TWI638721B - Electronic device - Google Patents

Abstract

An electronic device provided by the present invention includes an electronic device body and a protective sheet for protecting the surface of the electronic device body. The protective sheet includes a multilayer structure having a substrate (X), a layer (Y), and a layer (Z) each having one or more layers. The layer (Y) contains an aluminum atom, the layer (Z) contains a polymer (E), and at least one layer (Y) and the layer (Z) are adjacent and laminated, and the polymer (E) contains a monomer having a phosphorus atom unit. This electronic device is suitable for the case where the gas barrier property of the protective sheet can be maintained at a high level even under physical pressure.

Description

Electronic device

The invention relates to an electronic device with a protective sheet.

It is required that the protective member disposed on the surface of the electronic device is not detrimental to the characteristics of the electronic device. With the advent of electronic devices that can respond to thinner and lighter weight, thin protective sheets using multilayer structures have been developed as alternatives to thicker protective members represented by glass plates. One of the characteristics required for the protective sheet is a gas barrier. When gas barrier properties are required, the protective sheet is made of a multilayered structure with improved gas barrier properties.

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

Patent Document 1: International Publication No. 2011-122036

However, although the above-mentioned conventional multilayer structure has excellent initial gas barrier properties, when subjected to physical stress such as deformation and impact, the gas barrier film may have defects such as cracks and pinholes. Can not ensure gas barrier for a long time Sexual situation. The multilayer structure of a protective sheet for an electronic device is subjected to various physical pressures not only in the manufacturing stage and the distribution stage of the electronic device, but also in a period of long-term use. Therefore, an electronic device is required to maintain the gas barrier property of the multilayer structure to a high level even when subjected to physical pressure.

An object of the present invention is to provide an electronic device suitable for a case where the gas barrier property of a multilayer structure can be maintained at a high level even when subjected to physical pressure.

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

The electronic device of the present invention may have the following structure: at least one set of the above-mentioned substrate (X), the above-mentioned layer (Y), and the above-mentioned layer (Z), and the above-mentioned substrate (X) / the above-mentioned layer (Y) / The layers (Z) are sequentially stacked.

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

In the electronic device of the present invention, the polymer (E) may be a separate 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 general formula (I).

[In 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). In the infrared absorption spectrum of the layer (YA), it 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 ~ 1130cm ^-1 .

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

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

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

In the electronic device of the present invention, after the protective sheet is stretched unidirectionally for 5% at 23 ° C and 50% RH for 5 minutes, the multilayer structure is subjected to 20 ° C and 85% RH. The oxygen permeability measured under these conditions can be less than 4ml / (m ² ‧day‧atm).

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 this specification, "flexible" means that it can be wound along the outer peripheral side surface of a cylindrical core material with an outer diameter of 30 cm to form a wound body, and the object to be wound will not be caused by the winding. (E.g. protection sheet) damage.

According to the present invention, an electronic device can be obtained, which is suitable for a case where the gas barrier property of a multilayer structure can be maintained at a high level even under a physical pressure.

1‧‧‧ electronic device body

2‧‧‧sealing material

3‧‧‧protective film

10‧‧‧ electronic device

FIG. 1 is a cross-sectional view showing a type of electronic device of the present invention.

Hereinafter, embodiments of the present invention will be described. In addition, although the following description includes materials exhibiting a specific function, and specific materials (compounds, etc.) are exemplified, the present invention is not limited to the aspect using such materials. In addition, as long as the illustrated materials are not specifically mentioned, it means that they may be used individually by 1 type, and may use 2 or more types together.

[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 type of the electronic device of the present invention is shown in FIG. 1. The electronic device 10 includes an electronic device body 1, 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 covers the entire surface of the electronic device body 1. The protective sheet 3 is disposed on one surface of the electronic device body 1 through the sealing material 2. Although not shown, a protective sheet may be disposed on a surface opposite to the surface on which the protective sheet 3 is disposed. However, another protection member different from the protection sheet 3 may be disposed on the surface on the opposite side.

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, a liquid crystal display, an information display device such as an electronic paper, and an illumination device such as an organic EL light-emitting element. The sealing material 2 is suitable for the type, application, etc. of the electronic device body 1 When attached to any component. As the sealing material 2, EVA (ethylene-vinyl acetate resin), PVB (polyvinyl butyral), or the like is used. The protection sheet 3 only needs to be arranged in a manner that can protect the surface of the electronic device body 1, can be directly disposed on the surface of the electronic device body 1, or can be disposed on the surface of the electronic device body 1 by other members such as a sealing material 2.

The electronic device body 1 is typically a solar cell. Examples of solar cells include silicon-based solar cells, compound semiconductor solar cells, organic solar cells, and the like. Examples of the silicon-based solar cell include a monocrystalline silicon solar cell, a polycrystalline silicon solar cell, an amorphous silicon 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. In addition, the solar cell may be an integrated solar cell in which a plurality of unit cells are connected in series, or 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. In the roll-to-roll method, a flexible substrate (for example, a stainless steel substrate, a resin substrate, etc.) wound into a feed roller is sent out, and elements are formed on the substrate to produce an electronic device body 1. The electronic device body 1 is wound by a take-up roll. take. In this case, it is also possible to prepare in advance the form in which the protective sheet 3 is also a flexible (having a flexible) long sheet, and more specifically, the form of the rolled body of the long sheet. The protective sheet 3 sent out by the sending-out roller is laminated on the electronic device body 1 that is rolled up before the taking-up roller, and is rolled up together with the electronic device body 1. Alternatively, the electronic device main body 1 that has been taken up by the take-up roll may be separately taken out from the roll and laminated with the protective sheet 3. A preferred form of the present invention is that the electronic device itself is flexible.

The protective sheet 3 contains a multilayer structure described below. The protective sheet 3 may be composed only of a multilayer structure, or a member other than the multilayer structure may be further laminated. 3 protection sheets If it is suitable for protecting the layered laminated body on the surface of the electronic device and includes the following multilayer structure, the thickness and material thereof are not particularly limited.

[Multilayer Structure]

The multilayer structure system has a multilayer structure with more than one layer each of the substrate (X), the layer (Y), and the layer (Z). The layer (Y) contains aluminum atoms, 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 multilayer structure is excellent in the characteristic of suppressing a decrease in gas barrier properties of a film material due to physical pressure (hereinafter sometimes referred to as "bending resistance").

[Layer (Y)]

The layer (Y) included in the multilayer structure may also be a layer (YA) containing a reaction product obtained by reacting a metal oxide (A) containing at least aluminum 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 explains them in order.

[Floor (YA)]

When the layer (Y) of the multilayer structure is the above-mentioned layer (YA), in the infrared absorption spectrum of the layer (YA), the wave number (n ¹ ) having the largest infrared absorption in the range of 800 to 1400 cm ^-1 is 1080. The range is ~ 1130cm ^-1 .

Hereinafter, this wave number (n ¹ ) may be referred to as “maximum absorption wave number (n ¹ )”. The metal oxide (A) usually reacts with the phosphorus compound (B) in the form of metal oxide (A) particles.

Typically, the layer (YA) included in the multilayer structure has a structure in which metal oxide (A) particles are bonded to each other via a phosphorus atom derived from a phosphorus compound (B). via The form of phosphorus atom bonding includes a form of bonding through a phosphorus atom-containing atomic group, and includes a form of bonding through, for example, a phosphorus atom-containing metal group.

In the layer (YA) of the multilayer structure, the mole number of the metal atom that bonds the metal oxide (A) particles to each other and that is not derived from the metal atom (A) is based on the metal oxide ( A) A range of 0 to 1 times (for example, a range of 0 to 0.9 times) the number of moles of phosphorus atoms to which particles are bonded to each other is preferred, and may be, for example, 0.3 times or less, 0.05 times or less, 0.01 times or less, or 0 times.

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

Generally speaking, when a metal compound reacts with a phosphorus compound to generate a bond represented by MOP, a characteristic peak in the infrared absorption spectrum will be generated. The bond represented by MOP is a combination of a metal atom (M) constituting a metal compound and phosphorus The phosphorus atom (P) of the compound is bonded via an oxygen atom (O). The characteristic peak here shows an absorption peak at a specific wave number depending on the environment, structure, and the like around the bond. As a result of the review by the present inventors, it was learned that when the absorption peak based on the MOP bond is in the range of 1080 to 1130 cm ^-1 , the obtained multilayer structure will exhibit excellent gas barrier properties. And it was learned that especially when the absorption peak exhibits the absorption peak with the maximum absorption wave number in the region of 800 ~ 1400cm ^-1 where absorption from various atoms and oxygen atoms are usually seen, the resulting multilayer structure will exhibit More excellent gas barrier properties.

Furthermore, although the present 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), A bond represented by MOP is generated (the bond represented by MOP is a bond between a metal atom (M) and a phosphorus atom (P) constituting a metal oxide (A) via an oxygen atom (O)), then Because of the relatively fixed environment on the surface of the metal oxide (A) particles, in the infrared absorption spectrum of this layer (YA), the absorption peak based on the MOP bond will have the maximum absorption in the region of 800 ~ 1400cm ^-1 The shape of the absorption peak of the wave number appears in the range of 1080 ~ 1130 cm ^-1 .

In contrast, when a metal compound that does not form a metal oxide such as a metal alkoxide or a metal salt, and a phosphorus compound (B) are mixed in advance, and hydrolyzed and condensed, it is obtained from The complex in which the metal atom of the metal compound and the phosphorus atom from the phosphorus compound (B) are substantially uniformly mixed and reacted. In the infrared absorption spectrum, the maximum absorption wave number (n ¹ ) in the range of 800 to 1400 cm ^-1 is not 1080. The range is ~ 1130cm ^-1 .

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) included in the multilayer structure, absorption of stretching stretching vibrations of hydroxyl groups bonded to various atoms may be seen in a range of 2500 to 4000 cm ^-1 . Examples of the absorbed hydroxyl group can be seen in this range. Examples of the hydroxyl group exist on the surface of the metal oxide (A) and have an M-OH type, and a phosphorus atom (P) derived from a phosphorus compound (B). ), A hydroxyl group having a P-OH type, a hydroxyl group having a C-OH type from the polymer (C) described later, and the like. The amount of hydroxyl groups present in the layer (YA) may be related to the absorbance (α ² ) of the maximum absorption wave number (n ² ) based on the stretching and stretching vibration of the hydroxyl groups in the range of 2500 to 4000 cm ^-1 . Here, in the infrared absorption spectrum of the wave number (n ² ) -based layer (YA), the infrared absorption based on the hydroxyl stretching vibration in the range of 2500 to 4000 cm ^-1 has the largest wave number. Hereinafter, the wave number (n ² ) is sometimes referred to as “maximum absorption wave number (n ² )”.

The greater the amount of hydroxyl groups 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 effectively the metal oxide (A) particles can be bonded to each other via a 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 of the layer (YA) having the above-mentioned ratio [absorbance (α ² ) / absorbance (α ¹ )] can be adjusted by adjusting the mole number (N _M ) of the metal atoms constituting the metal oxide (A) described later, and It is obtained by the ratio of the molar number (N _P ) of phosphorus atoms derived from the phosphorus compound (B), heat treatment conditions, and the like. 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 group stretching vibration may satisfy the relationship of absorbance (α ² ′) / absorbance (α ¹ ′)> 0.2 in some cases.

In the infrared absorption spectrum of the layer (YA) of the multilayer structure, the half-value width of the maximum absorption peak at the above-mentioned maximum absorption wave number (n ¹ ) is large. From the viewpoint of gas barrier properties of the obtained multilayer structure, It is preferably 200 cm ^-1 or less, more preferably 150 cm ^-1 or less, even more preferably 130 cm ^-1 or less, even more preferably 110 cm ^-1 or less, still more preferably 100 cm ^-1 or less, particularly preferably 50 cm ^-1 or less. . Although the present 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) are passed to each other through a phosphorus atom derived from the phosphorus compound (B) and not through Metal atoms not derived from the metal oxide (A) are bonded to form a bond represented by MOP (the bond represented by the MOP is a metal atom (M) and a phosphorus atom (P) constituting the metal oxide (A) ) Is formed by the bonding of oxygen atom (O)), because of the relatively fixed environment on the surface of the metal oxide (A) particles, the maximum absorption wave number (n ¹ ) has a half value of the maximum absorption peak. Wide will become the above range. In addition, the half-value width of the absorption peak of the maximum absorption wave number (n ¹ ) in the present specification can be obtained by finding the absorbance (absorbance (α ¹ )) which has half of the absorbance (α ¹ ) in the absorption peak. / 2), 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 its infrared absorption spectrum by the KBr method. .

In the layer (YA) of the multilayer structure, the shape of each particle of the metal oxide (A) is not particularly limited, and examples include shapes such as a spherical shape, a flat shape, a polyhedron shape, a fibrous shape, and a needle shape. From the viewpoint of being a multilayer structure having more excellent gas barrier properties, a fibrous or needle-like shape is preferred. 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. For example, those having a nanometer size to a sub-micron size can be exemplified by the metal oxide (A). The size of the particles is preferably in the range of 1 to 100 nm.

The above-mentioned fine structure in the layer (YA) of the multilayer structure can be confirmed by observing the cross section of the layer (YA) with a transmission electron microscope (TEM). In addition, the particle size of each particle of the metal oxide (A) in the layer (YA) can be measured by the maximum length of the longest axis of each particle in the observation image of the layer (YA) section obtained by a transmission electron microscope (TEM) Calculate the average value of the maximum length of the particle with the axis perpendicular to it, and arbitrarily select 10 in the section observation image. By averaging the particle diameters of the individual particles, the above average particle diameter can be obtained.

An example of the layer (YA) in the multilayer structure is a structure in which the particles of the metal oxide (A) pass through the phosphorus atom derived from the phosphorus compound (B) and do not pass through the non-metal oxide ( A) A structure in which 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 other metal atoms. Here, the "structure obtained by bonding via a phosphorus atom derived from a phosphorus compound (B) and not via a metal atom not derived from a metal oxide (A)" means a metal oxide (A) particle to be bonded. The main chain of the intermolecular bond has a structure derived from a phosphorus atom of the phosphorus compound (B) and does not have a metal atom not derived from the metal oxide (A), and also includes a structure in which the side chain of the bond has a metal atom. Among them, the layer (YA) of the multilayer structure may also partially have the following structure: The particles of the metal oxide (A) are bonded to each other through a phosphorus atom and a metal atom derived from the phosphorus compound (B). Structure (the main chain of the interparticle bonding of the bonded metal oxide (A) has a structure derived from both a phosphorus atom and a metal atom of the phosphorus compound (B)).

In the layer (YA) of the multilayer structure, the bonding type between each particle of the metal oxide (A) and the phosphorus atom is exemplified by the metal atom (M) and the phosphorus atom constituting the metal oxide (A). (P) is a form in which an oxygen atom (O) is bonded. 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. If the specific bonding type between the two metal oxides (A) that are bonded is represented by (M α), one of the bonds constitutes the metal atom of the metal oxide (A) particle, and (M β) to represent another metal atom constituting the metal oxide (A) particle, and examples thereof include a bonding form of (M α) -OPO- (M β); (M α) -OP- [ OP] _n -O- (M β) bond type; (M α) -OPZPO- (M β) bond type; (M α) -OPZP- [OPZP] _n -O- (M β ) Bond type and so on. Furthermore, in the example of the above-mentioned 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. The description of other substituents on the phosphorus atom is omitted here. From the viewpoint of the gas barrier property of the obtained multilayer structure, it is preferable that among the layer (YA) of the multilayer structure, the particle of one metal oxide (A) and the number of other metal oxides (A) Particle bonding.

The metal oxide (A) may be a hydrolyzed condensate of a compound (L) containing a metal atom (M), and the metal atom (M) is bonded with a hydrolyzable characteristic group. Examples of this characteristic group include X ^{1 in} the formula (I) described later.

The hydrolyzed condensate of the compound (L) can be regarded substantially as a metal oxide. Therefore, in this specification, the hydrolysis-condensation product of a compound (L) may be called "metal oxide (A)". That is, in this specification, "metal oxide (A)" can be read as "hydrolyzed condensate of compound (L)", and "hydrolyzed condensate of compound (L)" can be read as "metal oxide (A)" .

[Metal Oxide (A)]

The metal atoms constituting the metal oxide (A) (these are sometimes collectively referred to as "metal atoms (M)") include metals having an atomic value of 2 or more (for example, 2 to 4 or 3 to 4) Atoms include, for example, metals of Group 2 of the periodic table, such as magnesium and calcium; metals of Group 12 of the periodic table, such as zinc; metals of Group 13 of the periodic table, such as aluminum; metals of Group 14 of the periodic table, such as silicon; , Titanium, zirconium and other transition metals. In addition, silicon is sometimes classified as a semi-metal, but silicon is included in the metal in this specification. The metal atom (M) constituting the metal oxide (A) may be one kind or two or more kinds, but it is necessary Must contain at least aluminum. In terms of ease of operation for producing the metal oxide (A) and excellent gas barrier properties of the obtained multilayer structure, the metal atom (M) which can be used in combination with aluminum is preferably selected from the group consisting of titanium and zirconium At least one of the groups.

The total proportion of aluminum, titanium and zirconium 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 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 produced by a liquid phase synthesis method, a gas phase synthesis method, a solid pulverization method, and the like, but if the shape, size controllability, and manufacturing efficiency of the obtained metal oxide (A) are considered Etc., preferably obtained by a liquid phase synthesis method.

In the liquid-phase synthesis method, a compound (L) obtained by bonding a hydrolyzable characteristic group to a metal atom (M) is used as a raw material, and hydrolyzed and condensed to synthesize a metal oxide (A) into a compound ( L) Hydrolyzed condensate. Among them, the metal atom (M) of the compound (L) must contain at least aluminum. When a hydrolyzed condensate of the compound (L) is produced by a liquid phase synthesis method, in addition to the method using the compound (L) itself as a raw material, the compound (L) obtained by partially hydrolyzing the compound (L) may also be used. Partial hydrolysate of compound (L), complete hydrolysate of compound (L), compound (L), partially hydrolyzed condensate of compound (L), partially hydrolyzed condensate, compound (L) A metal oxide (A) is produced by partially condensing a completely hydrolysate or a mixture of two or more of these as a raw material and subjecting it to condensation or hydrolysis condensation. The metal oxide (A) obtained in this manner is also referred to as "hydrolyzed condensate of compound (L)" in this specification. Hydrolysable properties The type of the energetic group is not particularly limited, and examples thereof include halogen atoms (F, Cl, Br, I, etc.), alkoxy groups, fluorenyloxy groups, difluorenylmethyl groups, and nitro groups. In terms of excellence, a halogen atom or an alkoxy group is preferred, and an alkoxy group is more preferred.

In terms of easy reaction control and excellent gas barrier properties of the obtained multilayer structure, the compound (L) preferably contains at least one compound (L ¹ ) represented by the following formula (II).

AlX ¹ _m R ¹ _(3-m) (II) [In 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 aromatic group, and an alkenyl group. In formula (II), when plural X ¹ are present, the X ¹ may be the same or different. In formula (II), when a plurality of R ¹ are present, the R ¹ may be the same or different. In formula (II), when plural R ² is present, these R ² may be the same or different. In formula (II), when a plurality of R ³ are present, these R ³ may be the same or different. In formula (II), when plural R ⁴ is present, these R ⁴ may be the same or different. m represents an integer from 1 to 3. A

Examples of the alkyl group represented by R ¹ , R ² , R ^3, and R ⁴ include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, third butyl, and 2- Ethylhexyl and the like. Examples of the aralkyl group represented by R ¹ , R ² , R ^3, and R ⁴ include benzyl, phenethyl, and trityl. 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. )Wait. Examples of the alkenyl group represented by R ¹ , R ² , R ³ and R ⁴ include a vinyl group and an allyl group. R ^{1 is} preferably, for example, an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 4 carbon atoms. X ^{1 is} preferably F, Cl, Br, I, R ² O-. Preferred examples of the compound (L ¹ ) are those in which X ¹ is a halogen atom (F, Cl, Br, I) or an alkoxy group (R ² O-) having 1 to 4 carbon atoms, and m is 3. In an example of the compound (L ¹ ), X ¹ is a halogen atom (F, Cl, Br, I) or an alkoxy group (R ² O-) having 1 to 4 carbon atoms, and m is 3.

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 as described in formula (II), respectively. In formula (III), n is equal to the atomic valence of M ¹ , and m represents an integer from 1 to n. A

Specific examples of the compound (L ¹ ) include, for example, aluminum chloride, aluminum triethoxide, aluminum tri-n-propoxide, aluminum tri-isopropoxide, aluminum tri-n-butoxide, aluminum tri-n-butoxide, Aluminum compounds such as aluminum tributoxide, aluminum triacetate, aluminum acetoacetone, and aluminum nitrate. Among these, the compound (L ¹ ) is preferably at least one compound selected from aluminum triisopropoxide and aluminum tributoxide. The compound (L ¹ ) may be used singly or in combination of two or more kinds.

The proportion of the compound (L ¹ ) in the compound (L) is not particularly limited. The proportion of the compound (L) 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%. For example, the compound (L) is composed only of the compound (L ¹ ).

The compound (L) other than the compound (L ¹ ) is not particularly limited as long as the effect of the present invention can be obtained, and examples thereof include bonding with a metal atom such as titanium, zirconium, magnesium, calcium, zinc, or silicon. Compounds formed from the above-mentioned hydrolyzable characteristic groups. In addition, there are cases where silicon is classified as a semi-metal, but this specification includes silicon as a metal. 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 tetra- (2-ethylhexanol), titanium tetramethoxide, Titanium compounds such as titanium tetraethoxide and titanium acetoacetone; zirconium compounds such as zirconium tetra-n-propoxide, zirconium tetrabutoxide and zirconium tetraacetonate.

By hydrolyzing the compound (L), at least a part of the hydrolyzable characteristic group of the compound (L) can be substituted with a hydroxyl group. Furthermore, the hydrolyzate thereof is condensed to form a compound in which a metal atom (M) is bonded via an oxygen atom (O). If this condensation is carried out repeatedly, compounds which can be regarded as substantially metal oxides are formed. Furthermore, the 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 Molar number ratio of hydrogen atom (except oxygen atom) to metal atom (M) ratio ([mole number of oxygen atom (O) bonded to metal atom (M) only) / [Mole number of metal atom (M)]) is 0.8 or more, and this compound is included in the metal oxide (A) in this specification. The above ratio of the metal oxide (A) is preferably 0.9 or more, more preferably 1.0 or more, and still more preferably 1.1 or more. The upper limit of the above ratio is not particularly limited, and if the atomic valence of the metal atom (M) is set to n, it is usually expressed as n / 2.

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

The hydrolyzed condensate can be produced from a specific raw material by, for example, a method used in the conventional sol-gel method. This raw material can be selected from the group consisting of compound (L), a local hydrolysate of compound (L), a complete hydrolysate of compound (L), a local hydrolyzed condensate of compound (L), and a partial hydrolysate of compound (L) At least one of the groups consisting of condensed persons (below (Sometimes called "compound (L) -based component"). These raw materials can be manufactured by a conventional method, and can also be used commercially. 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, as a part of the raw material, for example, a condensate obtained by hydrolyzing and condensing aluminum triisopropoxide into a 2 to 10-volume body can be used.

The number of molecules condensed in the hydrolysis-condensation product of the compound (L) can be controlled depending on the conditions when the compound (L) -based component is condensed or hydrolyzed and condensed. For example, the number of molecules to be condensed can be controlled according to the amount of water, the type of catalyst, the concentration, the temperature and time during condensation or hydrolysis and condensation.

As described above, the layer (YA) of the multilayer structure includes a reaction product (R), and the reaction product (R) is formed by reacting a metal oxide (A) containing at least aluminum with a phosphorus compound (B). Reaction product. Such a reaction product can be formed by mixing and reacting a metal oxide (A) and a phosphorus compound (B). The metal oxide (A) to be supplied (before being mixed) with the phosphorus compound (B) may be the metal oxide (A) itself or a composition containing the metal oxide (A) Type. A preferable example is a liquid (solution or dispersion) type obtained by dissolving or dispersing the metal oxide (A) in a solvent, and mixing the metal oxide (A) and the phosphorus compound (B).

A preferred method for producing a solution or dispersion of the metal oxide (A) is described below. Although here is a case where the metal oxide (A) does not contain metal atoms other than aluminum atoms, that is, a case where the metal oxide (A) is alumina is used as an example to explain the production of a dispersion liquid thereof Method, but similar solutions can also be used when manufacturing solutions and dispersions containing other metal atoms. A preferred dispersion of alumina can be obtained by: hydrolyzing and condensing aluminum alkoxide in an aqueous solution after adjusting the pH value with an acid catalyst as needed to form a slurry of alumina. It is degummed in the presence of a large amount of acid.

The temperature of the reaction system when the aluminum alkoxide is hydrolyzed and condensed is not particularly limited. The temperature of the reaction system is usually in the range of 2 to 100 ° C. The temperature of the liquid rises as soon as water comes in contact with the aluminum alkoxide. When the hydrolysis proceeds, alcohol is formed as a by-product. When the boiling point of the alcohol is lower than water, the alcohol will volatilize, causing the temperature of the reaction system to not rise Above the boiling point of alcohol. In this case, since the growth of alumina is slow, it is effective to remove the alcohol by heating to about 95 ° C. The reaction time will vary depending on the reaction conditions (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, and more preferably in the range of 0.5 to 6 hours. The reaction can be performed under various gas atmospheres such as air, carbon dioxide, nitrogen, and argon.

The amount of water used in the hydrolysis and condensation is preferably 1 to 200 mol times, and more preferably 10 to 100 mol times, relative to the aluminum alkoxide. When the amount of water is less than 1 mol times, the hydrolysis does not proceed sufficiently, so it is not good. On the other hand, when it exceeds 200 mol times, the manufacturing efficiency is lowered or the viscosity is increased, which is not preferable. When using a water-containing component (for example, hydrochloric acid, nitric acid, etc.), it is preferable to also consider the amount of water introduced due to the component to determine the amount of water used.

The acid catalyst used for the hydrolysis and condensation can be hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, benzoic acid, acetic acid, lactic acid, butyric acid, carbonic acid, oxalic acid, maleic acid, and the like. Among these, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, lactic acid, and butyric acid are preferable, and nitric acid and acetic acid are more preferable. When using an acid catalyst during hydrolysis and condensation, it is preferred to use an appropriate amount according to the type of acid so that the pH value before hydrolysis and condensation is in the range of 2.0 to 4.0.

The alumina slurry obtained by hydrolysis and condensation can also be used directly as an alumina dispersion. 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 used for degumming, monovalent inorganic acids and organic acids such as nitric acid, hydrochloric acid, perchloric acid, formic acid, acetic acid, and 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 nitric acid or hydrochloric acid is used as the acid for degumming, the amount is preferably 0.001 to 0.4 mole times, more preferably 0.005 to 0.3 mole times, relative to the aluminum atom. When it is less than 0.001 mol times, there may be problems such as inadequate degumming or taking a very long time. When it exceeds 0.4 mol times, the stability of the obtained alumina dispersion over time tends to decrease.

On the other hand, when acetic acid is used as the acid at the time of degumming, 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 mol times, unfavorable conditions such as inadequate degumming or a very long time may occur. When it exceeds 1.0 mol times, the stability of the obtained alumina dispersion over time tends to decrease.

The acid present at the time of degumming can be added during hydrolysis and condensation. However, when the acid disappears when the alcohol produced as a by-product during hydrolysis and condensation is removed, it is preferable to add it again so that the amount falls within the above range.

Degumming is performed in a range of 40 to 200 ° C, thereby degumming in a short period of time with an appropriate amount of acid to produce a dispersion of alumina having a specific particle size and excellent viscosity stability. If the temperature during degumming is less than 40 ° C, it will take a long time for degumming. If it exceeds 200 ° C, the increase in degumming speed due to increasing temperature is only a small amount. On the other hand, high pressure resistance is required. Containers and the like are economically unfavorable and therefore unfavorable.

After the degumming is completed, a solvent can be used for dilution, and a heating can be used for concentration to obtain a dispersion of alumina with a specific concentration. Among them, in the case of heating and concentration in order to suppress thickening and gelation, it is preferably performed at 60 ° C. or lower under reduced pressure.

The metal oxide (A) mixed with the phosphorus compound (B) (the composition containing the phosphorus-containing compound (B) when used as a composition) is preferably supplied without substantially containing a phosphorus atom. However, due to, for example, the influence of impurities during the preparation of the metal oxide (A), it may be supplied to be mixed with the phosphorus compound (B) (the composition containing the phosphorus-containing compound (B) when used as a composition). A small amount of phosphorus atoms are mixed into the metal oxide (A). Therefore, as long as the effect of the present invention is not impaired, the metal oxide (A) mixed with the phosphorus compound (B) (a composition containing the phosphorus compound (B) when used as a composition) may be supplied. Contains a small amount of phosphorus atoms. In order to obtain 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-containing compound (B) when used as a composition). The content rate of the phosphorus atom contained in the substance (A) is based on the molar number 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, even more preferably 5 mol% or less, particularly preferably 1 mol% or less, or 0 mol%.

The layer (YA) of the multilayer structure has a specific structure in which metal oxide (A) particles are bonded to each other via a phosphorus atom derived from a phosphorus compound (B), and the metal oxide in the layer (YA) The shape and size of the particles of (A) and the shape of the particles supplied to the metal oxide (A) mixed with the phosphorus compound (B) (a composition containing the phosphorus compound (B) when used as a composition) , Size can be the same or different. That is, the shape and size of the particles of the metal oxide (A) used as the raw material of the layer (YA) may be changed during the formation of the layer (YA). In particular, when the layer (YA) is formed using a coating liquid (U) described later, the coating liquid (U) may be used to form the liquid (S) described later, or the coating liquid may be used. (U) The shape and size may change in each step after coating on the base material (X).

[Phosphorus Compound (B)]

The phosphorus compound (B) contains a site that can react with the metal oxide (A), and typically contains a plurality of such sites. In a preferred example, the phosphorus compound (B) contains 2 to 20 such sites (atomic groups or functional groups). Examples of such a site include a site that can react with a functional group (for example, a hydroxyl group) existing on the surface of the metal oxide (A). 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 can initiate a condensation reaction (hydrolytic condensation reaction) with a hydroxyl group existing on the surface of the metal oxide (A). The functional group (for example, a hydroxyl group) existing on the surface of the metal oxide (A) is usually bonded to the metal atom (M) constituting the metal oxide (A).

As the phosphorus compound (B), for example, a structure in which a halogen atom or an oxygen atom is directly bonded to a phosphorus atom can be used. By using such a phosphorus compound (B), it is possible to interact with a hydroxyl group existing on the surface of the metal oxide (A). (Hydrolysis) condensation is performed, and bonding is performed. 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, phosphoric 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 derivatives include phosphoric acid, polyphosphoric acid, phosphorous acid, salts of phosphonic acid, (partial) ester compounds, halides (such as chlorides), and dehydrates (such as phosphorus pentoxide). Examples of derivatives of phosphonic acid include compounds in which a hydrogen atom directly bonded to a phosphorus atom of phosphonic acid (HP (= O) (OH) ₂ ) is substituted with an alkyl group which may have various functional groups (for example, Nitrilotris (methylene phosphonate), N, N, N ', N'-ethylenediamine tetra (methylenephosphonic acid), etc.), its salts, (partial) ester compounds , Halides and dehydrates. Furthermore, organic polymers having a phosphorus atom such as phosphorylated starch and a polymer (E) described later can also be used as the phosphorus compound (B). These phosphorus compounds (B) may be used individually by 1 type, and may use 2 or more types together. Among these phosphorus compounds (B), the coating liquid (U) when the coating liquid (U) described later is used to form the layer (YA) is more excellent in terms of the stability of the coating liquid (U) and the gas barrier properties of the obtained multilayer structure. In particular, it is preferable to use phosphoric acid alone or to use phosphoric acid together with phosphorus compounds other than them.

As described above, the layer (YA) of the multilayer structure includes a 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 a metal oxide (A) and a phosphorus compound (B). The phosphorus compound (B) to be supplied (before mixing) with the metal oxide (A) may be the phosphorus compound (B) itself, or may be in the form of a composition containing the phosphorus compound (B). The form of the composition of the phosphorus-containing compound (B) is preferred. A preferred example is a solution in which the phosphorus compound (B) is dissolved in a solvent, and the phosphorus compound (B) and the metal oxide (A) are mixed. Any solvent can be used at this time, and preferred solvents include water or a mixed solvent containing water.

In terms of obtaining a multilayer structure having more excellent gas barrier properties, it is preferable that the multilayer structure is supplied to a phosphorus compound (B) or a phosphorus-containing compound (B) mixed with the metal oxide (A). The metal atom content is low. The content rate of the metal atoms contained in the phosphorus compound (B) or the phosphorus-containing compound (B) mixed with the metal oxide (A) is determined by the phosphorus compound (B) or the phosphorus-containing compound. When the molar number of all phosphorus atoms contained in the composition of (B) is used as a reference (100 mol%), it is preferably 100 mol% or less, more preferably 30 mol% or less, and even more preferably 5 Molar% or less, particularly preferred is 1 mole% or less, or 0 mole%.

[Reaction product (R)]

The reaction product (R) includes a reaction product produced by a reaction of only the metal oxide (A) and the phosphorus compound (B). The reaction product (R) also includes a reaction product produced by a reaction between the metal oxide (A) and the phosphorus compound (B) and further other compounds. The reaction product (R) can be formed by a method described in a production method described later.

[Ratio of Metal Oxide (A) to Phosphorus Compound (B)]

In the layer (YA), the mole number N _M of the metal atom constituting the metal oxide (A) and the mole number N _P of the phosphorus atom derived from the phosphorus compound (B) satisfy 1.0 ≦ (mole number N _M ) / ( The relationship between the Mohr number N _P ) ≦ 3.6 is better, and the relationship of 1.1 ≦ (Mohr number N _M ) / (Molar number N _P ) ≦ 3.0 is more preferable. If the value of (Molar number N _M ) / (Molar number N _P ) exceeds 3.6, the metal oxide (A) will be excessive with respect to the phosphorus compound (B), and the particles of the metal oxide (A) will bond to each other. Insufficient junction, and the amount of hydroxyl groups existing on the surface of the metal oxide (A) will increase, so the gas barrier property and the stability thereof tend to decrease. On the other hand, if the value of (Molar number N _M ) / (Molar number N _P ) is less than 1.0, the phosphorus compound (B) will be excessive relative to the metal oxide (A), and will not participate in the metal oxide (A). (A) The remaining phosphorus compound (B) to be bonded is increased, and the amount of the hydroxyl group derived from the phosphorus compound (B) is likely to be increased, and the gas barrier property and the stability thereof tend to decrease.

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 used to form the layer (YA). The ratio of the mole number N _M to the mole number N _P in the layer (YA) is usually the ratio in the coating liquid, and the mole number of the metal atom constituting the metal oxide (A) and the phosphorus compound ( B) The molar ratio of phosphorus atoms 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 acid anhydride group, and a salt of a carboxyl group. The polymer (C) in the layer (YA) of the multi-layered structure can also interact with the particles of the metal oxide (A) and the phosphorus atoms derived from the phosphorus compound (B) via the functional group (f). One or both are bonded directly or indirectly. In addition, the reaction product (R) in the layer (YA) of the multilayer structure may include a polymer (C) produced by reacting the polymer (C) with the metal oxide (A) and the phosphorus compound (B). )section. In addition, in the present specification, a polymer satisfying the requirements of the phosphorus compound (B) and containing a functional group (f) is not included 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 constituent units include functional units such as vinyl alcohol units, acrylic units, methacrylic units, maleic acid units, itaconic units, maleic anhydride units, and phthalic anhydride units. (f) More than one constituent unit. The polymer (C) may contain only one kind of constituent unit having a functional group (f), or may contain two kinds of constituent units having a functional group (f).

In order to obtain a multilayer structure having more excellent gas barrier properties and stability, the proportion of the constituent units having functional groups (f) in the total constituent units of the polymer (C) is preferably 10 mol% or more It is more preferably 20 mol% or more, even more preferably 40 mol% or more, particularly preferably 70 mol% or more, and 100 mol%.

When the polymer (C) is constituted by a structural unit having a functional group (f) and other structural units other than that, the type of the other structural unit is not particularly limited. Examples of the other constituent units include (meth) methyl acrylate units, methyl methacrylate units, ethyl acrylate units, ethyl methacrylate units, butyl acrylate units, and butyl methacrylate units. Acrylate-derived constituent units; vinyl formate units and vinyl acetate Ester units and other units derived from vinyl esters; styrene units and p-styrenesulfonic acid units and other units derived from aromatic ethylene; ethylene units, propylene units, and isobutene units and other units derived from olefins Wait. When the polymer (C) contains two or more kinds of 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 partially saponified product of polyvinyl acetate, polyethylene glycol, poly (hydroxyethyl methacrylate), polysaccharides such as starch, and the like Polysaccharide derivatives derived from polysaccharides. Specific examples of the polymer (C) having a carboxyl group, a carboxylic anhydride group, or a salt of a carboxyl group include polyacrylic acid, polymethacrylic acid, poly (acrylic acid / methacrylic acid), and salts thereof. Specific examples of the polymer (C) containing a structural unit not containing a functional group (f) include an ethylene-vinyl alcohol copolymer, an ethylene-maleic anhydride copolymer, and a styrene-maleic anhydride. Copolymers, isobutylene-maleic anhydride alternating copolymers, ethylene-acrylic acid copolymers, saponifications of ethylene-ethyl acrylate copolymers, etc. In order to obtain a multilayer structure having more excellent gas barrier properties and stability, the polymer (C) is preferably selected from the group consisting of polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polysaccharides, polyacrylic acid, and polyacrylic acid salts , Polymethacrylic acid, and at least one polymer of the group consisting of polymethacrylic acid salts.

The molecular weight of the polymer (C) is not particularly limited. In order to obtain a multilayer structure having more excellent gas barrier properties and mechanical properties (dropping impact strength, etc.), the number average molecular weight of the polymer (C) is preferably 5,000 or more, more preferably 8,000 or more, and even 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 rate 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, even more preferably 30% by mass or less, or 20% by mass. %the following. The polymer (C) may or may not react with other components in the layer (YA). In addition, in this specification, when a polymer (C) reacts with another component, it will also appear as a polymer (C). For example, when the polymer (C) is bonded to the metal oxide (A) and / or a phosphorus atom derived from the phosphorus compound (B), the polymer (C) 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 bonding with the metal oxide (A) and / or the phosphorus atom by the mass of the layer (YA).

The layer (YA) of the multilayer structure may be a reaction product (R) formed by reacting only a metal oxide (A) containing at least aluminum with a phosphorus compound (B) (containing a polymer (C) portion (1), it may consist 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, for example, carbonates, hydrochlorides, nitrates, bicarbonates, sulfates, bisulfates, borate, aluminates, and other inorganic acid metal salts; oxalate, acetate, and tartrate Metal salts of organic acids, such as stearates; acetoacetone metal complexes (such as aluminum acetone aluminum acetone, etc.), cyclopentadienyl metal complexes (titanocene, etc.), cyano metal complexes Laminated clay compounds; Crosslinking agents; Polymer compounds other than polymer (C); Plasticizers; Antioxidants; UV absorbers; Flame retardants, etc.

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

[Thickness of layer (YA)]

The thickness of the layer (YA) of the multilayer 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, and It is more preferably 1.0 μm or less, and may be 0.9 μm or less. By thinning the layer (YA), the dimensional change of the multilayer structure during printing, lamination, and other processing can be suppressed to be low, and the flexibility of the multilayer structure is increased, and its mechanical properties can be made close to the substrate Its own mechanical properties.

In a 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 can be 2ml / (m ² ‧day ‧Atm) or less. 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). In addition, the thickness of each layer (YA) is preferably 0.05 μm or more (for example, 0.15 μm or more) from the viewpoint that the multilayer structure has better gas barrier properties. The thickness of the layer (YA) can be controlled by the concentration of a coating solution (U) to be described later used for forming the layer (YA), and the coating method thereof.

[Layer (YB) and Layer (YC)]

The layer (Y) included in the multilayer structure may be a layer (YB) that is a vapor-deposited layer of aluminum or a layer (YC) that is a vapor-deposited layer of alumina. These vapor-deposited layers can be produced by the same method as the inorganic vapor-deposited layer described later.

[Layer (Z)]

The layer (Z) of the multilayer structure contains a polymer (E), and the polymer (E) contains a monomer unit having a phosphorus atom. By forming the layer (Z) so that the layer (Z) and the layer (Y) are adjacent to each other, 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 phosphorus atom-containing acidic group include a phosphate group, a polyphosphate group, a phosphite group, and a phosphonic acid group. Among the plurality of phosphorus atoms in the polymer (E), at least one phosphorus atom contains a site that can react with the metal oxide (A). In a preferred example, the polymer (E) contains about 10 to 1,000 such phosphorus atoms. Examples of the site of the phosphorus atom that can react with the metal oxide (A) include the site of the structure described for the phosphorus compound (B).

The polymer (E) is not particularly limited as long as it satisfies the above conditions. As a preferred example, a single polymer or copolymer of a (meth) acrylic acid ester containing a phosphate group at a side chain terminal may be mentioned. These polymers can be obtained by synthesizing (meth) acrylic monomers having a phosphate group at the end of the side chain, and polymerizing these alone or copolymerizing with other vinyl-containing monomers. .

The (meth) acrylic acid ester containing a phosphate group at a side chain terminal used in the present invention may be at least one compound represented by the following general formula (IV).

[Wherein, in formula (IV), R ⁵ and R ⁶ are hydrogen atoms or an alkyl group selected from methyl, ethyl, n-propyl, and isopropyl groups, and a part of hydrogen atoms contained in the alkyl group may pass other atoms 2, substituted by functional groups. In addition, n is a natural number, and is typically an integer of 1 to 6. A

As 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 general formula (IV), examples of monomers applicable to the present invention include acrylic acid phosphooxyethyl methacrylate, methacrylic acid phosphooxyethyl ester, and acrylic acid. Acid phosphooxy polyoxyethylene glycol ester, methacrylic acid phosphooxy polyoxyethylene glycol ester, acrylic acid phosphooxy polyoxypropylene glycol ester, methacrylic acid phosphooxy polyoxypropylene glycol ester , 3-chloro-2-acid phosphorusoxypropyl acrylate, and 3-chloro-2-acid phosphorusoxypropyl methacrylate, and the like. Among these, a single polymer of methacrylic acid phosphoroxyethyl ester is preferable from the viewpoint of obtaining a multilayer structure having excellent bending resistance. However, the monomers usable in the present invention are not limited to these. Part of these monomers can be appropriately purchased from uni-chemical Co., Ltd. under the trade name Phosmer.

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

The other vinyl monomer that can be copolymerized with the monomer represented by the general formula (IV) is not particularly limited as long as it is copolymerizable with the monomer represented by the general formula (IV), and a conventional one can be used. Examples of such vinyl monomers include acrylic acid, acrylates, methacrylic acid, methacrylates, acrylonitrile, methacrylonitrile, styrene, core-substituted styrenes, alkyl vinyl ethers, and alkane Vinyl esters, perfluoroalkylvinylethers, perfluoroalkylvinylesters, maleic acid, maleic anhydride, fumaric acid, itaconic acid, maleic acid Diene diimide or phenyl maleimide diimide and the like. Of these vinyl monomers, particularly preferred are methacrylates, acrylonitrile, styrenes, maleimide, phenylmaleimide.

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

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

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

(b) The carbon chain of the substituent is bonded to a phosphorus atom (phosphoric acid group, phosphinic acid group, or phosphorus atom in the ester) in the 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 carbocyclic ring.

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

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

The carbon number contained in the carbon chain of the substituent bonded to the phosphorus atom may be in a range of 2 to 30 (for example, a 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- Propenyl, 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 more than one oxycarbonyl group 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. Moreover, in addition to the above-mentioned hydrocarbon chain having a carbon-carbon double bond on the carbocyclic ring, one or more saturations may be bonded. Hydrocarbon chain (e.g. methyl, ethyl, propyl, etc.). Examples of the substituent bonded to a phosphorus atom include the above-mentioned hydrocarbon chain having a carbon-carbon double bond, such as vinyl, and 4-vinylbenzyl, etc., which are bonded to the above-mentioned carbon ring Carbon ring.

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

The polymer (E) can also be obtained by polymerizing vinylphosphonic acid-based monomers or copolymerizing with other vinyl-containing monomers. The polymer (E) can also be obtained by hydrolyzing a vinylphosphonic acid derivative such as a phosphonic acid halide, an ester, etc. alone or after copolymerization.

Examples of suitable vinylphosphonic acid monomers include alkenylphosphonic acids such as vinylphosphonic acid and 2-propylene-1-phosphonic acid; 4-vinylbenzylphosphonic acid and 4-vinylphenylphosphine Alkenyl aromatic phosphonic acids such as acids; 6-[(2-phosphonoacetyl) oxy] hexyl acrylate (6-[(2-phosphonoacetyl) oxy] hexylacrylate), phosphoromethylmethacrylate, Phosphine (meth) acrylates such as 11-phosphine undecyl methacrylate, 1,1-diphosphine ethyl methacrylate; vinyl phosphinic acid, 4-vinyl benzyl phosphinic acid, etc. Phosphonic acids and so on. Among them, poly (vinylphosphonic acid), which is a separate polymer of vinylphosphonic acid, is preferable from the viewpoint of obtaining a multilayer structure excellent in bending resistance. However, the usable monomers are not limited to these.

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

Other vinyl monomers that can be copolymerized with vinylphosphonic acid monomers, as long as they are The copolymerizable with the vinylphosphonic acid monomer is not particularly limited, and a known one can be used. Examples of such vinyl monomers include acrylic acid, acrylates, methacrylic acid, methacrylates, acrylonitrile, methacrylonitrile, styrene, core-substituted styrenes, alkyl vinyl ethers, Alkyl vinyl esters, perfluoro-alkyl vinyl ethers, perfluoro-alkyl vinyl esters, maleic acid, maleic anhydride, fumaric acid, itaconic acid, cis Butene difluorene imine or phenyl maleimide diimine, etc. Among these vinyl monomers, methacrylic acid esters, acrylonitrile, styrenes, maleimide, and phenylmaleimide are particularly preferable.

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

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

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

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

The molecular weight of the polymer (E) is not particularly limited. 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 in this range, then A high level of both the effect of improving the bending resistance of the layer (Z) and the viscosity stability of the coating liquid (V) containing the polymer (E) described later can be achieved. In addition, when the molecular weight of the polymer (E) per phosphorus atom is in the range of 150 to 500, the effect of improving the bending resistance produced by laminating the layer (Z) may be further enhanced.

The layer (Z) of the multilayer structure may be composed of only 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 carbonate, hydrochloride, nitrate, bicarbonate, sulfate, bisulfate, and borate; oxalate, acetate, tartrate, and stearate Metal salts of organic acids, etc .; metal complexes such as acetoacetone metal complexes (magnesium acetoacetone, etc.), cyclopentadienyl metal complexes (titanocene, etc.), metal complexes such as cyano metal complexes; Layered clay compounds; cross-linking agents; polymer compounds other than polymer (E); plasticizers; antioxidants; ultraviolet absorbers; flame retardants, etc.

In the layer (Z) in the multilayer structure, the content of the other components is preferably 50% by mass or less, more preferably 20% by mass or less, even 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 performed using a polymerization initiator in a solvent in which both the monomer component as a raw material and the produced polymer are dissolved. Examples of the polymerization initiator include 2,2-azobisisobutyronitrile, 2,2-azobis (2,4-dimethylvaleronitrile) (2,2-azobis (2,4-dimethylvaleronitrile)) Azo series such as dimethyl 2,2-azobis (2-methylpropionate), dimethyl 2,2-azobisisobutyrate Initiators, peroxide-based initiators such as lauroyl peroxide, benzoyl peroxide, tert-butyl peroctoate, etc. . when In the case of copolymerization with other vinyl monomers, an appropriate solvent can be selected according to the combination of comonomers. If necessary, two or more mixed solvents may be used.

An example of the polymerization reaction is to drop a mixed solution composed of a monomer, a polymerization initiator, and a solvent into a solvent, and proceed at a polymerization temperature of 50 to 100 ° C. After the drop is completed, it is maintained at the polymerization temperature for about 1 to 24 hours or At the above temperature, stirring is continued to complete the polymerization.

When the monomer component is 1, the solvent is preferably used at a weight ratio of about 1.0 to 3.0, and the polymerization initiator is preferably used at a weight ratio of about 0.005 to 0.05. A more preferred weight ratio solvent is 1.5 to 2.5, and a polymerization initiator is about 0.01. If the amount of the solvent or polymerization initiator used is outside the above range, problems such as gelation of the polymer and insolubility in various solvents may occur, and coating with a solution may not be performed.

The layer (Z) of the multilayer structure can be formed by applying a solution of the polymer (E). Any solvent can be used at this time, and preferred solvents include water, alcohols, or mixed solvents 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, and if it is 1.0 μm or more, the bending resistance improvement effect becomes saturated. Therefore, it is preferable to limit the thickness of the layer (Z) to 1.0 μm in terms of economy. The thickness of the layer (Z) can be controlled by the concentration of the coating solution (V) used later to form the layer (Z) and the coating method thereof.

[Substrate (X)]

The material of the substrate (X) included in the multilayer structure is not particularly limited, and substrates composed of various materials can be used. Examples of the material of the substrate (X) include resins such as thermoplastic resins and thermosetting resins; metals; and metal oxides. The substrate may be a composite structure or a multilayer structure composed of a plurality of materials.

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

The layered substrate includes, for example, a single layer or a plurality of layers including at least one layer 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. Of the substrate. Among these, a substrate containing a thermoplastic resin film layer is preferred. In this case, the substrate may be a single layer or a plurality of layers. A multilayer structure (laminated structure) using such a substrate is excellent in various characteristics required for use as a protective sheet.

Examples of the thermoplastic resin film forming the thermoplastic resin film layer include polyolefin resins such as polyethylene and polypropylene; polyethylene terephthalate and polyethylene-2,6-naphthalene dicarboxylate (polyethylene-2 , 6-naphthalate), polybutylene terephthalate, copolymers of these, etc .; Polyamide resins such as nylon-6, nylon-66, nylon-12; polyvinyl alcohol, ethylene- Hydroxyl-containing polymers such as ethylene-vinyl alcohol copolymer; polystyrene; poly (meth) acrylate; polyacrylonitrile; polyvinyl acetate; polycarbonate; polyarylate (Polyarylate); regenerated cellulose; polyfluorene imine; polyetherfluorene imine; polyfluorene; polyetherfluorene; polyetheretherketone; a film obtained by processing a thermoplastic resin such as an ionic polymer resin.

When a transparent protective sheet is sought, as the material of the base material (X), a thermoplastic resin having translucency is preferably used. Examples of translucent thermoplastic resins include polyethylene terephthalate, polycarbonate, polymethyl methacrylate, polystyrene, and polymethylmethacrylate. Methyl acrylate / styrene copolymer, syndiotactic polystyrene, cyclic polyolefin, cyclic olefin copolymer, polyvinyl acetate, polyimide, polypropylene, polyethylene, polynaphthalene Ethylene glycol formate, polyvinyl acetal, polyvinyl butyral, polyvinyl alcohol, polyvinyl chloride, polymethylpentene, etc. 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 an unstretched film. Since the obtained multilayer structure is excellent in processability (printing, lamination, etc.), a stretched film is preferred, and a biaxially stretched film is particularly preferred. The biaxially stretched film may be a biaxially stretched film produced by any of a simultaneous biaxially stretching method, a sequential biaxially stretching method, and a tubular stretching method.

The inorganic vapor deposition layer is preferably one having barrier properties against oxygen and water vapor. As the inorganic vapor-deposited layer, those having light-shielding properties such as metal vapor-deposited layers such as aluminum and those having transparency can be suitably used. The inorganic vapor-deposited layer can be formed by vapor-depositing an inorganic substance on a substrate for vapor deposition, and the entire laminated body having the inorganic vapor-deposited layer formed on the substrate for vapor deposition can be used as the base material (X) having a multilayer structure. Examples of the inorganic vapor-deposited layer having transparency include a layer formed of an inorganic oxide such as aluminum oxide, silicon oxide, silicon oxynitride, magnesium oxide, tin oxide, or a mixture thereof; silicon nitride, silicon carbonitride (silicon carbonitride) and other inorganic nitrides; silicon carbide and other inorganic carbides. Among these, a layer formed of aluminum oxide, silicon oxide, magnesium oxide, and silicon nitride is preferable from the viewpoint of excellent barrier properties against oxygen and water vapor.

The preferred thickness of the inorganic vapor-deposited layer varies depending on the types of components constituting the inorganic vapor-deposited layer, and is usually in the range of 2 to 500 nm. Select the barrier properties and mechanical properties of the multilayer structure within this range. A thickness with good mechanical properties is sufficient. If 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 and water vapor tends to decrease, and the inorganic vapor-deposited layer may not exhibit sufficient barrier properties. When the thickness of the inorganic vapor-deposited layer exceeds 500 nm, the barrier properties of the inorganic vapor-deposited layer tend to be lowered when the multilayer structure is stretched or bent. The thickness of the inorganic vapor deposition layer is preferably in a range of 5 to 200 nm, and even more preferably in a range of 10 to 100 nm.

Examples of the method for forming the inorganic vapor deposition layer include a vacuum vapor deposition method, a sputtering method, an ion plating method, and a chemical vapor deposition method (CVD). Among these, a vacuum deposition method is preferable from a viewpoint of productivity. The heating method in vacuum deposition is preferably any one of an electron beam heating method, a resistance heating method, and an induction heating method. In addition, in order to improve the adhesion to the substrate for the deposition with the inorganic vapor deposition layer and the denseness of the inorganic vapor deposition layer, a plasma assisted method or an ion beam assisted method can be used for vapor deposition. . In addition, in order to improve the transparency of the inorganic vapor deposition layer, during vapor deposition, a reaction vapor deposition method in which oxygen is blown to generate a reaction can be used.

When the thickness of the substrate (X) is layered, from the viewpoint of good mechanical strength and processability of the obtained multilayer structure, a range of 1 to 1000 μm is preferred, and a range of 5 to 500 μm is more preferred. A more preferable range is 9 to 200 μm.

[Next layer (H)]

In the multilayer structure, the layer (Y) and / or the layer (Z) may be laminated in a direct contact with the substrate (X), and the layer (Y) and / or the layer (Z) may also be disposed on the substrate (X) Adhesive layer (H) between layer (Y) and / or layer (Z) is laminated on substrate (X). With this configuration, the adhesion between the substrate (X) and the layer (Y) and / or the layer (Z) may be improved in some cases. Next layer (H) can also be Adhesive resin is formed. The adhesive layer (H) made 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 on the surface of the substrate (X). The adhesive is preferably a two-liquid reactive polyurethane adhesive that mixes and reacts a polyisocyanate component and a polyol component. In addition, by adding a small amount of conventional additives such as a silane coupling agent to the anchor coating agent and the adhesive, the adhesion may be further improved. Preferable examples of the silane coupling agent include a silane coupling agent having a reactive group such as an isocyanate group, an epoxy group, an amine group, a ureido group, or a mercapto group. The base layer (X) and the layer (Y) and / or the layer (Z) are strongly bonded by the bonding layer (H), and when the multilayer structure is subjected to processing such as printing and lamination, it can be effectively suppressed Deterioration of gas barrier properties and appearance.

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

[Construction of multilayer structure]

The multilayer structure (laminate) may be composed of only the substrate (X), layer (Y), and layer (Z), or may be composed of only the substrate (X), layer (Y), layer (Z), and adhesive layer ( H) composition. The multilayer structure may include a plurality of layers (Y) and / or a plurality of layers (Z). Furthermore, the multilayer structure may further include members other than the base material (X), the layer (Y), the layer (Z), and the adhesive layer (H) (for example, other layers such as a thermoplastic resin film layer and an inorganic vapor-deposited layer). A multilayer structure having such other components (other layers, etc.) can be manufactured by, for example, directly or via the layer (Y), the layer (Y) And the layer (Z) is laminated on the base material (X), and then the other member (other layer, etc.) is further formed directly or via an adhesive layer. By including such other members (other layers, etc.) in the multilayer structure, the characteristics of the multilayer structure can be improved or new characteristics can be provided. For example, heat-sealing properties can be imparted to the multilayer structure, or barrier properties and mechanical properties can be further improved.

In particular, when the outermost layer of the multilayer structure is a polyolefin layer, heat-sealing properties can be imparted to the multilayer structure, and mechanical properties of the multilayer structure can be improved. From the viewpoints of heat sealability, improvement of mechanical properties, etc., the polyolefin is preferably polypropylene or polyethylene. In addition, in order to improve the mechanical properties of the multilayer structure, it is preferable to laminate at least one film selected from the group consisting of a film made of polyester, a film made of polyamide, and A film made of a polymer containing hydroxyl groups. From the viewpoint of improving mechanical properties, the polyester is preferably polyethylene terephthalate (PET), the polyamide is preferably nylon-6, and the hydroxyl-containing polymer is preferably ethylene-ethylene Alcohol copolymer. Furthermore, if necessary, a layer composed of an anchor coating and an adhesive may be provided between the layers.

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 other layers 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), A polymer layer (for example, an ethylene-vinyl alcohol copolymer layer), an inorganic vapor-deposited film layer, a thermoplastic elastomer layer, and an adhesive layer. As long as the multilayer structure includes a base material, a layer (Y), and a layer (Z), and at least one set of the layer (Y) and the layer (Z) are adjacent and laminated, the other layers and the layer (Y) and the layer ( The number of Z) and the stacking order are not particularly limited. A preferred example is a structure having at least one set of substrate (X), layer (Y), and layer (Z) laminated in the order of substrate (X) / layer (Y) / layer (Z). Multi-layered structure.

[Protection sheet for electronic devices]

According to a preferred embodiment of the present invention, the protective sheet can realize one or both of the following properties. A preferred example is a multilayer having a thickness of layer (Y) (the total thickness of each layer (Y) when the multilayer structure has two or more layers (Y)) is 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. In addition, the measurement conditions of the oxygen permeability are explained in detail by examples.

(Performance 1) The oxygen permeability of the protective sheet under the 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) After protecting the protective sheet at 23 ° C and 50% RH under a condition of 5% unidirectional stretching for 5 minutes, the oxygen permeability of the protective sheet at 20 ° C and 85% RH 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-mentioned multilayer structure, it has excellent gas barrier properties, and can maintain gas barrier properties at a high level even when subjected to physical pressure such as deformation and shock. In addition to the gas barrier property, the protective sheet in the electronic device of the present invention may have a barrier property against water vapor. In this case, the water vapor barrier property can be maintained at a high level even when subjected to physical pressure such as deformation and impact.

The protective sheet in the electronic device of the present invention can also be used as a film called a substrate film such as an LCD substrate film, an organic EL substrate film, and an electronic paper substrate film. The electronic device to be protected is not limited to those listed above, and may be, for example, an 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 made of a resin that is less prone to scars. Again, as The surface protective layer of a device such as a solar cell which is sometimes used outdoors is preferably made of a resin having high weather resistance (for example, light resistance). Moreover, when it is necessary to protect a surface through which light must be transmitted, a surface protective layer having high light transmittance is preferred. Examples of the material of the surface protective layer (surface protective film) include acrylic resin, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, ethylene-tetrafluoroethylene copolymer, polytetrafluoroethylene , 4-fluorinated ethylene-perchloroalkoxy copolymer, 4-fluorinated ethylene-6-fluorinated propylene copolymer, 2-ethylene-4-fluorinated ethylene copolymer, poly3-fluorinated vinyl chloride, polyfluorinated Vinylidene, polyvinyl fluoride. An example of the protective sheet includes an acrylic resin layer disposed on one surface. Furthermore, 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 preferable example of the weather-resistant surface protective layer is an acrylic resin layer to which a UV absorber is added. Examples of the ultraviolet absorber include conventional ultraviolet absorbers such as benzotriazole-based, diphenylketone-based, salicylate-based, cyanoacrylate-based, nickel-based, and triazine-based ultraviolet absorbers. Further, other stabilizers, light stabilizers, antioxidants, and the like may be used in combination.

When a protective sheet is to be bonded to a sealing material that seals the main body of the electronic device, the protective sheet preferably contains a resin layer for bonding that can improve the adhesion to the sealing material. Examples of the resin layer for bonding include polyethylene terephthalate (EVA easily adheres to a PET film) which can improve the adhesion to EVA.

The layers constituting the protective sheet can be bonded using, for example, a conventional adhesive and the aforementioned adhesive layer.

[Manufacturing method of multilayer structure]

A method for manufacturing the multilayer structure will be described below.

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

Furthermore, when the layer (Y) of the multilayer structure is a layer (YB) that is a vapor-deposited layer of aluminum or a layer (YC) that is a vapor-deposited layer of alumina, the layer (YB) and the layer (YC) It is formed by the vapor deposition method, so detailed description is omitted. In the following, the case where the layer (Y) of the multilayer structure is a layer (YA) containing a reaction product (R) will be described, and the reaction product (R) is a metal oxide containing at least aluminum ( A) It reacts with a phosphorus compound (B). In addition, the method of forming the layer (Z) (step (IV) described later) can use the same formation regardless of whether the layer (Y) is any of the layer (YA), the layer (YB), and the layer (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 manufacturing the multilayer structure preferably includes steps (I), (II), (III), and (IV). In step (I), a metal oxide (A) containing at least aluminum, at least one compound containing a site capable of reacting with the metal oxide (A), and a solvent are mixed to prepare a metal oxide containing ( A) the coating solution (U) of the at least one compound and the solvent. In step (II), a coating liquid (U) is applied on the substrate (X), thereby forming a precursor layer of the layer (YA) on the substrate (X). In 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). In step (IV), a coating solution (V) containing a polymer (E) is applied to form a layer (Z), and the polymer (E) contains a monomer unit having a phosphorus atom. Furthermore, typically, the above steps are performed in the order of (I), (II), (III), (IV). When the layer (Z) is formed between the substrate (X) and the layer (YA) In time, step (IV) may be performed before step (II). As described later, the step may be performed after step (IV). Step (III).

[Step (I)]

In the step (I), at least one compound containing a site capable of reacting with the metal oxide (A) is hereinafter sometimes referred to as "at least one compound (Z)". In step (I), at least the metal oxide (A), at least one compound (Z), and a solvent are mixed. From one viewpoint, in the step (I), a raw material containing the metal oxide (A) and at least one compound (Z) is reacted in a solvent. This 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 solution (U), the mole number N _M of the metal atom (M) constituting the metal oxide (A) and the mole number N _P of the phosphorus atom contained in the phosphorus compound (B), satisfy 1.0 ≦ ( The relationship between Mohr number N _M ) / (Mohr number N _P ) ≦ 3.6. The preferable range of the value of (Molar number N _M ) / (Molar number N _P ) is as described above, and therefore repeated descriptions are omitted.

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

The ratio of (the mole number of the metal atom contained in at least one compound (Z)) / (the mole number of the phosphorus atom contained in the phosphorus compound (B)) is set to a range of 0 to 1 (for example, 0 to 0.9 Range), thereby obtaining a multilayer structure having more excellent gas barrier properties. In order to advance Step by step to improve the gas barrier properties of the multilayer structure, this is more preferably 0.3 or less, more preferably 0.05 or less, still more preferably 0.01 or less, and also 0. Typically, at least one compound (Z) is composed of only a phosphorus compound (B). In step (I), the above ratio can be easily reduced.

Step (I) preferably includes 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 a phosphorus compound (B).

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

Step (b) may be performed before step (a), may be performed simultaneously with step (a), or may be performed after step (a). Each step will be described more specifically below.

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

Step (a) may include a step of condensing (for example, hydrolytic condensation) of at least one selected from the group consisting of the compound (L) and the hydrolysate of the compound (L). Specifically, step (a) may include a step of condensing or hydrolytically condensing at least one selected from the group consisting of the partial condensation of materials such as the following compounds (L), Compound (L) A local hydrolyzate of the compound, a complete hydrolyzate of the compound (L), a local hydrolyzed condensate of the compound (L), and a complete hydrolyzate of the compound (L).

Another example of the method for preparing the liquid (S) includes a method including the following steps. First, metal is vaporized into metal atoms by thermal energy, and the metal atoms are brought into contact with a reactive gas (oxygen), thereby generating molecules and clusters of metal oxides. Thereafter, these are cooled instantaneously, thereby producing particles of the metal oxide (A) having a small particle diameter. Next, the particles are dispersed in water or an organic solvent to obtain a liquid (S) (a dispersion liquid containing a metal oxide (A)). In order to improve the dispersibility to water or organic solvents, the particles of the metal oxide (A) may be subjected to a surface treatment, or a stabilizer such as a surfactant may be added. The dispersibility of the metal oxide (A) can also be improved by controlling the pH.

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

The type of the organic solvent that can be used in step (a) is not particularly limited, and for example, alcohols such as methanol, ethanol, isopropanol, and 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, and even more preferably in the range of 2 to 20% by mass. Inside.

In step (b), a solution (T) of the phosphorus-containing compound (B) is prepared. The solution (T) can be prepared by dissolving the phosphorus compound (B) in a solvent. When the solubility of the phosphorus compound (B) is low In this case, heat treatment and ultrasonic treatment can be used to promote dissolution.

The solvent used for the preparation of the solution (T) can be appropriately selected according to the type of the phosphorus compound (B), but water is preferred. As long as the dissolution of the phosphorus compound (B) is not hindered, the solvent may contain alcohols such as methanol and ethanol; Alkanes, tris Ethers such as trioxane and dimethoxyethane; ketones such as acetone, methyl ethyl ketone; glycols such as ethylene glycol and propylene glycol; Diol derivatives such as n-butyl cyperidine; glycerol; acetonitrile; fluorenamines such as dimethylformamide; dimethylsulfoxide; sulfolane and the like.

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, and even more preferably in the range of 0.1 to 90% by mass. . 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 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 local reactions, it is preferable to perform mixing while suppressing the addition rate and stirring vigorously. At this time, the solution (T) may be added to the liquid (S) while stirring, and the liquid (S) may also be added to the solution (T) while stirring. The temperature of the liquid (S) and the temperature of the solution (T) during the mixing in step (c) are preferably 50 ° C or lower, both 30 ° C or lower, and 20 ° C or lower. Since the temperatures at the time of mixing are 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 multilayer structure can be improved. Furthermore, stirring may be continued for about 30 minutes from the point of completion of mixing, whereby the coating liquid (U) having excellent storage stability may be obtained.

The coating liquid (U) may contain a polymer (C). Contain coating liquid (U) The method of the polymer (C) is not particularly limited. For example, the polymer (C) may be added to the liquid (S), the solution (T), or the mixed solution of the liquid (S) and the solution (T) in a powder or pellet state, and then dissolved. Further, a solution of the polymer (C) may be added to the liquid (S), the solution (T), or a mixed solution of the liquid (S) and the solution (T) to be mixed. Further, a liquid (S), a solution (T), or a mixed liquid of the liquid (S) and the solution (T) may be added to the solution of the polymer (C) and mixed. Since the polymer (C) is contained in either the liquid (S) or the solution (T) before step (c), when the liquid (S) and the solution (T) are mixed in step (c), the metal The reaction rate of the oxide (A) and the phosphorus compound (B) is moderated, and as a result, a coating liquid (U) having excellent stability over time may be obtained.

When the coating solution (U) contains the polymer (C), a multilayer structure including a layer (YA) containing the polymer (C) can be easily produced.

The coating liquid (U) may optionally contain at least one acid compound (D) selected from the group consisting of acetic acid, hydrochloric acid, nitric acid, trifluoroacetic acid, and trichloroacetic acid. Hereinafter, the at least one acid compound (D) may be simply referred to as "acid compound (D)". The method for making the coating liquid (U) contain the acid compound (D) is not particularly limited. For example, the acid compound (D) can be directly added to the liquid (S), the solution (T), or the mixed solution of the liquid (S) and the solution (T) for mixing. Further, a solution of the acid compound (D) may be added to the liquid (S), the solution (T), or the mixed solution of the liquid (S) and the solution (T) to be mixed. Alternatively, a liquid (S), a solution (T), or a mixed liquid of the liquid (S) and the solution (T) may be added to the solution of the acid compound (D) and mixed. Since either the liquid (S) or the solution (T) contains the acid compound (D) before step (c), when the liquid (S) and the solution (T) are mixed in step (c), the metal The reaction rate of the oxide (A) and the phosphorus compound (B) is moderated, and as a result, a coating liquid (U) having excellent stability over time may 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 the precipitation and aggregation of the reactants in the coating liquid (U) can be suppressed. Therefore, by using the coating liquid (U) containing the acid compound (D), the appearance of the obtained multilayered structure may be improved. 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 within a range of 0.1 to 5.0% by mass, and more preferably within a range of 0.5 to 2.0% by mass. In these ranges, the effect obtained by adding 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 remaining amount.

The liquid obtained by mixing in step (c) can be directly used as the coating liquid (U). In this case, usually, the solvent contained in the liquid (S) and the solution (T) becomes the solvent of the coating liquid (U). In addition, the liquid obtained by mixing in step (c) may be processed to prepare a coating liquid (U). It is also possible to perform processes such as adding an organic solvent, adjusting pH, adjusting viscosity, adding additives, and the like.

An organic solvent may be added to the liquid obtained by mixing in the step (c) so as not to hinder the stability of the obtained coating liquid (U). By adding an organic solvent, it may become easy to apply the coating liquid (U) to the substrate (X) in step (II). The organic solvent is preferably one which can be uniformly mixed in the obtained coating liquid (U). Examples of preferred organic solvents include alcohols such as methanol, ethanol, n-propanol, and isopropanol; tetrahydrofuran, Alkanes, tris Ethers such as alkane and dimethoxyethane; ketones such as acetone, methyl ethyl ketone, methylvinylketone, methyl isoacetone; glycols such as ethylene glycol and propylene glycol; Diol derivatives such as kisperidine, n-butyl cyperidine; glycerol; acetonitrile; dimethylformamide, dimethylacetamide, and other amines; dimethylmethylene sulfonium; cyclobutane Wait.

From the viewpoint of the storage stability of the coating liquid (U) and the coating property of the coating liquid (U) to the substrate, the solid content concentration of the coating liquid (U) is preferably in the range of 1 to 20% by mass. , More preferably in the range of 2 to 15% by mass, and even more preferably in the range of 3 to 10% by mass. The solid content concentration of the coating solution (U) can be calculated as follows: For example, a certain amount of the coating solution (U) is added to a petri dish, and the volatile components such as solvents are removed from the petri dish at a temperature of 100 ° C. The mass of the remaining solid content is calculated by dividing the mass of the coating liquid (U) initially added. In this case, it is preferable to measure the amount of solid content remaining after drying for a certain period of time, and use the mass at the time when the mass difference between the two consecutive times is negligible as the mass of the remaining solid content to calculate the solid content concentration.

From the viewpoint of the storage stability of the coating liquid (U) and the gas barrier properties of the multilayer structure, the pH of the coating liquid (U) is preferably in the range of 0.1 to 6.0, and more preferably in the range of 0.2 to 5.0. A more preferable range is 0.5 to 4.0.

The pH of the coating solution (U) 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.

The state of the coating solution (U) changes with time, and eventually becomes a gel-like composition, or there is a tendency to cause precipitation. The time until it changes to this state depends on the composition of the coating liquid (U). In order to stably coat the coating liquid (U) on the coating substrate (X), the coating liquid (U) preferably has a stable viscosity over a long period of time. The solution (U) is preferably prepared so that the viscosity at the end of step (I) is used as a reference viscosity, and the solution is left at 25 ° C for 2 days. The viscosity measured by a viscometer (B-type viscometer: 60 rpm) is 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 in many cases.

For the method of adjusting the viscosity of the coating liquid (U) to be within the above range, methods such as adjusting the concentration of solid components, adjusting the pH value, and adding a viscosity modifier can be used. Examples of viscosity modifiers include carboxymethyl cellulose, starch, bentonite, tragacanth gum, stearates, alginates, methanol, ethanol, n-propanol, and isopropanol.

As long as the effect of the present invention can be obtained, the coating liquid (U) may contain other substances than those described above. For example, the coating liquid (U) may contain carbonate, hydrochloride, nitrate, bicarbonate, sulfate, bisulfate, borate, aluminate and other inorganic metal salts; oxalate, acetate, and tartaric acid. Metal salts of organic acids such as salts and stearates; acetoacetone metal complexes (such as aluminum acetone aluminum acetone, etc.), cyclopentadienyl metal complexes (titanocene, etc.), cyano metal complexes, etc. Metal complexes; layered clay compounds; crosslinking agents; polymer compounds other than polymers (C); plasticizers; antioxidants; ultraviolet absorbers; flame retardants, etc.

[Step (II)]

In step (II), the precursor solution layer is formed on the substrate (X) by applying the coating solution (U) on the substrate (X). The coating liquid (U) may also be directly coated on at least one side of the substrate (X). Before applying the coating solution (U), the surface of the substrate (X) may be treated with a conventional anchor coating agent, or a conventional adhesive may be applied to the surface of the substrate (X). To form an adhesive layer (H) on the surface of the substrate (X) in advance. In addition, the coating liquid (U) may be applied to the layer (Z) previously formed on the substrate (X) through the step (IV) described later, so as to drive the layer (Z) on the layer (Z). Physical layer.

In addition, the coating liquid (U) may be subjected to a deaeration and / or a defoaming treatment as necessary. The method of degassing and / or defoaming is, for example, a method using vacuum, heating, centrifugation, ultrasound, etc., and a method including vacuum is preferably used.

In step (II), the viscosity of the coating solution (U) at the time of coating is the viscosity measured by a Brookfieid-type rotary viscometer (SB-type viscometer: rotor No. 3, rotation speed 60 rpm), and the coating is applied. The temperature is preferably 3000 mPa‧s or less, and more preferably 2000 mPa‧s or less. When the viscosity is 3,000 mPa · s or less, a multilayer structure having improved flatness of the coating liquid (U) and more excellent appearance can be obtained. In step (II), the viscosity of the coating liquid (U) at the time of coating can be adjusted according to the concentration, temperature, stirring time and stirring intensity after mixing in step (c). For example, by extending the stirring after the mixing in step (c), the viscosity may be reduced in some cases.

The method for applying the coating liquid (U) to the substrate (X) is not particularly limited, and a conventional method can be adopted. Preferred methods include, for example, a casting method, a dipping method, a roll coating method, a gravurel coating method, a screen coating method, a reverse coating method, and a spray coating method. (spray coating), kiss coating, die coating, metal bar coating, sealed doctor blade, chamber doctor coating, curtain coating Cloth coating (curtain coating), etc.

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

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

When a plurality of area layers (YA) are formed on the substrate (X) having a three-dimensional shape, the above method can be used to form layers (precursor layers) on each surface individually. Alternatively, a plurality of layers (layer (YA) precursor layer) are simultaneously formed by applying the coating solution (U) to a plurality of surfaces of the substrate (X) and drying them simultaneously.

[Step (III)]

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

In step (III), a reaction in which the particles of the metal oxide (A) are bonded to each other via a phosphorus atom (a phosphorus atom derived from a phosphorus compound (B)) is performed. From another viewpoint, in step (III), a reaction for generating a reaction product (R) is performed. In order for the reaction to proceed sufficiently, the temperature of the heat treatment is 140 ° C or higher, more preferably 170 ° C or higher, and even more preferably 190 ° C or higher. If the heat treatment temperature is low, the time required to obtain a sufficient degree of reactivity is long, and this may cause a decrease in productivity. The preferable upper limit of the heat treatment temperature varies depending on the type of the substrate (X) and the like. For example, when using a thermoplastic resin film made of a polyamide resin as the base material (X), the temperature of the heat treatment The temperature is preferably 190 ° C or lower. When a thermoplastic resin film made 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 may be performed 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. An example of the heat treatment is performed in a range of 140 to 220 ° C for 0.1 second to 1 hour. In another example, the heat treatment is performed in a range of 170 to 200 ° C. for 5 to 300 seconds (for example, 10 to 300 seconds).

The method of the present invention for manufacturing a multilayer structure may also include the step of irradiating the precursor layer or the layer (YA) with ultraviolet rays. The ultraviolet irradiation may be performed at any step after the step (II) (for example, after the solvent removal of the applied coating solution (U) is substantially completed). This method is not particularly limited, and a known method can be used. The wavelength of the ultraviolet light to be irradiated is preferably in a range of 170 to 250 nm, more preferably in a range of 170 to 190 nm and / or in a range of 230 to 250 nm. Instead of the ultraviolet irradiation, irradiation with radiation such as an electron beam and a gamma ray may be performed. By performing the ultraviolet irradiation, the gas barrier performance of the multilayer structure may be exhibited at a higher level.

In order to arrange the adhesive layer (H) between the substrate (X) and the layer (YA), before applying the coating liquid (U), the surface of the substrate (X) is treated with a conventional anchor coating agent. When applying a conventional adhesive to the surface of the substrate (X), it is preferable to perform a curing treatment. Specifically, the substrate (X) coated with the coating liquid (U) is preferably left at a relatively low temperature for a long time after the coating liquid (U) is applied and before the heat treatment step of step (III). . The temperature for the aging treatment is preferably less than 110 ° C, more preferably 100 ° C or less, and even more preferably 90 ° C or less. The temperature of the ripening treatment is preferably 10 ° C or higher, more preferably 20 ° C or higher, and even more preferably 30 ° C or higher. Ripening 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 aging treatment, the adhesion between the substrate (X) and the layer (YA) becomes stronger.

[Step (IV)]

In step (IV), a layer (Z) is formed on the substrate (X) (or on the layer (Y)) by applying a coating liquid (V), the coating liquid (V) containing a polymer (E ), Which contains a monomer unit having a phosphorus atom. Usually, the coating solution (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 when the polymer (E) is prepared can be used as it is. When the solubility of the polymer (E) is low, dissolution can be promoted by applying heat treatment and ultrasonic treatment.

The solvent used in the coating liquid (V) may be appropriately selected according to the type of the polymer (E), and is preferably water, alcohol, or a mixed solvent thereof. As long as the dissolution of the polymer (E) is not hindered, the solvent may contain tetrahydrofuran, Alkanes, tris Ethers such as alkane, dimethoxyethane; ketones such as acetone, methyl ethyl ketone; glycols such as ethylene glycol, propylene glycol; glycols such as methyl cyperidine, ethyl cyperidine, n-butyl cyperidine Derivatives; glycerol; acetonitrile; fluorenamines such as dimethylformamide; dimethylsulfine; cyclamidine and the like.

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, and more preferably 0.5 to 50, from the viewpoint of solution storage stability and coatability. It is more preferably within a 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).

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

The pH of the coating liquid (V) 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.

In addition, when it is necessary to control the viscosity of the coating liquid (V), methods such as adjusting the concentration of solid components, adjusting the pH value, and adding a viscosity modifier can be used. Examples of viscosity modifiers include carboxymethyl cellulose, starch, bentonite, tragacanth, stearates, alginates, methanol, ethanol, n-propanol, and isopropanol.

In addition, the coating liquid (V) may be deaerated and / or deaerated as necessary. The method of degassing and / or defoaming is, for example, a method using vacuum, heating, centrifugation, ultrasound, etc., and a method including vacuum is preferably used.

In step (IV), the viscosity of the coating liquid (V) at the time of coating is the viscosity measured by a Brookfield-type rotational viscometer (SB-type viscometer: rotor No. 3, rotation speed 60 rpm), and the The temperature at this time is preferably 1000 mPa · s or less, and more preferably 500 mPa · s or less. When the viscosity is 1000 mPa · s or less, a multilayered structure with improved flatness of the coating liquid (V) and more excellent appearance can be obtained. In step (IV), the viscosity of the coating liquid (V) at the time of coating can be adjusted by the concentration and temperature.

The method for applying the solution of the coating solution (V) to the substrate (X) or the layer (Y) is not particularly limited, and a conventional method can be adopted. Preferred methods include, for example, casting, dipping, roll coating, gravure coating, screen printing, reverse coating, spray coating, anastomotic coating, die coating, and metal. Bar coating method, sealed doctor blade coating method, curtain coating Law, etc.

Generally, in step (IV), the layer (Z) is formed by removing the solvent in the coating solution (V). The method of removing the solvent is not particularly limited, and a conventional drying method can be used. Specifically, drying methods such as a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method can be used alone or in combination. The drying temperature is preferably 0 to 15 ° C or higher than the flow start temperature of the substrate (X). 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 normal pressure or reduced pressure. The solvent may be removed by a heat treatment in 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 solution (V) can be applied to one side and the solvent can be removed to form a first layer. The first layer (Z) is formed by coating the coating liquid (V) on the other surface and removing the solvent, 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 surfaces of the base material (X) having a three-dimensional shape are laminated with or without the layer (Y), the layer (Z) can be formed on each of the surfaces by using the method described above. Alternatively, the coating liquid (V) is simultaneously applied to a plurality of surfaces and dried, thereby forming a plurality of layers (Z) simultaneously.

As mentioned above, typically, the steps are performed in the order of (I), (II), (III), (IV), but when the layer (Z) is formed on the substrate (X) and the layer (Y) In between, step (IV) may be performed before step (II), and step (III) may be performed after step (IV). From the viewpoint of obtaining a multilayer structure having excellent appearance, it is preferable to perform step (IV) after step (III).

The multilayer structure obtained in this way can be directly used to form the container wall structure. Multilayer structure. However, as described above, a multilayer structure may be formed by further forming or forming other members (such as other layers) on the multilayer structure. This component can be attached using conventional methods.

In one aspect, the method for manufacturing a multilayer structure may include the following steps: forming a layer (Y) containing an aluminum atom (W), and forming a coating solution (V) containing a polymer (E) In step (IV) of the above-mentioned layer (Z), the polymer (E) contains a monomer unit having a phosphorus atom. As described above, when the layer (Y) is the layer (YA), the step (W) may include steps (I), (II), and (III). When the layer (Y) is the layer (YB) or the layer (YC), the step (W) may include a step of forming such layers by a vapor deposition method.

[Example]

Hereinafter, the present invention will be described more specifically using examples, but the present invention is not limited to the following examples. In addition, each measurement and evaluation of an Example and a comparative example was implemented 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, for the layer (YA) laminated on the substrate (X), a Fourier-Transform Infrared Spectrometer ("Perkin Elmer", "Spectrum One") was used to measure the infrared absorption spectrum. Infrared absorption spectrum is measured in ATR (Total Reflection Measurement) mode in the range of 700 ~ 4000cm ^-1 . When the thickness of the layer (YA) is 1 μm or less, in the infrared absorption spectrum by the ATR method, the absorption peak from the substrate (X) is detected, and it is impossible to correctly obtain the absorption intensity from the layer (YA) only. Happening. In this case, the infrared absorption spectrum of only the substrate (X) is measured and subtracted, thereby removing only the peak from the layer (X). When layer (YA) is laminated on layer (Z), the same method can be used. In addition, when the layer (YA) is formed inside the multilayer structure (for example, when the laminated sequence of the substrate (X) / layer (YA) / layer (Z) is provided), the infrared absorption spectrum of the layer (YA) may be Measure before forming the layer (Z), or after forming the layer (Z), peel it off at the interface of the layer (YA), and measure the infrared absorption spectrum of the exposed layer (YA).

Based on the infrared absorption spectrum of the layer (YA) obtained in this way, the maximum absorption wave number (n ¹ ) in the range of 800 to 1400 cm ^-1 and the absorbance (α of the maximum absorption wave number (n ¹ )) were obtained. ¹ ). And the maximum absorption wave number (n ² ) based on the hydroxyl group stretching vibration in the range of 2500 to 4000 cm ^-1 and the absorbance (α ² ) of the maximum absorption wave number (n ² ) were obtained. The half-value width of the absorption peak of the maximum absorption wave number (n ¹ ) is obtained by the following method: Find the absorbance (absorbance (α ¹ ) / 2) that is one and a half of the absorbance (α ¹ ) in the absorption peak. The wave number at two points is calculated by calculating the difference between the wave numbers. In addition, when the absorption peak of the maximum absorption wave number (n ¹ ) overlaps with the absorption peaks from other components, the Gaussian function is used to separate the absorption peaks from the components using the least square method, and then the maximum absorption is obtained in the same manner as above The full width at half maximum of the absorption peak at the wave number (n ¹ ).

(2) Appearance of multilayer structure

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

A: Colorless, transparent and uniform, excellent appearance.

B: Slight cloudiness or unevenness was seen, but the appearance was good.

(3) Manufacturing method of protective film

An acrylic resin single-layer film (thickness: 50 μm) was prepared by applying a two-component adhesive (manufactured by Mitsui Chemicals Co., Ltd., A-520 (trade name) and A-50 (trade name)) and drying it. This is laminated with the obtained multilayer structure to obtain a laminate. Then, quasi The multilayer structure of this laminated body was prepared by coating and drying the above-mentioned two-liquid type adhesive, and this was combined with a polyethylene terephthalate film (TOYO TEXTILE CO., LTD. Name) Q1A15. Hereinafter, EVA is easy to adhere to PET film) (thickness: 50 μm). This polyethylene terephthalate film has improved adhesion to ethylene-vinyl acetate copolymer (hereinafter referred to as EVA). By. In this way, a protective sheet having an (outside) acrylic resin layer / adhesive layer / multilayer structure / adhesive layer / EVA with a PET film (inside) structure was obtained. Furthermore, the multilayer structure has the layer (Y) side (the multilayer structure without the layer (Y) is the side with the layer (Z) or the layer (Y ')), which is more important than the substrate (X) Layered more outwardly.

(4) Oxygen permeability of protective sheet (Om)

A sample for measuring oxygen permeability was cut out of the obtained protective sheet. The oxygen permeability was measured using an oxygen transmission amount measuring device ("MOCON OX-TRAN2 / 20" manufactured by Modern Control). Specifically, the laminated body is installed on the device such that the acrylic resin layer constituting the laminated body of the protective sheet faces the oxygen supply side, and the EVA of the laminated body easily adheres the PET layer to the carrier gas side. Then measure the oxygen permeability at the temperature of 20 ° C, the humidity on the oxygen supply side is 85% RH, the humidity on the carrier gas side is 100% RH, the oxygen pressure is 1 atmosphere, and the carrier gas pressure is 1 atmosphere (unit: ml / (m ² ‧day‧atm)).

(5) Oxygen permeability of the protective sheet after 5% stretching and holding (Of)

For the obtained protective sheet, after being left to stand at 23 ° C and 50% RH for more than 24 hours, it was stretched in the longitudinal direction by 5% under the same conditions, and maintained in the stretched state for 5 minutes, thereby obtaining protection after stretching. sheet. The oxygen permeability was measured using an oxygen transmission amount measuring device ("MOCON OX-TRAN2 / 20" manufactured by Modern Control). Specifically, a protective sheet is provided so that the layer (Y) or the layer (Y ') faces the oxygen supply side, and the substrate (X) faces the carrier gas side. The temperature is 20 ° C, and the humidity on the oxygen supply side is 85% RH. 2. Measure the oxygen permeability (unit: ml / (m ² ‧day‧atm)) under the condition that the humidity on the carrier gas side is 85% RH, the oxygen pressure is 1 atmosphere, and the carrier gas pressure is 1 atmosphere. The carrier gas system uses nitrogen containing 2% by volume of hydrogen.

[Production Example of Coating Solution (U)]

The manufacturing example of the coating liquid (U) for manufacturing a layer (YA) is shown.

While stirring 230 parts by mass of distilled water, the temperature was raised to 70 ° C. 88 parts by mass of aluminum isopropoxide was dropped into the distilled water over 1 hour, the liquid temperature was gradually raised to 95 ° C., and the isopropyl alcohol produced was distilled off, thereby performing hydrolysis condensation. After adding 4.0 parts by mass of a 60% by mass nitric acid aqueous solution to the obtained liquid, and stirring at 95 ° C for 3 hours, the aggregates of the particles of the hydrolyzed condensate were degummed, 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 liquid thus obtained, 58.19 parts by mass of distilled water, 19.00 parts by mass of methanol, and 0.50 parts by mass of a 5% by mass aqueous solution of polyvinyl alcohol were added, and the mixture was stirred in a uniform manner to obtain a dispersion ( S1). In addition, 3.66 parts by mass of an 85% by mass phosphoric acid aqueous solution was used as the solution (T1). Next, both the dispersion (S1) and the solution (T1) were adjusted to 15 ° C. Next, while maintaining the liquid temperature of 15 ° C., the solution (T1) was dropped while stirring the dispersion liquid (S1) to obtain a coating liquid (U1). The obtained coating solution (U1) was maintained at 15 ° C, and in this state, stirring was continued until the viscosity became 1500 mPa · s. In addition, in this coating liquid (U1), the molar number (N _M ) of metal atoms constituting the metal oxide (A) (alumina) and the molar number of phosphorus atoms constituting the phosphorus compound (B) (phosphoric acid) are included. The number (N _P ) ratio (Molar number (N _M ) / Molar number (N _P )) was 1.15.

The coating liquid (U2), coating liquid (U3), and coating liquid (U4) were obtained by the same method except that the ratios of N _M / N _P were 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 nitrogen-substituted, and 12 g of methyl ethyl ketone (hereinafter sometimes abbreviated as "MEK") was charged. As a solvent, immerse in an oil bath, heat to 80 ° C, and begin refluxing. From this point on, a small amount of nitrogen was continuously flowed throughout the polymerization. Next, a mixed solution of 8.5 g of methacrylic acid phosphorus oxyethyl ester (hereinafter sometimes abbreviated as "PHM"), MEK 5 g, and 100 mg of azobisisobutyronitrile was prepared, and the mixture was dropped at a constant speed from the dropping funnel over 10 minutes. . After the dropping was completed, the temperature was maintained at 80 ° C., and stirring was continued for about 12 hours to obtain a yellow viscous liquid polymer solution.

The polymer solution was poured into about 10-fold amount of 1,2-dichloroethane, the supernatant liquid was removed by decantation, and the precipitate was recovered to separate the polymer. The recovered polymer was dissolved in tetrahydrofuran, which is a good solvent for the polymer (hereinafter sometimes abbreviated as "THF"), and it was reprecipitated in about 10 times the amount of 1,2-dichloroethane. This was repeated 3 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. As a result, 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 isopropanol at a concentration of 10% by weight to obtain a coating solution (V1).

By the same method as the preparation of the coating liquid (V1), a coating liquid (V2) composed of a separate polymer of methacrylic acid phosphoryloxypolyoxypropylene glycol ester (hereinafter sometimes abbreviated as "PHP") was obtained. Furthermore, in the same manner, a coating solution (V3) of a copolymer obtained by copolymerizing PHM and acrylonitrile (hereinafter sometimes abbreviated as "AN") at a mole ratio of 2/1 and 1/1, and Coating liquid (V4).

[Production example of coating liquid (V5 ~ 8)]

A round bottom flask (inner volume: 50 ml) equipped with a stirrer and a thermometer was replaced with nitrogen, 2.5 g of water was charged as a solvent, and 10 g of vinylphosphonic acid (hereinafter abbreviated as "VPA") and 2.5 g of water were stirred while stirring. And a mixed solution of 25 mg of 2,2'-azobisisobutylphosphonium dihydrochloride (2,2'-azobis (2-amidinopropane) HCl, hereinafter sometimes abbreviated as "AIBA") was dropped into a round bottom flask. From this point on throughout the polymerization, a trace amount of nitrogen is continuously circulated. The round bottom flask was immersed in an oil bath and allowed to react at 80 ° C for 3 hours. The reaction mixture was diluted with 15 g of water and filtered through a cellulose membrane (manufactured by 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 to obtain a white polymer. The molecular weight of this polymer was measured by colloidal permeation chromatography, using a 1.2 wt% NaCl aqueous solution as a solvent, and a polymer concentration of 0.1 wt%. 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 solution (V5).

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

[Example 1]

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

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

For the obtained multilayer structure (B1), a measurement sample having a size of 15 cm × 10 cm was cut out. Then, the sample was left to stand at 23 ° C and 50% RH for more than 24 hours, and then stretched in the long axis direction by 5% under the same conditions, and kept stretched for 5 minutes, thereby obtaining a multilayer structure (B1 ). As a result of measuring the moisture permeability of the multilayer structure (B1) after the stretching as described above, the moisture permeability of the multilayer structure (B1) after stretching was 0.2 g / (m ² ‧day).

About the obtained multilayer structure (B1), the protective sheet was produced by the method mentioned above, and it 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 multilayer structure obtained in Example 2 was measured in the same manner as in Example 1. As a result, the moisture permeability of the multilayer structure was 0.2 g / (m ² ‧day). The 5% tensile moisture permeability of the multilayer structure obtained in Example 2 was measured in the same manner as in Example 1. As a result, the moisture permeability of the multilayer structure after stretching was 0.2 g / (m ² ‧day).

[Examples 3 to 6, 37, 38]

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

[Examples 7 to 12]

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

[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 for the heat treatment and the coating liquid (V) were changed in accordance with Table 1.

[Examples 19 to 24]

The coating liquid (U) and the coating liquid (V) used were changed in accordance with Table 1, and 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) were changed.

[Examples 25 and 26]

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

[Examples 27 and 28]

A multilayer structure and a protective sheet were obtained in the same manner as in Example 1 except that the coating layer (Y) and the layer (Z) were changed on the two areas of the substrate, and the coating liquid (V) was changed in accordance with Table 1. The moisture permeability of the obtained multilayer structure (A1) was measured in the same manner as in Example 1. As a result, it was 0.1 g / (m ² · day) or less.

[Examples 29 and 30]

The base material is 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) is changed according to Table 1, Except for this, a multilayer structure and a protective sheet were obtained in the same manner as in Example 1.

[Examples 31 and 32]

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

[Examples 33 and 34]

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

[Examples 35 and 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 solution (V) was changed in accordance with Table 1. The alumina layer is formed by a vacuum evaporation method.

[Examples 39 and 40]

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

[Comparative Example 1]

Comparative Example 1 was defined as Example 1 in which the layer (Z) was not formed.

The moisture permeability of the multilayer structure obtained in Comparative Example 1 was measured in the same manner as in Example 1. As a result, the moisture permeability of the multilayer structure was 0.3 g / (m ² ‧day). The 5% tensile moisture permeability of the multilayer 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 a comparative example 2, a layer (Z) was not formed in Example 13.

[Comparative Example 3]

Comparative Example 3 was defined as Example 15 in which the layer (Z) was not formed.

[Comparative Example 4]

The case where the layer (Z) was not formed in Example 17 was used as Comparative Example 4.

[Comparative Example 5]

Comparative Example 5 was defined as Example 19 in which the layer (Z) was not formed.

[Comparative Example 6]

The case where the layer (Z) was not formed in Example 21 was used as Comparative Example 6.

[Comparative Example 7]

Comparative Example 7 was defined as Example 23 in which the layer (Z) was not formed.

[Comparative Example 8]

The case where the layer (Z) was not formed in Example 27 was used as Comparative Example 8.

[Comparative Example 9]

The case where the layer (Z) was not formed in Example 29 was used as Comparative Example 9.

[Comparative Example 10]

The case where the layer (Z) was not formed in Example 31 was used as Comparative Example 10.

[Comparative Example 11]

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

[Comparative Example 12]

The case where the layer (Z) was not formed in Example 35 was used as Comparative Example 12.

[Comparative Examples 13, 14]

The layer (Y) was a layer (Y ′) of a silicon oxide vapor-deposited layer having a thickness of 0.03 μm, and the coating solution (V) was changed in accordance with Table 1, except that a multilayer was obtained in the same manner as in Example 1. Structure and protective sheet. The silicon 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 solution (V) was changed in accordance with Table 1. That is, in Comparative Example 17, a multilayer structure and a protective sheet of Comparative Example 17 having a layer (Y1) (0.5 μm) / PET (12 μm) / layer (Z1) (0.3 μm) structure were produced.

[Comparative Example 19]

The comparative example 14 is the one in which the layer (Z) is not formed in the comparative example 14.

[Comparative Example 20]

The comparative example 20 is the one in which the layer (Z) is not formed, that is, the substrate (PET) is the only one.

The manufacturing conditions and evaluation results of the above examples and comparative examples are shown in Tables 1 and 2 below. In the table, "-" means "unused", "uncalculated", "not implemented", "unmeasured", and so on.

As can be seen from the table, the protective sheet of each example maintained good gas barrier properties even after being subjected to strong physical pressure (5% stretching) after the protective sheet was produced. On the other hand, when the protective sheet of the comparative example is subjected to strong physical pressure (5% stretching), all of them have a significant decrease in gas barrier properties.

In addition, in order to review the flexibility of the protective sheet produced in the above example, a test was carried out about 20 turns around the outer peripheral surface of a cylindrical stainless steel core material having an outer diameter of 30 cm. As a result, no damage was confirmed. The protective sheet produced in each example is one having flexibility.

[Example of Electronic Device Manufacturing]

First, a multilayer structure was produced by the same method as in Example 2. Next, an amorphous silicon solar battery unit placed on a 10 cm square reinforced glass was sandwiched by an ethylene-vinyl acetate copolymer having a thickness of 450 μm, and the multilayer structure (Z1) was opposed to each other and bonded to it. In this way, a solar cell module is manufactured. The bonding was performed by evacuating at 150 ° C. for 3 minutes and then performing compression bonding for 9 minutes. The solar cell module produced in this way will exhibit good operation and still exhibit good electrical output characteristics over a long period of time.

Claims (11)

An electronic device includes an electronic device body and a protective sheet for protecting the surface of the electronic device body. The protective sheet includes a multilayer structure having a substrate (X), a layer (Y), and a layer (Z) each having more than one layer. The layer (Y) contains aluminum atoms, the layer (Z) contains a polymer (E), and at least one group of the layer (Y) and the layer (Z) are adjacent and laminated, and the polymer (E) contains A monomer unit of a phosphorus atom; the layer (Y) is a layer (YA) containing a reaction product (R), and the reaction product (R) is a metal oxide (A) containing aluminum reacted with a phosphorus compound (B) The resulting reaction product. For example, the electronic device of the scope of application for patent 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 layers (Z) are sequentially laminated. For example, the electronic device according to the first patent application range, wherein the polymer (E) is a single polymer or copolymer of (meth) acrylates having a phosphate group at the end of a side chain. For example, the electronic device of claim 3, wherein the polymer (E) is a separate polymer of acid phosphoxy ethyl (meth) acrylate. For example, the electronic device of the scope of patent application, wherein the polymer (E) has a repeating unit represented by the following general formula (I), [In formula (I), n represents a natural number]. The patentable scope of application of the electronic device according to item 1, wherein the layer (YA) of infrared absorption spectrum, 800 ~ 1400cm ^-1 in the infrared absorption as a range of the maximum number ^(n-1) wave located at 1080 ~ 1130cm ^-1 Range. For example, the electronic device according to item 1 of the patent application scope, wherein the substrate (X) includes at least one layer selected from the group consisting of a thermoplastic resin film layer, a paper layer, and an inorganic vapor-deposited layer. For example, the electronic device of the first patent application range, wherein the oxygen permeability of the protective sheet under the conditions of 20 ° C. and 85% RH is 2 ml / (m ² .day. Atm) or less. For example, for the electronic device in the first scope of the patent application, the protective sheet is maintained at 23 ° C. and 50% RH for 5 minutes in a unidirectionally stretched state for 5%, and then the protective sheet is subjected to The oxygen permeability measured under the conditions of ℃ and 85% RH is 4 ml / (m ² .day.atm) or less. For example, the electronic device under the scope of patent application is a photoelectric conversion device, an information display device or a lighting device. For example, the electronic device of the scope of application for a patent, wherein the protective sheet is flexible.