To 18.66 parts by mass of the dispersion obtained in this manner, 58.19 parts by mass of distilled water, 19.00 parts by mass of methanol, and 0.50 parts by mass of a 5 mass% aqueous polyvinyl alcohol solution were added to be uniformly stirred to obtain a dispersion ( S1). Further, 3.66 parts by mass of an 85% by mass aqueous phosphoric acid solution was used as the solution (T1). Next, both the dispersion (S1) and the solution (T1) were adjusted to 15 °C. Then, while maintaining the liquid temperature of 15 ° C, the solution (T1) was dropped while stirring the dispersion (S1) to obtain a coating liquid (U1). The obtained coating liquid (U1) was maintained at 15 ° C, and stirring was continued in this state until the viscosity became 1500 mPa ‧ s. Further, in the coating liquid (U1), the molar number (N _M ) of the metal atom constituting the metal oxide (A) (alumina) and the molar atom constituting the phosphorus atom of the phosphorus compound (B) (phosphoric acid) The ratio of the number (N _P ) (the number of moles (N _M ) / the number of moles (N _P )) was 1.15.

The coating liquid (U2), the coating liquid (U3), and the coating liquid (U4) were respectively obtained in the same manner except that the ratio of N _M /N _P was changed to 4.48, 1.92, and 0.82, respectively.

[Production Example of Coating Liquid (V1~4)]

First, a round bottom flask (internal volume: 50 ml) equipped with a stirrer, a reflux condenser, a dropping funnel, and a thermometer was substituted with nitrogen, and charged with methyl ethyl ketone (hereinafter sometimes abbreviated as "MEK") 12 g. As a solvent, it was immersed in an oil bath and heated to 80 ° C and started to reflux. From this point on, a small amount of nitrogen gas is continuously circulated throughout the polymerization process. Next, a mixed solution of 8.5 g of methacrylic acid phosphonium oxyethyl ester (hereinafter abbreviated as "PHM"), MEK 5 g, and 100 mg of azobisisobutyronitrile was prepared, and the mixture was dropped from the dropping funnel at a constant rate for 10 minutes. . After the completion of the dropping, the temperature was maintained at 80 ° C, and stirring was continued for about 12 hours to obtain a polymer solution having a yellow sticky liquid.

The polymer solution was poured into about 10 times the amount of 1,2-dichloroethane, and the supernatant was removed by decantation, and the precipitate was recovered to separate the polymer. The recovered polymer is dissolved in a good solvent of the polymer, tetrahydrofuran (hereinafter sometimes abbreviated as "THF"), and reprecipitated in about 10 times the amount of 1,2-dichloroethane, and this is repeated three times. Operate for refining. The molecular weight of the purified polymer was measured by gel permeation chromatography using THF as a solvent at a polymer concentration of 1% by weight, and the number average molecular weight was about 10,000 in terms of polystyrene.

The purified polymer was dissolved in a mixed solvent of water and isopropyl alcohol at a concentration of 10% by weight to obtain a coating liquid (V1).

A coating liquid (V2) composed of a single polymer of methacrylic acid phosphopolyoxypropylene glycol ester (hereinafter sometimes abbreviated as "PHP") was obtained by the same method as the coating liquid (V1). Further, in the same manner, a coating liquid (V3) of a copolymer obtained by copolymerizing PHM and acrylonitrile (hereinafter abbreviated as "AN") at a molar ratio of 2/1 and 1/1, respectively, and Coating liquid (V4).

[Production Example of Coating Liquid (V5~8)]

A round bottom flask (internal volume: 50 ml) equipped with a stirrer and a thermometer was replaced with nitrogen, and 2.5 g of water was added as a solvent, and vinylphosphonic acid (hereinafter sometimes abbreviated as "VPA") 10 g and water 2.5 g were stirred. And a mixed solution of 2,2'-azobis(2-amidinopropane)HCl (hereinafter sometimes abbreviated as "AIBA") 25 mg was dropped into a round bottom flask. From this point on, the entire process of polymerization was continuously circulated with a small amount of nitrogen. After the round bottom flask was immersed in an oil bath and reacted at 80 ° C for 3 hours, the reaction mixture was diluted with 15 g of water, and filtered through a cellulose film (SPECTRUM® LABORATORIES, INC., "Spectra/Por" (trade name)). . Next, the solvent of the filtrate was distilled off by an evaporator, and vacuum-dried at 50 ° C for 24 hours, whereby a white polymer was obtained. The polymer was subjected to colloidal permeation chromatography using a 1.2 wt% aqueous solution of NaCl as a solvent, and the molecular weight was measured at a polymer concentration of 0.1% by weight. As a result, the number average molecular weight was about 10,000 in terms of polyethylene glycol.

The purified polymer was dissolved in a mixed solvent of water and methanol at a concentration of 10% by weight to obtain a coating liquid (V5).

A coating liquid (V6) composed of a single polymer of 4-vinylbenzylphosphonic acid (hereinafter sometimes abbreviated as "VBPA") was obtained by the same method as the preparation of the coating liquid (V5). Further, in the same manner, a coating liquid (V7) of a copolymer obtained by copolymerizing VPA and methacrylic acid (hereinafter sometimes abbreviated as "MA") at a molar ratio of 2/1 and 1/1, respectively, was obtained. And a coating liquid (V8).

[Example 1]

A polyethylene terephthalate film ("lumirror P60" (trade name), thickness 12 μm or less, sometimes abbreviated as "PET") manufactured by TORAY Co., Ltd. was prepared as a substrate. The coating liquid (U1) was applied onto the substrate (PET) by a bar coater so that the thickness after drying became 0.5 μm, and dried at 110 ° C for 5 minutes. Subsequently, heat treatment was performed at 180 ° C for 1 minute to obtain a structure (A1) having a structure of layer (Y1) (0.5 μm) / PET (12 μm). Then, the coating liquid (V1) was applied to the layer (Y1) of the structure (A1) by a bar coater so that the thickness after drying became 0.3 μm, and dried at 110 ° C for 5 minutes, thereby obtaining a layer ( Z1) (0.3 μm) / layer (Y1) (0.5 μm) / PET (12 μm) structure of the multilayer structure (B1).

The moisture permeability (water vapor permeability; WVTR) of the obtained multilayered structure (B1) was measured using a water vapor transmission amount measuring device ("MOCON PERMATRAN 3/33" manufactured by Modern Control Co., Ltd.). Specifically, the multilayer structure is provided such that the layer (Z1) faces the water vapor supply side and the PET layer faces the carrier gas side, and the humidity at the temperature of 40 ° C, the water supply side is 90% RH, and the humidity of the carrier gas side. The moisture permeability (unit: g/(m ² ‧day)) was measured under the condition of 0% RH. The multilayer structure (B1) has a moisture permeability of 0.2 g/(m ² ‧day).

With respect to the obtained multilayered structure (B1), a sample for measurement of a size of 15 cm × 10 cm was cut out. Then, the sample was placed under conditions of 23 ° C and 50% RH for 24 hours or more, and then stretched by 5% in the long axis direction under the same conditions, and kept in a stretched state for 5 minutes, thereby obtaining a multilayer structure (B1). ). The moisture permeability of the multilayered structure (B1) after the stretching was measured by the above method, and the moisture permeability of the multilayered structure (B1) after stretching was 0.2 g/(m ² ‧day).

With respect to the obtained multilayered structure (B1), a protective sheet was produced by the above method and evaluated.

[Example 2]

A multilayer structure and a protective sheet were obtained in the same manner as in Example 1 except that the coating liquid (V) was changed to V5.

The moisture permeability of the multilayered structure obtained in Example 2 was measured in the same manner as in Example 1. As a result, the moisture permeability of the multilayered structure was 0.2 g/(m ² ‧day). Further, the 5% tensile strength after stretching of the multilayered structure obtained in Example 2 was measured in the same manner as in Example 1. As a result, the moisture permeability of the multilayered structure after stretching was 0.2 g/(m ² ‧day).

[Examples 3 to 6, 37, 38]

The multilayer structure and the protective sheet were obtained in the same manner as in Example 1 except that the thickness of the layer (Z) and the coating liquid (V) were changed in accordance with Table 1.

[Examples 7 to 12]

A multilayer structure and a protective sheet were obtained in the same manner as in Example 1 except that the coating liquid (V) to be used was changed in accordance with Table 1.

[Examples 13 to 18]

A multilayer structure and a protective sheet were obtained in the same manner as in Example 1 except that the conditions of the heat treatment and the coating liquid (V) were changed in accordance with Table 1.

[Examples 19 to 24]

A multilayer structure and a protective sheet were obtained in the same manner as in Example 1 except that the coating liquid (U) and the coating liquid (V) to be used were changed in accordance with Table 1.

[Examples 25 and 26]

A multilayer structure and a protective sheet were obtained in the same manner as in Example 1 except that the heat treatment step was carried out after the formation of the layer (Z).

[Examples 27 and 28]

The multilayer structure and the protective sheet were obtained in the same manner as in Example 1 except that the coating liquid (V) was changed in the two-layer layer (Y) and the layer (Z) of the substrate. The moisture permeability of the obtained multilayered structure (A1) was measured in the same manner as in Example 1 and found to be 0.1 g/(m ² ‧day) or less.

[Examples 29, 30]

The base material was a stretched nylon film ("EMBLEM ONBC" (trade name) manufactured by Unitika Co., Ltd., thickness: 15 μm, sometimes abbreviated as "ONY"), and the coating liquid (V) was changed in accordance with Table 1. A multilayer structure and a protective sheet were obtained in the same manner as in Example 1 except for the above.

[Examples 31, 32]

The multilayer structure and the protective sheet were obtained in the same manner as in Example 1 except that the substrate was subjected to vapor deposition on the surface of the PET, and the coating liquid (V) was changed in accordance with Table 1. .

[Examples 33, 34]

A multilayer structure and a protective sheet were obtained in the same manner as in Example 1 except that the substrate was a ruthenium oxide vapor-deposited layer deposited on the surface of the PET, and the coating liquid (V) was changed in accordance with Table 1.

[Examples 35, 36]

A multilayer structure and a protective sheet were obtained in the same manner as in Example 1 except that the layer (Y) was an alumina vapor-deposited layer having a thickness of 0.03 μm, and the coating liquid (V) was changed in accordance with Table 1. The aluminum oxide layer is formed by a vacuum evaporation method.

[Examples 39, 40]

The layer (Y) was formed after the formation of the layer (Z), and the coating liquid (V) was changed in accordance with Table 1, except that the multilayer structure and the protective sheet were obtained in the same manner as in Example 1. .

[Comparative Example 1]

As the comparative example 1, the layer (Z) was not formed in Example 1.

The moisture permeability of the multilayered structure obtained in Comparative Example 1 was measured in the same manner as in Example 1. As a result, the moisture permeability of the multilayered structure was 0.3 g/(m ² ‧day). Further, the moisture permeability after stretching of 5% of the multilayered structure obtained in Comparative Example 1 was measured in the same manner as in Example 1. As a result, the moisture permeability of Comparative Example 1 after stretching was 5.7 g/(m ² ‧day).

[Comparative Example 2]

As the comparative example 2, the layer (Z) was not formed in Example 13.

[Comparative Example 3]

As the comparative example 3, the layer (Z) was not formed in Example 15.

[Comparative Example 4]

As the comparative example 4, the layer (Z) was not formed in Example 17.

[Comparative Example 5]

As the comparative example 5, the layer (Z) was not formed in Example 19.

[Comparative Example 6]

As the comparative example 6, the layer (Z) was not formed in Example 21.

[Comparative Example 7]

As the comparative example 7, the layer (Z) was not formed in Example 23.

[Comparative Example 8]

As the comparative example 8, the layer (Z) was not formed in Example 27.

[Comparative Example 9]

As the comparative example 9, the layer (Z) was not formed in Example 29.

[Comparative Example 10]

As the comparative example 10, the layer (Z) was not formed in Example 31.

[Comparative Example 11]

As the comparative example 11, the layer (Z) was not formed in Example 33.

[Comparative Example 12]

As the comparative example 12, the layer (Z) was not formed in Example 35.

[Comparative Examples 13, 14]

The layer (Y) was a layer (Y') which is a cerium oxide vapor-deposited layer having a thickness of 0.03 μm, and the coating liquid (V) was changed in accordance with Table 1, and a multilayer was obtained in the same manner as in Example 1. Structure and protective sheet. The ruthenium oxide layer is formed by a vacuum evaporation method.

[Comparative Examples 15, 16]

A multilayer structure and a protective sheet were obtained in the same manner as in Example 1 except that the layer (Y) was not formed, and the coating liquid (V) was changed in accordance with Table 1.

[Comparative Examples 17, 18]

A multilayer structure and a protective sheet were obtained in the same manner as in Example 1 except that the layer (Z) was formed on PET, and the coating liquid (V) was changed in accordance with Table 1. That is, in Comparative Example 17, a multilayered structure of Comparative Example 17 having a structure of layer (Y1) (0.5 μm) / PET (12 μm) / layer (Z1) (0.3 μm) and a protective sheet were produced.

[Comparative Example 19]

As the comparative example 19, the layer (Z) was not formed in Comparative Example 14.

[Comparative Example 20]

As the comparative example 20, those in which the layer (Z) was not formed in Comparative Example 15, that is, only the substrate (PET) were used.

The manufacturing conditions and evaluation results of the above examples and comparative examples are shown in Table 1 and Table 2 below. Furthermore, in the table, "-" means "unused", "unable to calculate", "not implemented", "unable to measure", and the like.

It can be understood from the table that the protective sheets of the respective examples maintain good gas barrier properties even after being subjected to strong physical pressure (5% stretching) after the protective sheet is produced. On the other hand, when the protective sheet of the comparative example was subjected to a strong physical pressure (5% stretching), all of them showed a significant decrease in gas barrier properties.

In addition, in order to examine the flexibility of the protective sheet produced in the above-described embodiment, a test was performed in which about 20 turns of the outer peripheral surface of a cylindrical stainless steel core material having an outer diameter of 30 cm was wound, and no damage was observed. The protective sheet produced in each of the examples has flexibility.

[Electronic device manufacturing example]

First, a multilayer structure was produced in the same manner as in Example 2. Next, the amorphous tantalum solar cell unit provided on the tempered glass of 10 cm square was sandwiched by an ethylene-vinyl acetate copolymer having a thickness of 450 μm, and laminated to the layer (Z1) of the multilayered structure. In order to make a solar cell module. The bonding was carried out by vacuuming at 150 ° C for 3 minutes and then pressing for 9 minutes. The solar cell module fabricated in this manner exhibits good motion and exhibits good electrical output characteristics over a long period of time.

1‧‧‧Electronic device body

2‧‧‧ Sealing material

3‧‧‧Protection film

10‧‧‧Electronic devices

Claims (12)

An electronic device comprising: an electronic device body; and a protective sheet for protecting a surface of the electronic device body, wherein the protective sheet comprises a multilayer structure having one or more layers of a substrate (X), a layer (Y) and a layer (Z) The layer (Y) contains an aluminum atom, the layer (Z) contains a polymer (E), and at least one of the layers (Y) is laminated adjacent to the layer (Z), and the polymer (E) contains A monomer unit of a phosphorus atom. An electronic device according to claim 1, which has the following structure: at least one group of the substrate (X), the layer (Y) and the layer (Z), and the substrate (X)/the layer ( Y) / The layer (Z) is layered in sequence. The electronic device of claim 1, wherein the polymer (E) is a single polymer or copolymer of a (meth) acrylate having a phosphate group at the end of the side chain. The electronic device of claim 3, wherein the polymer (E) is a separate polymer of acid phosphoxy ethyl (meth) acrylate. The electronic device of claim 1, wherein the polymer (E) has a repeating unit represented by the following formula (I). [In the formula (I), n represents a natural number]. An electronic device according to claim 1, wherein the layer (Y) is a layer (YA) containing a reaction product (R), and the reaction product (R) is a metal oxide (A) containing aluminum and A reaction product obtained by reacting a phosphorus compound (B). In the infrared absorption spectrum of the layer (YA), the maximum absorption of infrared rays (n ¹ ) in the range of 800 to 1400 cm ^-1 is in the range of 1080 to 1130 cm ^{-1 .} The scope. The electronic device of claim 1, wherein the layer (Y) is an aluminum deposited layer (YB) or an aluminum oxide deposited layer (YC). The electronic device according to claim 1, wherein the substrate (X) comprises at least one layer selected from the group consisting of a thermoplastic resin film layer, a paper layer, and an inorganic vapor deposition layer. The patentable scope of application of the electronic device according to item 1, wherein the protective sheet at 20 ℃, oxygen permeability at 85% RH it was 2ml / (m ² ‧day‧atm) or less. The electronic device of claim 1, wherein the protective sheet is held at a temperature of 23 ° C and 50% RH for 5 minutes in a state of uniaxially stretching 5% for 5 minutes. The oxygen permeability measured under the conditions of °C and 85% RH is 4 ml/(m ² ‧day‧atm) or less. An electronic device as claimed in claim 1, which is a photoelectric conversion device, an information display device or a lighting device. The electronic device of claim 1, wherein the protective sheet has flexibility.