WO2017209107A1 - Layered sheet, packaging material, and molded article - Google Patents

Layered sheet, packaging material, and molded article Download PDF

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Publication number
WO2017209107A1
WO2017209107A1 PCT/JP2017/020039 JP2017020039W WO2017209107A1 WO 2017209107 A1 WO2017209107 A1 WO 2017209107A1 JP 2017020039 W JP2017020039 W JP 2017020039W WO 2017209107 A1 WO2017209107 A1 WO 2017209107A1
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WIPO (PCT)
Prior art keywords
layer
gas barrier
group
laminated sheet
compound
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PCT/JP2017/020039
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French (fr)
Japanese (ja)
Inventor
伊織 竹内
未悠 松井
雅之 樫村
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凸版印刷株式会社
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Application filed by 凸版印刷株式会社 filed Critical 凸版印刷株式会社
Priority to JP2018520918A priority Critical patent/JP6947173B2/en
Publication of WO2017209107A1 publication Critical patent/WO2017209107A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • B65D65/40—Applications of laminates for particular packaging purposes

Definitions

  • the present invention relates to a laminated sheet, a packaging material, and a molded product.
  • This application claims priority on May 31, 2016 based on Japanese Patent Application No. 2016-108159 for which it applied to Japan, and uses the content here.
  • packaging materials used for packaging foods and non-food products such as pharmaceuticals and electronic components have been designed to prevent the alteration of contents and to permeate gases such as oxygen and water vapor in order to maintain their functions and properties. It is required to have a gas barrier property for blocking.
  • an inorganic vapor deposition film in which an inorganic vapor deposition layer is provided on at least one surface of a substrate such as a polyester film is widely used (for example, Patent Document 1).
  • Patent Document 1 an inorganic vapor deposition film as proposed in Patent Document 1 is stressed by bending, stretching, or the like, the inorganic vapor deposition layer is damaged, and the gas barrier property tends to be lowered.
  • Patent Document 2 an aqueous solution or a water / alcohol mixed solution containing a water-soluble polymer and at least one of at least one alkoxide, a hydrolyzate thereof, and tin chloride on an inorganic vapor deposition layer is used as a main agent.
  • a gas barrier laminated film provided with a gas barrier film formed by applying a coating agent to be heated and drying.
  • This gas barrier laminate film exhibits high gas barrier properties, and retains a certain degree of gas barrier properties even after bending, stretching, etc., by coating the inorganic vapor deposition layer with a flexible gas barrier coating. It is also disclosed that it has heat resistance, moisture resistance and water resistance.
  • the heat and moisture resistance of the gas barrier coating disclosed in Patent Document 2 is not sufficient, and when exposed to a high temperature and high humidity atmosphere, the gas barrier coating may swell and the gas barrier properties may deteriorate.
  • the flexibility of this gas barrier coating is not sufficient, and when the gas barrier laminated film is processed such as bending or stretching, it can be processed to an inorganic vapor deposition layer depending on the type and degree of processing. May cause damage to gas barrier properties.
  • the present invention has been made in view of the above circumstances, and an object thereof is to provide a laminated sheet having a layer excellent in flexibility and heat and humidity resistance, a packaging material using the same, and a molded product.
  • the laminated sheet according to the first aspect of the present invention includes a base material, a hydroxyl group-containing polymer compound (A), an epoxy group-containing silane coupling agent (B), and the epoxy group-containing silane coupling agent (B).
  • the ratio of the hydroxyl group-containing polymer compound (A) to the total mass of the silicon compound (C) with respect to the SiO 2 equivalent is 25 to 30% by mass, and the epoxy group-containing silane coupling agent compound (B). The ratio is 5 to 30% by mass.
  • the silicon compound (C) may contain at least one compound (C1) selected from the group consisting of a compound represented by the following formula (c1) and a hydrolyzate thereof.
  • Si (OR 1 ) 4 (c1) (In the formula, R 1 is an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl group having 1 to 4 carbon atoms, and four R 1 in the formula may be the same or different.)
  • the epoxy group-containing silane coupling agent (B) includes at least one compound (B1) selected from the group consisting of a compound represented by the following formula (b1) and a hydrolyzate thereof. You may go out.
  • the laminated sheet according to the first aspect may further include a gas barrier layer formed from an inorganic material.
  • the packaging material according to the second aspect of the present invention includes the laminated sheet according to the first aspect.
  • the packaging material according to the second aspect may be a packaging material for hot water treatment.
  • the molded product according to the third aspect of the present invention includes the packaging material according to the second aspect.
  • the molded product according to the third aspect may be a vertical bag-filling sealing bag, a vacuum packaging bag, a pouch with a spout, a laminated tube container, an infusion bag, a container lid, a paper container, or a vacuum insulator.
  • each aspect of the present invention it is possible to provide a laminated sheet having a layer excellent in flexibility and heat and humidity resistance, a packaging material and a molded product using the same.
  • FIG. 1 is a cross-sectional view schematically showing a laminated sheet 10 according to the first embodiment of the present invention.
  • the laminated sheet 10 includes a base material 1, a gas barrier layer 3 formed of an inorganic material, and a layer 5 (hereinafter also referred to as “layer of composition (I)”) formed of the following composition (I).
  • layer of composition (I) a hydroxyl group-containing polymer compound (A), an epoxy group-containing silane coupling agent (B), and another silicon compound (C) other than the epoxy group-containing silane coupling agent (B) Including the hydroxyl group-containing polymer compound (A), the epoxy group-containing silane coupling agent (B), and the total amount of the silicon compound (C) in terms of SiO 2.
  • I a composition in which the ratio of the epoxy group-containing silane coupling agent compound (B) is 5 to 30% by mass.
  • the gas barrier layer 3 is laminated on one surface of the substrate 1, and the layer 5 of the composition (I) is laminated on the gas barrier layer 3.
  • the substrate 1 examples include plastics, papers, rubbers, and the like.
  • the substrate 1 is preferably a plastic film from the viewpoint of adhesion between the substrate 1 and the gas barrier layer 3 and the like.
  • plastics examples include polyester (eg, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), etc.), polyolefin (eg, polyethylene, polypropylene, etc.), polystyrene, polyamide (eg, 66-nylon, etc.), polycarbonate, polyacrylonitrile, polyimide, etc. Engineering plastics and the like.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • polyolefin eg, polyethylene, polypropylene, etc.
  • polystyrene polyamide
  • polycarbonate eg, 66-nylon, etc.
  • the plastic film may be either stretched or unstretched, and preferably has sufficient mechanical strength and dimensional stability. In particular, a film arbitrarily stretched in the biaxial direction is preferably used.
  • the base material 1 is preferably a polyamide film or a polyester film, and more preferably a polyester film, in consideration of price, moisture resistance, filling suitability, texture, and discardability.
  • the surface of the substrate 1 may be subjected to a surface activation treatment such as corona treatment, flame treatment, and plasma treatment.
  • the thickness of the substrate 1 can be appropriately set according to the use of the laminated sheet 10.
  • the laminated sheet 10 is not particularly limited. However, in consideration of suitability as a packaging material and processability, it is preferably 3 to 200 ⁇ m and more preferably 6 to 30 ⁇ m. .
  • the gas barrier layer 3 is formed from an inorganic material.
  • an inorganic material capable of constituting a layer for imparting gas barrier properties such as oxygen barrier property and water vapor barrier property to the laminated sheet 10 is appropriately selected.
  • metal for example, aluminum
  • inorganic oxidation Form example, aluminum oxide, silicon oxide, magnesium oxide, tin oxide, etc.
  • the gas barrier layer 3 is preferably a deposited film obtained by depositing the inorganic material on the substrate 1 by a deposition method.
  • an aluminum oxide vapor deposition film is a reactive vapor deposition, reactive sputtering, or reactive ion plate that forms a thin film in the presence of a mixed gas of oxygen gas and inert gas such as carbon dioxide gas using aluminum as an evaporation material. It can be formed by ting or the like.
  • a mixed gas of oxygen gas and inert gas such as carbon dioxide gas using aluminum as an evaporation material. It can be formed by ting or the like.
  • some aluminum may exist as it is, or aluminum peroxide may exist.
  • the thickness of the gas barrier layer 3 varies depending on the use of the laminated sheet 10 and the film thickness of the layer 5 of the composition (I), but is preferably 5 to 300 nm, more preferably 10 to 50 nm. If the thickness of the gas barrier layer 3 is less than the lower limit (5 nm) of the above range, the continuity of the gas barrier layer 3 may be impaired. When the thickness of the gas barrier layer 3 exceeds the upper limit (300 nm) of the above range, the flexibility of the gas barrier layer 3 is lowered, and there is a possibility that cracking may occur due to external factors such as bending and pulling after film formation.
  • the layer 5 of the composition (I) is a layer formed from the composition (I).
  • the composition (I) comprises a hydroxyl group-containing polymer compound (A), an epoxy group-containing silane coupling agent (B), and another silicon compound (C) other than the epoxy group-containing silane coupling agent (B). including.
  • the hydroxyl group-containing polymer compound (A) is not particularly limited as long as it is a polymer compound having a hydroxyl group.
  • the hydroxyl group-containing polymer compound (A) is preferably a vinyl alcohol polymer from the viewpoint of gas barrier properties.
  • a vinyl alcohol polymer is a polymer containing vinyl alcohol units. Examples of the vinyl alcohol polymer include polyvinyl alcohol (hereinafter also referred to as “PVA”), an ethylene-vinyl alcohol copolymer, a modified vinyl alcohol polymer, and the like.
  • the degree of polymerization of the vinyl alcohol polymer is preferably 500 or more and 3000 or less, and more preferably 1000 or more and 3000 or less.
  • PVA is particularly preferable.
  • the gas barrier property is particularly excellent.
  • PVA is a material generally obtained by saponifying polyvinyl acetate.
  • the PVA may be completely saponified PVA in which only a few percent of acetate groups remain, or may be partially saponified PVA in which the remaining amount of acetate groups is larger than that.
  • the degree of saponification is high, it is preferable because the water resistance of the layer 5 of the composition (I) is high, and completely saponified PVA is particularly preferable.
  • There are various degrees of polymerization of PVA ranging from 300 to several thousand.
  • PVA having any degree of polymerization may be used, but PVA having a high degree of polymerization is preferred because of its high water resistance.
  • the degree of polymerization of PVA is preferably 500 or more and 3000 or less, and more preferably 1000 or more and 3000 or less.
  • the epoxy group-containing silane coupling agent (B) is not particularly limited as long as it is an silane coupling agent having an epoxy group, and is selected from the group consisting of a compound represented by the following formula (b1) and a hydrolyzate thereof, for example. And at least one compound (B2) selected from the group consisting of a compound represented by the following formula (b2) and a hydrolyzate thereof. Among these, the compound (B1) is preferable.
  • R 3 is (It is an organic group containing an epoxy group, and R 4 is an alkyl group having 1 to 5 carbon atoms.)
  • R 2 is preferably CH 3 , C 2 H 5 , or C 2 H 4 OCH 3 .
  • R 3 include 2- (3,4-epoxycyclohexyl) ethyl group and 3-glycidoxypropyl group.
  • Specific examples of the compound represented by the formula (b1) include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropyltriethoxysilane.
  • Specific examples of the compound represented by the formula (b2) include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethyldiethoxysilane, and the like. These can be used alone or in combination of two or more. Among these, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane are preferable, and 3-glycidoxypropyltrimethoxysilane is more preferable from the viewpoint of achieving both flexibility and heat and humidity resistance. .
  • OR 2 becomes OH.
  • the hydrolyzate of the compound represented by the formula (b1) or (b2) can be obtained by a known method.
  • the hydrolysis of the compound represented by the formula (b1) or (b2) is typically performed using an acid or alkali catalyst, alcohol and water. In view of easy control of hydrolysis, it is preferable to use an acid catalyst. At this time, in order to further control the hydrolysis, a generally known catalyst or the like may be added.
  • Examples of the silicon compound (C) include at least one compound (C1) selected from the group consisting of a compound represented by the following formula (c1) and a hydrolyzate thereof.
  • Si (OR 1 ) 4 (c1) (In the formula, R 1 is an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl group having 1 to 4 carbon atoms, and four R 1 in the formula may be the same or different.)
  • R 1 is preferably CH 3 , C 2 H 5 , or C 2 H 4 OCH 3 .
  • the compounds represented by the formula (c1) can be used alone or in combination of two or more.
  • OR 1 becomes OH.
  • the hydrolyzate of the compound represented by the formula (c1) can be obtained by a known method.
  • the hydrolysis of the compound represented by the formula (c1) is typically performed using an acid or alkali catalyst, alcohol and water. In view of easy control of hydrolysis, it is preferable to use an acid catalyst. At this time, in order to further control the hydrolysis, a generally known catalyst or the like may be added.
  • composition (I) may be used in addition to the hydroxyl group-containing polymer compound (A), the epoxy group-containing silane coupling agent (B), and the silicon compound (C) as long as the gas barrier property and heat and humidity resistance are not impaired.
  • Other components may be further included. Examples of other components include additives such as plasticizers, resins, dispersants, surfactants, softeners, stabilizers, antiblocking agents, film forming agents, pressure-sensitive adhesives, oxygen absorbers, and viscosity minerals. .
  • the content of the hydroxyl group-containing polymer compound (A) includes the mass of the hydroxyl group-containing polymer compound (A), the mass of the epoxy group-containing silane coupling agent (B), and the silicon compound (C).
  • the mass ratio of the mass of the hydroxyl group-containing polymer compound (A) to the total mass of the epoxy group-containing silane coupling agent (B) and the silicon compound (C) in terms of SiO 2 ((A) / [ (B) + (C)]) is preferably in the range of 25/75 to 30/70.
  • the gas barrier property of the layer 5 of the composition (I) is excellent. Moreover, it is excellent also in the softness
  • the content of the hydroxyl group-containing polymer compound (A) is not more than the upper limit (30% by mass) of the above range, the heat and moisture resistance of the layer 5 of the composition (I) is excellent, and the gas barrier property is high even under high temperature and high humidity conditions.
  • the SiO 2 equivalent amount of the silicon compound (C), all the silicon atoms contained in the silicon compound (C) is a SiO 2 mass assuming that became SiO 2, silicon atoms having a silicon compound (C) It is calculated from the quantity.
  • the content of the epoxy group-containing silane coupling agent (B) is the mass of the hydroxyl group-containing polymer compound (A), the mass of the epoxy group-containing silane coupling agent (B), and the silicon compound (C) in terms of SiO 2.
  • the total mass with respect to the amount is preferably 5 to 30% by mass, more preferably 5 to 25% by mass, and still more preferably 10 to 20% by mass.
  • the content of the epoxy group-containing silane coupling agent (B) is less than the lower limit (5% by mass) of the above range, the heat and humidity resistance may be insufficient, and the upper limit (30% by mass) of the above range. If it is too high, the flexibility of the layer 5 of the composition (I) may be reduced, or the functional group of the epoxy group-containing silane coupling agent (B) may become pores and gas barrier properties may be reduced. .
  • the hydrolyzate of the compound represented by the formula (b1) or (b2) is used as the epoxy group-containing silane coupling agent (B)
  • the content of the epoxy group-containing silane coupling agent (B) is hydrolyzed. Calculated based on the mass of the previous compound.
  • the silicon compound (C) when using a hydrolyzate of the compound represented by formula (c1), SiO 2 equivalent amount of the silicon compound (C) is calculated based on the weight of the unhydrolyzed compounds.
  • the total mass of the hydroxyl group-containing polymer compound (A), the epoxy group-containing silane coupling agent (B), and the silicon compound (C) in terms of SiO 2 is the total mass. 70 mass% or more is preferable with respect to the mass of solid content, and 90 mass% or more is more preferable. The upper limit of this content is not specifically limited, 100 mass% may be sufficient.
  • the thickness of the layer 5 of the composition (I) varies depending on the use of the laminated sheet 10, but is preferably 5 to 300 nm, more preferably 10 to 50 nm.
  • the thickness of the layer 5 of the composition (I) is not less than the lower limit (5 nm)
  • the heat and humidity resistance is excellent. It is excellent in a softness
  • the laminated sheet 10 can be manufactured, for example, by a manufacturing method including the following steps ( ⁇ 1) and ( ⁇ 2).
  • ⁇ 1 A step of forming the gas barrier layer 3 made of an inorganic material on one surface of the substrate 1.
  • ⁇ 2 A hydroxyl group-containing polymer compound (A), an epoxy group-containing silane coupling agent (B), a silicon compound (C), and a solvent on the surface of the substrate 1 on which the gas barrier layer 3 is formed.
  • the coating liquid (a) containing is formed, the coating film comprised from the said coating agent (a) is formed, the said coating film is dried, and the layer 5 of composition (I) is formed.
  • Step ( ⁇ 1) As a method for forming the gas barrier layer 3, a known method can be used.
  • a known vapor deposition method can be used.
  • the vapor deposition method include a vacuum vapor deposition method, a sputtering method, an ion plating method, a chemical vapor deposition method, and the like.
  • a heating means of the vacuum deposition apparatus by the vacuum deposition method an electron beam heating method, a resistance heating method, an induction heating method, or the like is preferable.
  • reactive vapor deposition may be performed by blowing oxygen gas or the like at the time of vapor deposition.
  • the coating liquid (a) is the same as the composition (I) except that it contains a solvent.
  • a solvent water or a mixed solvent of water and an organic solvent is preferable, and a mixed solvent of water and a lower alcohol having 1 to 5 carbon atoms is more preferable.
  • the coating method of the coating liquid (a) is not particularly limited.
  • casting method dipping method, roll coating method, gravure coating method, screen printing method, reverse coating method, spray coating method, kit coating method, die coating method.
  • Metal ring bar coating method chamber doctor combined coating method, curtain coating method and the like.
  • the method for drying the coating film is not particularly limited, and examples thereof include a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method. Drying may be performed by any one of these methods alone or in combination.
  • the drying temperature is not particularly limited, but when the above-mentioned water or a mixed solvent of water and an organic solvent is used as a solvent, it is usually preferably 50 to 160 ° C.
  • the pressure during drying is usually preferably normal pressure or reduced pressure, and is preferably normal pressure from the viewpoint of facility simplicity.
  • coating and drying of the coating liquid (a) for forming each layer are continuous. It may be performed continuously, or may be performed discontinuously through a winding process and a curing process.
  • the laminated sheet 10 includes the gas barrier layer 3 formed of an inorganic material and the layer 5 of the composition (I) on the substrate 1, the laminated sheet 10 is excellent in gas barrier properties such as oxygen barrier properties and water vapor barrier properties. Further, the layer 5 of the composition (I) is excellent in flexibility. Therefore, the abuse resistance of the laminated sheet 10 is high, and the gas barrier property is not easily deteriorated even after abuse such as bending and stretching.
  • the layer 5 of the composition (I) is excellent in heat and humidity resistance. Therefore, the gas barrier property can be exhibited at a high level even under high temperature and high humidity. Further, the gas barrier property can be maintained at a high level even after hot water treatment such as boil treatment and retort treatment.
  • FIG. 2 is a cross-sectional view schematically showing a laminated sheet 20 according to the second embodiment of the present invention.
  • the laminated sheet 20 includes a substrate 1, a gas barrier layer 3 formed of an inorganic material, a layer 5 of the composition (I), and a layer formed of the following composition (II) (hereinafter referred to as “composition (II). )) And 7).
  • the layer 7 of the composition (II) is provided between the gas barrier layer 3 and the layer 5 of the composition (I).
  • composition (II) A hydroxyl group-containing polymer compound (A) and a silicon compound (C) other than the epoxy group-containing silane coupling agent (B), and the epoxy group-containing silane coupling agent (B) No composition.
  • the composition (II) comprises an epoxy group-containing silane coupling agent (B), a mass of the hydroxyl group-containing polymer compound (A), a mass of the epoxy group-containing silane coupling agent (B), and a silicon compound (C ) Less than 5% by mass with respect to the total mass with the SiO 2 equivalent.
  • the laminated sheet 20 is the same as that of the first embodiment except that the laminated sheet 20 further includes a layer 7 of the composition (II).
  • composition (II) The hydroxyl group-containing polymer compound (A) and the silicon compound (C) in the composition (II) are the same as those described for the composition (I), and the preferred embodiments are also the same.
  • the composition (II) may further contain other components other than the hydroxyl group-containing polymer compound (A), the epoxy group-containing silane coupling agent (B), and the silicon compound (C) as necessary. Examples of the other components include the same as those mentioned for the composition (I).
  • the content of the hydroxyl group-containing polymer compound (A) is 25 to 30% by mass with respect to the total of the hydroxyl group-containing polymer compound (A) and the silicon compound (C) in terms of SiO 2.
  • the content is 27 to 30% by mass.
  • the content of the hydroxyl group-containing polymer compound (A) is not less than the lower limit of the above range, the gas barrier property and flexibility of the layer 7 of the composition (II) are more excellent.
  • the content of the hydroxyl group-containing polymer compound (A) is not more than the upper limit of the above range, the heat and humidity resistance of the layer 7 of the composition (II) is more excellent.
  • the content of the hydroxyl group-containing polymer compound (A) and the epoxy group-containing silane coupling agent (B) contains the epoxy group-containing silane coupling agent (B)
  • the total mass of the mass and the SiO 2 equivalent of the silicon compound (C) is preferably less than 5% by mass, and more preferably less than 3% by mass.
  • the content of the epoxy group-containing silane coupling agent (B) is within the above range, the gas barrier property is more excellent.
  • the total mass of the hydroxyl group-containing polymer compound (A) and the silicon compound (C) in terms of SiO 2 is preferably 70% by mass or more, and 90% by mass with respect to the total solid content. The above is more preferable. The upper limit of this content is not specifically limited, 100 mass% may be sufficient.
  • the thickness of the layer 7 of the composition (II) varies depending on the use of the laminated sheet 10, but is preferably 5 to 300 nm, more preferably 10 to 50 nm.
  • the thickness of the layer 7 of the composition (II) is not less than the lower limit (5 nm)
  • the gas barrier property in a state where abuse is not performed is excellent. It is excellent in a softness
  • the laminated sheet 20 can be manufactured, for example, by a manufacturing method including the following steps ( ⁇ 1), ( ⁇ 2), and ( ⁇ 3).
  • Step ( ⁇ 1) The step ( ⁇ 1) can be performed in the same manner as the step ( ⁇ 1).
  • the step ( ⁇ 2) can be performed in the same manner as the step ( ⁇ 2) except that the coating solution (b) is used instead of the coating solution (a).
  • the coating liquid (b) is the same as the composition (II) except that it contains a solvent.
  • the solvent of the coating liquid (b) water or a mixed solvent of water and an organic solvent is preferable, and a mixed solvent of water and a lower alcohol having 1 to 5 carbon atoms is more preferable.
  • Step ( ⁇ 3) The step ( ⁇ 3) can be performed in the same manner as the step ( ⁇ 2).
  • the laminated sheet 20 includes the gas barrier layer 3 formed of an inorganic material and the layer 5 of the composition (I) on the substrate 1, it has excellent gas barrier properties as in the first embodiment.
  • the layer 5 of the composition (I) is excellent in flexibility and heat and humidity resistance.
  • the layer 7 of the composition (II) there is a tendency that gas barrier properties in a state where abuse is not performed are more excellent.
  • FIG. 3 is a cross-sectional view schematically showing a laminated sheet 30 according to the third embodiment of the present invention.
  • the laminated sheet 30 includes a base material (first base material) 1, a gas barrier layer 3 formed from an inorganic material, a layer 5 of the composition (I), and another base material (second base material) 9. With.
  • the other base material 9 is laminated on the layer 5 of the composition (I) via an adhesive layer 11.
  • the laminated sheet 30 is the same as that of the first embodiment except that the laminated sheet 30 further includes another base material 9 and an adhesive layer 11.
  • the laminated sheet 30 may further include a layer 7 of the composition (II) between the gas barrier layer 3 and the layer 5 of the composition (I). In this case, the laminated sheet 30 is the same as that of the second embodiment except that the laminated sheet 30 further includes another base material 9 and an adhesive layer 11.
  • the other base material 9 is laminated
  • the other base material 9 is appropriately selected depending on the purpose and is not particularly limited, but plastic films and papers are usually preferable. Plastic films and papers may be used alone or in combination of two or more. For example, plastic films and paper may be laminated and used, or two or more kinds of plastic films may be laminated and used.
  • the laminated sheet 30 When the laminated sheet 30 is used in a molded product such as a vertical bag-filling sealing bag, a vacuum packaging bag, a pouch with a spout, a laminated tube container, an infusion bag, a container lid, a paper container, a vacuum insulator, etc. It is preferable that a heat-sealable layer is disposed as the other base material 9 on the outermost layer of the sheet 30. Thereby, the lamination sheet 30 becomes a structure which has heat-sealing property, and the process to a molded article becomes easy. A polyolefin layer is preferred as the heat-sealable layer.
  • the polyolefin is not particularly limited as long as it is a structure suitable for heat sealing, and examples thereof include low density polyethylene (LDPE) and unstretched polypropylene (CPP).
  • LDPE low density polyethylene
  • CPP unstretched polypropylene
  • the thickness of the heat-sealable layer is not particularly limited, but typically can be appropriately set within a range of 5 to 300 ⁇ m, preferably within a range of 10 to 100 ⁇ m.
  • the adhesive layer 11 is a layer that adheres the layer 5 of the composition (I) and another substrate 9.
  • the material of the adhesive layer 11 is not particularly limited, and can be appropriately selected from known adhesives used in, for example, a dry laminating method, a wet laminating method, and an extrusion laminating method.
  • the laminated sheet 30 can be manufactured by, for example, a manufacturing method including the following steps ( ⁇ 1), ( ⁇ 2), and ( ⁇ 3).
  • ( ⁇ 1) A step of forming the gas barrier layer 3 made of an inorganic material on one surface of the substrate 1.
  • the coating liquid (a) containing is formed, the coating film comprised from the said coating agent (a) is formed, the said coating film is dried, and the layer 5 of composition (I) is formed.
  • ( ⁇ 3) A step of laminating another base material 9 via the adhesive layer 11 on the surface of the base material 1 on which the gas barrier layer 3 and the layer 5 of the composition (I) are formed.
  • Step ( ⁇ 1) The step ( ⁇ 1) can be performed in the same manner as the step ( ⁇ 1).
  • the step ( ⁇ 2) can be performed in the same manner as the step ( ⁇ 2).
  • the laminated sheet 30 includes the gas barrier layer 3 formed of an inorganic material and the layer 5 of the composition (I) on the substrate 1, it has excellent gas barrier properties as in the first embodiment.
  • the layer 5 of the composition (I) is excellent in flexibility and heat and humidity resistance.
  • the other base material 9 can impart properties such as strength, sealing properties, easy-opening properties at the time of sealing, design properties, and light blocking properties.
  • the laminated sheet of this invention does not need to have the gas barrier layer 3 formed from an inorganic material.
  • gas barrier layer 3 formed from an inorganic material.
  • the gas barrier layer 3 and the layer 5 of the composition (I) are laminated in this order on one surface of the substrate 1 is shown, but the arrangement of each layer is not limited to this.
  • the gas barrier layer 3 and the layer 5 of the composition (I) may be provided on both surfaces of the substrate 1, respectively, the gas barrier layer 3 is provided on one surface of the substrate 1, and the composition (I ) Layer 5 may be provided.
  • a gas barrier layer 3 is provided between the substrate 1 and the layer 5 of the composition (I).
  • the layer 7 of the composition (II) in the second embodiment and the other substrate 9 in the third embodiment may be provided on both surfaces of the substrate 1.
  • the laminated sheet of the present invention may further have an anchor coat layer between the base material 1 and the gas barrier layer 3 for the purpose of improving their adhesion.
  • the material constituting the anchor coat layer include urethane resins, epoxy resins, acrylic resins, and polyester resins.
  • other additives such as a curing agent and a silane coupling agent may be added to these depending on the application.
  • a combination of an acrylic polyol, an isocyanate compound, and a silane coupling agent is preferable. When an anchor coat layer composed of this combination is used, stable and high adhesion can be obtained between the substrate and the vapor deposition layer.
  • the thickness of the anchor coat layer is not particularly limited as long as the thickness on the surface of the substrate 1 is uniform, but is preferably 0.01 to 2 ⁇ m, more preferably 0.05 to 0.5 ⁇ m. .
  • the thickness of the anchor coat layer is not less than the lower limit (0.01 ⁇ m) of the above range, the uniformity of the thickness of the anchor coat layer is high and the adhesion of the gas barrier layer 3 to the substrate 1 is more excellent. If the thickness of the anchor coat layer is less than or equal to the upper limit (2 ⁇ m) of the above range, the anchor coat layer retains sufficient flexibility and does not easily crack due to external factors such as abuse.
  • a layer other than the layer 7 of the composition (II) is replaced with the layer 7 of the composition (II) between the gas barrier layer 3 and the layer 5 of the composition (I). Or may be further included with the layer 7 of the composition (II).
  • the laminated sheet of the present invention further has other layers other than the other substrate 9 and the adhesive layer 11 on the layer 5 of the composition (I) (on the side opposite to the substrate 1 side). May be.
  • a printing layer or a vapor deposition layer can be provided for the purpose of providing design properties, providing light blocking properties, providing moisture resistance, and the like.
  • the laminated sheet of the present invention can exhibit high gas barrier properties even under high temperature and high humidity, and can maintain gas barrier properties at a high level even after hot water treatment such as boil treatment and retort treatment.
  • post-processing such as printing process, dry lamination, melt extrusion lamination, thermocompression lamination using the laminated sheet of the present invention is used in the packaging field of foods, pharmaceuticals, etc. It is possible to provide a packaging material with a wide practical range.
  • the use of the laminated sheet of the present invention is not limited to this, and can be used for uses other than packaging materials.
  • Applications other than packaging materials include, for example, LCD substrate films, organic EL substrate films, electronic paper substrate films, electronic device sealing films, PDP films, LED films, IC tag films, solar cell bags Sheets, films related to electronic devices such as protective films for solar cells, optical communication members, flexible films for electronic devices, diaphragms for fuel cells, sealing films for fuel cells, substrate films for various functional films, and the like.
  • the packaging material according to the present invention includes the above-described laminated sheet of the present invention.
  • the packaging material of this invention may be comprised only from the lamination sheet of this invention, and the structure containing the lamination sheet of this invention and another material may be sufficient as it. Examples of other materials include a thermoplastic resin film and paper.
  • the packaging material of the present invention is not particularly limited and can be used as a packaging material for various articles.
  • the packaging material of this embodiment is preferably used as a packaging material for articles that are easily deteriorated by the influence of oxygen, water vapor, etc., and in particular, is preferably used as a packaging material for food.
  • they can be preferably used as packaging materials for non-food products, for example, chemicals such as agricultural chemicals and pharmaceuticals, medical tools, machine parts, precision materials, and the like.
  • the laminated sheet of the present invention is excellent in heat and humidity resistance, and when subjected to hot water treatment, the gas barrier property and interlayer adhesion are not easily deteriorated. Therefore, the packaging material of the present invention is useful as a packaging material for hot water treatment. Examples of the hot water treatment include boil treatment and retort treatment.
  • the boil treatment is a method of sterilizing with wet heat to preserve foods and the like.
  • Examples of the boil treatment include a method of sterilizing a packaging material in which foods and the like are packaged at 60 to 100 ° C. and atmospheric pressure for 10 to 120 minutes, depending on the contents.
  • the boil treatment is preferably carried out using a hot water tank, and there are a batch type in which it is immersed in a hot water tank at a constant temperature and taken out after a fixed time, and a continuous type in which the hot water tank is sterilized through a tunnel type.
  • retort treatment is a method of sterilizing microorganisms such as molds, yeasts, and bacteria in order to preserve foods and the like.
  • examples of the retort treatment include a method in which a packaging material in which food or the like is packaged is subjected to a pressure sterilization treatment at 105 to 140 ° C. and 0.15 to 0.3 MPa for 10 to 120 minutes.
  • the retort apparatus used for the retort treatment includes a steam type using heated steam, a hot water type using pressurized superheated water, and the like, which are properly used depending on the sterilization conditions of food or the like as the contents.
  • the contents to be packaged with the hot water packaging material are not particularly limited, and may be food or non-food.
  • the food include curry, cooking seasoning sauce, and processed meat products.
  • non-food include medical products such as infusion preparations, and industrial products such as semiconductors and precision materials.
  • the molded product according to the present invention includes the packaging material of the present invention described above.
  • the molded article include a container, a member constituting a part of the container, and the like, and specific examples include a vertical bag filling and sealing bag, a vacuum packaging bag, a pouch with a spout, a laminate tube container, an infusion bag, and a container. Examples thereof include lid materials, paper containers, and vacuum insulators.
  • the molded product of the present invention can be manufactured by a known method.
  • vacuum packaging bags, spout pouches, laminated tube containers, infusion bags, container lids, paper containers, vacuum insulators, etc. heat sealing of packaging materials is usually performed. . Therefore, as a packaging material constituting these molded articles, one in which a heat-sealable layer is usually disposed on one or both outermost layers is preferable.
  • 0.1N hydrochloric acid is added to tetraethoxysilane (Si (OC 2 H 5 ) 4 , hereinafter referred to as “TEOS”), and the mixture is stirred for 30 minutes to be hydrolyzed to a solid content of 3% by mass (in terms of SiO 2 ).
  • TEOS hydrolysis solution was prepared.
  • 0.1N hydrochloric acid was added to 3-glycidoxypropyltrimethoxysilane (hereinafter referred to as “GPTMS”), and the mixture was stirred for 30 minutes for hydrolysis to prepare a GPTMS hydrolysis solution having a solid content of 3% by mass.
  • GPTMS hydrolysis solution having a solid content of 3% by mass.
  • a PVA solution, a GPTMS hydrolyzed solution, and a TEOS hydrolyzed solution are mixed so that PVA / GPTMS / TEOS (in terms of SiO 2 ) is 25/5/70 in terms of solid mass ratio to prepare a coating liquid (a1). did.
  • Preparation Example 2 A coating liquid (a2) was prepared in the same manner as in Preparation Example 1 except that PVA / GPTMS / TEOS (SiO 2 conversion) was 25/15/60.
  • Preparation Example 3 A coating solution (a3) was prepared in the same manner as in Preparation Example 1 except that PVA / GPTMS / TEOS (SiO 2 conversion) was 25/25/50.
  • Preparation Example 4 A coating liquid (a4) was prepared in the same manner as in Preparation Example 1 except that PVA / GPTMS / TEOS (SiO 2 conversion) was 25/30/45.
  • Preparation Example 5 A coating liquid (a5) was prepared in the same manner as in Preparation Example 1, except that PVA / GPTMS / TEOS (SiO 2 conversion) was 27.5 / 5 / 67.5.
  • Preparation Example 6 A coating liquid (a6) was prepared in the same manner as in Preparation Example 1, except that PVA / GPTMS / TEOS (SiO 2 equivalent) was 27.5 / 7 / 65.5.
  • Preparation Example 7 A coating solution (a7) was prepared in the same manner as in Preparation Example 1, except that PVA / GPTMS / TEOS (SiO 2 conversion) was 27.5 / 30 / 42.5.
  • Preparation Example 8 A coating solution (a8) was prepared in the same manner as in Preparation Example 1, except that PVA / GPTMS / TEOS (SiO 2 conversion) was set to 30/5/65.
  • Preparation Example 9 A coating solution (a9) was prepared in the same manner as in Preparation Example 1, except that PVA / GPTMS / TEOS (SiO 2 equivalent) was 30 / 17.5 / 52.5.
  • Preparation Example 10 A coating solution (a10) was prepared in the same manner as in Preparation Example 1, except that PVA / GPTMS / TEOS (SiO 2 equivalent) was 30/30/40.
  • Preparation Example 11 A coating solution (a11) was prepared in the same manner as in Preparation Example 1, except that GPTMS was changed to 3-glycidoxypropyltriethoxysilane (hereinafter referred to as “GPTES”).
  • GPTES 3-glycidoxypropyltriethoxysilane
  • Preparation Example 12 The PVA solution and the TEOS hydrolysis solution were mixed so that the PVA / TEOS (SiO 2 conversion) was 25/75 in terms of solid content, and the same as in Preparation Example 1 except that the GPTMS hydrolysis solution was not added. Thus, a coating liquid (b1) was prepared.
  • a coating solution (b2) was prepared in the same manner as in Preparation Example 1, except that PVA / GPTMS / TEOS (SiO 2 equivalent) was 20 / 17.5 / 62.5.
  • a coating solution (b3) was prepared in the same manner as in Preparation Example 1, except that PVA / GPTMS / TEOS (SiO 2 equivalent) was 35 / 17.5 / 47.5.
  • a coating liquid (b4) was prepared in the same manner as in Preparation Example 1 except that PVA / GPTMS / TEOS (SiO 2 equivalent) was 27.5 / 35 / 37.5.
  • a coating solution (b5) was prepared in the same manner as in Preparation Example 1, except that GPTMS was changed to 3-aminopropyltrimethoxysilane (hereinafter referred to as “APTMS”).
  • Example 1 On a biaxially stretched polyethylene terephthalate film (PET: manufactured by Toray, Lumirror (registered trademark) P60, thickness 12 ⁇ m, inner corona treatment), metal aluminum is evaporated by an electron beam heating vacuum deposition apparatus, and oxygen gas is present there. Then, aluminum oxide was vapor-deposited to form a vapor-deposited film (gas barrier layer) having a thickness of 20 nm.
  • PET biaxially stretched polyethylene terephthalate film
  • Lumirror registered trademark
  • a coating liquid (a1) is applied onto the gas barrier layer with a bar coater, and dried at 120 ° C. for 1 minute with a dryer to form a film (layer (a1)) having a film thickness of about 0.3 ⁇ m.
  • a laminated sheet having the configuration of [PET / gas barrier layer / layer (a1)] was obtained.
  • Example 2 [PET / gas barrier layer / layer (a2)] was performed in the same manner as in Example 1 except that the coating liquid (a2) was used instead of the coating liquid (a1) to form a film (layer (a2)). A laminated sheet having the structure is obtained.
  • Example 3 [PET / gas barrier layer / layer (a3)] was performed in the same manner as in Example 1 except that the coating liquid (a3) was used instead of the coating liquid (a1) to form a film (layer (a3)). A laminated sheet having the structure is obtained.
  • Example 4 [PET / gas barrier layer / layer (a4)] The same operation as in Example 1 was performed except that the coating liquid (a4) was used instead of the coating liquid (a1) to form a film (layer (a4)). A laminated sheet having the structure is obtained.
  • Example 5 [PET / gas barrier layer / layer (a5)] was performed in the same manner as in Example 1 except that the coating liquid (a5) was used instead of the coating liquid (a1) to form a film (layer (a5)). A laminated sheet having the structure is obtained.
  • Example 6 [PET / gas barrier layer / layer (a6)] was performed in the same manner as in Example 1 except that the coating liquid (a6) was used instead of the coating liquid (a1) to form a film (layer (a6)). A laminated sheet having the structure is obtained.
  • Example 7 [PET / gas barrier layer / layer (a7)] The same operation as in Example 1 was performed except that the coating liquid (a7) was used instead of the coating liquid (a1) to form a film (layer (a7)). A laminated sheet having the structure is obtained.
  • Example 8 [PET / gas barrier layer / layer (a8)] was performed in the same manner as in Example 1 except that the coating liquid (a8) was used instead of the coating liquid (a1) to form a film (layer (a8)). A laminated sheet having the structure is obtained.
  • Example 9 [PET / gas barrier layer / layer (a9)] was performed in the same manner as in Example 1 except that the coating liquid (a9) was used instead of the coating liquid (a1) to form a film (layer (a9)). A laminated sheet having the structure is obtained.
  • Example 10 [PET / gas barrier layer / layer (a10)] was performed in the same manner as in Example 1 except that the coating liquid (a10) was used instead of the coating liquid (a1) to form a film (layer (a10)). A laminated sheet having the structure is obtained.
  • Example 11 [PET / gas barrier layer / layer (a11)] The same operation as in Example 1 was performed except that the coating liquid (a11) was used instead of the coating liquid (a1) to form a film (layer (a11)). A laminated sheet having the structure is obtained.
  • Example 12 [PET / gas barrier layer / layer (b1)] The same operation as in Example 1 was performed except that the coating liquid (b1) was used instead of the coating liquid (a1) to form a film (layer (b1)). The laminated body which has a structure of] was obtained. Next, the coating liquid (a9) is applied onto the layer (b1) of the obtained laminate by a bar coater, and dried at 120 ° C. for 1 minute with a dryer to form a 0.3 ⁇ m-thick film (layer (a9 )) To form a laminated sheet having a structure of [PET film / gas barrier layer / layer (b1) / layer (a9)].
  • Comparative Example 1 On a biaxially stretched polyethylene terephthalate film (PET: manufactured by Toray, Lumirror (registered trademark) P60, thickness 12 ⁇ m, inner corona treatment), metal aluminum is evaporated by an electron beam heating vacuum deposition apparatus, and oxygen gas is present there. Then, aluminum oxide was vapor-deposited to form a vapor-deposited film (gas barrier layer) having a thickness of 20 nm.
  • PET polyethylene terephthalate film
  • Lumirror registered trademark
  • the coating liquid (b1) is applied onto the gas barrier layer with a bar coater, and dried at 120 ° C. for 1 minute with a dryer to form a film (layer (b1)) having a film thickness of about 0.6 ⁇ m.
  • a laminated sheet having the configuration of [PET / gas barrier layer / layer (b1)] was obtained.
  • Comparative Example 2 A laminated sheet was obtained in the same manner as in Comparative Example 1 except that the coating liquid (b2) was used instead of the coating liquid (b1) to form a film (layer (b2)).
  • Comparative Example 3 A laminated sheet was obtained in the same manner as in Comparative Example 1 except that the coating liquid (b3) was used instead of the coating liquid (b1) to form a film (layer (b3)).
  • Comparative Example 4 A laminated sheet was obtained in the same manner as in Comparative Example 1 except that the coating liquid (b4) was used instead of the coating liquid (b1) to form a film (layer (b4)).
  • Comparative Example 5 A laminated sheet was obtained by performing the same operation as in Comparative Example 1 except that the coating liquid (b5) was used instead of the coating liquid (b1) to form a film (layer (b5)).
  • LLDPE linear low density polyethylene
  • a two-component curable adhesive Takelac A525 (main agent) / Takenate A52 (hardener) manufactured by Mitsui Chemicals, Inc. was used.
  • Ny a stretched nylon film, Emblem ONMB (15 ⁇ m) manufactured by Unitika Ltd. was used.
  • CPP a polypropylene film manufactured by Toray Film Processing Co., Ltd., Treffan ZK93FM (60 ⁇ m) was used.
  • LLDPE a linear low-density polyethylene film, TUX-TCS (60 ⁇ m) manufactured by Mitsui Chemicals, Inc., Toro Cello Co., Ltd. was used.
  • the oxygen permeability of the sample was measured under the conditions of a temperature of 30 ° C. and a relative humidity of 70% using an oxygen permeation tester (OXTRAN 2/20, manufactured by Modern Control). The measurement method was expressed in units of cm 3 (STP) / (m 2 ⁇ day ⁇ MPa) in accordance with JIS K-7126 “Method B (isobaric method)” and ASTM D3985-81. .
  • (STP) means standard conditions (0 ° C., 1 atm) for defining the volume of oxygen.
  • a laminate film (configuration: laminated sheet / adhesive / LLDPE) was cut into a size of 200 mm long ⁇ 150 mm wide to prepare a sample.
  • the sample was subjected to the following abuse test.
  • the sample was stretched 5% in the machine direction at a speed of 100 ⁇ m / second using Tensilon manufactured by Toyo Baldwin, and the stretched state was maintained for 1 minute. Then, the film was returned to the original position at the same speed and stretched. .
  • the oxygen permeability and the water vapor permeability were measured by the measurement method described above.
  • (A) component represents a hydroxyl group-containing polymer compound (A)
  • Si agent represents a silane coupling agent
  • (C) component represents a silicon compound (C).
  • the laminated sheets of Examples 1 to 12 had high gas barrier properties in the state of the base paper. Further, the difference between the oxygen permeability and water vapor permeability of the base paper and the values of oxygen permeability and water vapor permeability after stretching and after retorting were small, and the film was excellent in flexibility and heat and humidity resistance.
  • the coating liquid used for forming the coating does not contain an epoxy group-containing silane coupling agent (B), Comparative Example 1, a polymer compound (A), an epoxy group-containing silane coupling agent (B), and a silicon compound (C )
  • the laminated sheet of the present invention has a high gas barrier property even under high temperature and high humidity, and can maintain the gas barrier property at a high level even after hot water treatment such as boil treatment and retort treatment. In addition, gas barrier properties are unlikely to deteriorate even after abuse such as bending or stretching. Therefore, by using the laminated sheet of the present invention, post-processing such as a printing process, dry lamination, melt extrusion lamination, thermocompression lamination, etc. is provided to provide a packaging material with a wide practical range used in the packaging field of foods, pharmaceuticals, etc. It is possible.
  • the laminated sheet of the present invention can be used for applications other than packaging materials.
  • Applications other than packaging materials include, for example, LCD substrate films, organic EL substrate films, electronic paper substrate films, electronic device sealing films, PDP films, LED films, IC tag films, solar cell bags Sheets, films related to electronic devices such as protective films for solar cells, optical communication members, flexible films for electronic devices, diaphragms for fuel cells, sealing films for fuel cells, substrate films for various functional films, and the like.

Abstract

A layered sheet is provided with: a substrate; and a layer formed from a composition including a hydroxyl-group-containing polymer compound (A), an epoxy-group-containing silane coupling agent (B), and another silicon compound (C) other than the epoxy-group-containing silane coupling agent (B); the ratio of the hydroxyl-group-containing polymer compound (A) being 25-30% by mass and the ratio of the epoxy-group-containing silane coupling agent compound (B) being 5-30% by mass with respect to the total of the mass of the hydroxyl-group-containing polymer compound (A), the mass of the epoxy-group-containing silane coupling agent (B), and an SiO2 equivalent quantity of the silicon compound (C).

Description

積層シート、包装材料、および成形品Laminated sheets, packaging materials, and molded products
　本発明は、積層シート、包装材料および成形品に関する。
　本願は、２０１６年５月３１日に、日本に出願された特願２０１６－１０８１５９号に基づき優先権を主張し、その内容をここに援用する。 The present invention relates to a laminated sheet, a packaging material, and a molded product.
This application claims priority on May 31, 2016 based on Japanese Patent Application No. 2016-108159 for which it applied to Japan, and uses the content here.
　近年、食品および医薬品や電子部材等の非食品等の包装に用いられる包装材料は、内容物の変質を抑制し、それらの機能や性質を保持するために、酸素、水蒸気等のガスの透過を遮断するガスバリア性を備えることが求められている。 In recent years, packaging materials used for packaging foods and non-food products such as pharmaceuticals and electronic components have been designed to prevent the alteration of contents and to permeate gases such as oxygen and water vapor in order to maintain their functions and properties. It is required to have a gas barrier property for blocking.
　食品および非食品等の包装に用いられるガスバリア性シートとして、ポリエステルフィルム等の基材の少なくとも片面に無機蒸着層を設けた無機蒸着フィルムが広く用いられている（例えば特許文献１）。
　しかし、特許文献１で提案されているような無機蒸着フィルムは、折り曲げ、延伸等によりフィルムに応力を加えると、無機蒸着層がダメージを受け、ガスバリア性が低下しやすい。 As a gas barrier sheet used for packaging foods and non-foods, an inorganic vapor deposition film in which an inorganic vapor deposition layer is provided on at least one surface of a substrate such as a polyester film is widely used (for example, Patent Document 1).
However, when an inorganic vapor deposition film as proposed in Patent Document 1 is stressed by bending, stretching, or the like, the inorganic vapor deposition layer is damaged, and the gas barrier property tends to be lowered.
　特許文献２では、無機蒸着層の上に、水溶性高分子と、１種以上のアルコキシド、その加水分解物、及び塩化錫の少なくともいずれか１つとを含む水溶液或いは水／アルコール混合溶液を主剤とするコーティング剤を塗布し、加熱乾燥して形成されるガスバリア性被膜を設けたガスバリア性積層フィルムが提案されている。
　このガスバリア性積層フィルムは、高いガスバリア性を示し、柔軟なガスバリア性被膜で無機蒸着層が被覆されていることで、折り曲げ、延伸等の後でもある程度のガスバリア性を保持する。また、耐熱性、耐湿性、耐水性を有すると開示されている。 In Patent Document 2, an aqueous solution or a water / alcohol mixed solution containing a water-soluble polymer and at least one of at least one alkoxide, a hydrolyzate thereof, and tin chloride on an inorganic vapor deposition layer is used as a main agent. There has been proposed a gas barrier laminated film provided with a gas barrier film formed by applying a coating agent to be heated and drying.
This gas barrier laminate film exhibits high gas barrier properties, and retains a certain degree of gas barrier properties even after bending, stretching, etc., by coating the inorganic vapor deposition layer with a flexible gas barrier coating. It is also disclosed that it has heat resistance, moisture resistance and water resistance.
日本国特開平９－１２３３３８号公報Japanese Laid-Open Patent Publication No. 9-123338 日本国特許第２７９００５４号公報Japanese Patent No. 2790054
　しかし、特許文献２に開示のガスバリア性被膜の耐熱湿性は十分とはいえず、高温高湿雰囲気に曝されると、ガスバリア性被膜が膨潤し、ガスバリア性が劣化してしまうことがある。また、このガスバリア性被膜の柔軟性も十分とはいえず、ガスバリア性積層フィルムに対して折り曲げや延伸等の加工を施したときに、その加工の種類や程度によっては、無機蒸着層にまで加工によるダメージが到達し、ガスバリア性が損なわれることがある。 However, the heat and moisture resistance of the gas barrier coating disclosed in Patent Document 2 is not sufficient, and when exposed to a high temperature and high humidity atmosphere, the gas barrier coating may swell and the gas barrier properties may deteriorate. In addition, the flexibility of this gas barrier coating is not sufficient, and when the gas barrier laminated film is processed such as bending or stretching, it can be processed to an inorganic vapor deposition layer depending on the type and degree of processing. May cause damage to gas barrier properties.
　本発明は、上記事情を鑑みてなされたものであって、柔軟性および耐熱湿性に優れた層を備える積層シート、これを用いた包装材料および成形品の提供を目的とする。 The present invention has been made in view of the above circumstances, and an object thereof is to provide a laminated sheet having a layer excellent in flexibility and heat and humidity resistance, a packaging material using the same, and a molded product.
　本発明の第一態様に係る積層シートは、基材と、水酸基含有高分子化合物（Ａ）と、エポキシ基含有シランカップリング剤（Ｂ）と、前記エポキシ基含有シランカップリング剤（Ｂ）以外の他のケイ素化合物（Ｃ）とを含む組成物から形成された層と、を備え、前記水酸基含有高分子化合物（Ａ）の質量と、前記エポキシ基含有シランカップリング剤（Ｂ）の質量と、前記ケイ素化合物（Ｃ）のＳｉＯ２換算量との合計質量に対し、前記水酸基含有高分子化合物（Ａ）の割合が２５～３０質量％、前記エポキシ基含有シランカップリング剤化合物（Ｂ）の割合が５～３０質量％である。
　上記第一態様において、前記ケイ素化合物（Ｃ）が、下記式（ｃ１）で表される化合物およびその加水分解物からなる群から選ばれる少なくとも１種の化合物（Ｃ１）を含んでいてもよい。
　Ｓｉ（ＯＲ１）４　・・・（ｃ１）
（式中、Ｒ１は炭素数１～４のアルキル基または炭素数１～４のアルコキシアルキル基であり、式中の４つのＲ１は同じであっても異なっていてもよい。）
　上記第一態様において、前記エポキシ基含有シランカップリング剤（Ｂ）が、下記式（ｂ１）で表される化合物およびその加水分解物からなる群から選ばれる少なくとも１種の化合物（Ｂ１）を含んでいてもよい。
　Ｒ３Ｓｉ（ＯＲ２）３　・・・（ｂ１）
（式中、Ｒ２は炭素数１～４のアルキル基または炭素数１～４のアルコキシアルキル基であり、式中の３つのＲ２は同じであっても異なっていてもよく、Ｒ３はエポキシ基を含む有機基である。）
　上記第一態様に係る積層シートは、無機材料から形成されるガスバリア層をさらに備えていてもよい。
　本発明の第二態様に係る包装材料は、上記第一態様に係る積層シートを含む。
　上記第二態様に係る包装材料は、熱水処理用包装材料であってもよい。
　本発明の第三態様に係る成形品は、上記第二態様に係る包装材料を備える。
　上記第三態様に係る成形品は、縦製袋充填シール袋、真空包装袋、スパウト付パウチ、ラミネートチューブ容器、輸液バッグ、容器用蓋材、紙容器または真空断熱体であってもよい。 The laminated sheet according to the first aspect of the present invention includes a base material, a hydroxyl group-containing polymer compound (A), an epoxy group-containing silane coupling agent (B), and the epoxy group-containing silane coupling agent (B). A layer formed from a composition containing another silicon compound (C), and a mass of the hydroxyl group-containing polymer compound (A) and a mass of the epoxy group-containing silane coupling agent (B). The ratio of the hydroxyl group-containing polymer compound (A) to the total mass of the silicon compound (C) with respect to the SiO 2 equivalent is 25 to 30% by mass, and the epoxy group-containing silane coupling agent compound (B). The ratio is 5 to 30% by mass.
In the first aspect, the silicon compound (C) may contain at least one compound (C1) selected from the group consisting of a compound represented by the following formula (c1) and a hydrolyzate thereof.
Si (OR 1 ) 4 (c1)
(In the formula, R 1 is an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl group having 1 to 4 carbon atoms, and four R 1 in the formula may be the same or different.)
In the first aspect, the epoxy group-containing silane coupling agent (B) includes at least one compound (B1) selected from the group consisting of a compound represented by the following formula (b1) and a hydrolyzate thereof. You may go out.
R 3 Si (OR 2 ) 3 (b1)
(Wherein R 2 is an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl group having 1 to 4 carbon atoms, and three R 2 in the formula may be the same or different, and R 3 is An organic group containing an epoxy group.)
The laminated sheet according to the first aspect may further include a gas barrier layer formed from an inorganic material.
The packaging material according to the second aspect of the present invention includes the laminated sheet according to the first aspect.
The packaging material according to the second aspect may be a packaging material for hot water treatment.
The molded product according to the third aspect of the present invention includes the packaging material according to the second aspect.
The molded product according to the third aspect may be a vertical bag-filling sealing bag, a vacuum packaging bag, a pouch with a spout, a laminated tube container, an infusion bag, a container lid, a paper container, or a vacuum insulator.
　本発明の上記各態様によれば、柔軟性および耐熱湿性に優れた層を備える積層シート、これを用いた包装材料および成形品を提供できる。 According to each aspect of the present invention, it is possible to provide a laminated sheet having a layer excellent in flexibility and heat and humidity resistance, a packaging material and a molded product using the same.
本発明の第一実施形態に係る積層シートを模式的に示す断面図である。It is sectional drawing which shows typically the lamination sheet which concerns on 1st embodiment of this invention. 本発明の第二実施形態に係る積層シートを模式的に示す断面図である。It is sectional drawing which shows typically the lamination sheet which concerns on 2nd embodiment of this invention. 本発明の第三実施形態に係る積層シートを模式的に示す断面図である。It is sectional drawing which shows typically the lamination sheet which concerns on 3rd embodiment of this invention.
≪積層シート≫
　以下、本発明の積層シートについて、添付の図面を用い、実施形態を示して説明する。 ≪Laminated sheet≫
Hereinafter, the laminated sheet of the present invention will be described with reference to the accompanying drawings.
＜第一実施形態＞
　図１は、本発明の第一実施形態に係る積層シート１０を模式的に示す断面図である。
　積層シート１０は、基材１と、無機材料から形成されたガスバリア層３と、以下の組成物（Ｉ）から形成された層（以下「組成物（Ｉ）の層」ともいう）５とを備える。
　組成物（Ｉ）：水酸基含有高分子化合物（Ａ）と、エポキシ基含有シランカップリング剤（Ｂ）と、前記エポキシ基含有シランカップリング剤（Ｂ）以外の他のケイ素化合物（Ｃ）とを含み、前記水酸基含有高分子化合物（Ａ）と前記エポキシ基含有シランカップリング剤（Ｂ）と前記ケイ素化合物（Ｃ）のＳｉＯ２換算量との合計に対し、前記水酸基含有高分子化合物（Ａ）の割合が２５～３０質量％、前記エポキシ基含有シランカップリング剤化合物（Ｂ）の割合が５～３０質量％である組成物。
　ガスバリア層３は、基材１の一方の面上に積層され、組成物（Ｉ）の層５は、ガスバリア層３上に積層されている。 <First embodiment>
FIG. 1 is a cross-sectional view schematically showing a laminated sheet 10 according to the first embodiment of the present invention.
The laminated sheet 10 includes a base material 1, a gas barrier layer 3 formed of an inorganic material, and a layer 5 (hereinafter also referred to as “layer of composition (I)”) formed of the following composition (I). Prepare.
Composition (I): a hydroxyl group-containing polymer compound (A), an epoxy group-containing silane coupling agent (B), and another silicon compound (C) other than the epoxy group-containing silane coupling agent (B) Including the hydroxyl group-containing polymer compound (A), the epoxy group-containing silane coupling agent (B), and the total amount of the silicon compound (C) in terms of SiO 2. Is a composition in which the ratio of the epoxy group-containing silane coupling agent compound (B) is 5 to 30% by mass.
The gas barrier layer 3 is laminated on one surface of the substrate 1, and the layer 5 of the composition (I) is laminated on the gas barrier layer 3.
（基材）
　基材１の材質としては、例えばプラスチック類、紙類、ゴム類等が挙げられる。
　基材１としては、基材１とガスバリア層３等との密着性の観点から、プラスチック類のフィルムが好ましい。 (Base material)
Examples of the material of the substrate 1 include plastics, papers, rubbers, and the like.
The substrate 1 is preferably a plastic film from the viewpoint of adhesion between the substrate 1 and the gas barrier layer 3 and the like.
　プラスチック類としては、例えばポリエステル（例えばポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）等）、ポリオレフィン（例えばポリエチレン、ポリプロピレン等）、ポリスチレン、ポリアミド（例えば６６－ナイロン等）、ポリカーボネート、ポリアクリロニトリル、ポリイミド等のエンジニアリングプラスチック等が挙げられる。これらの樹脂材料の１種を単独で、または２種以上をブレンドしてフィルム状に加工したものを基材１として使用できる。 Examples of plastics include polyester (eg, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), etc.), polyolefin (eg, polyethylene, polypropylene, etc.), polystyrene, polyamide (eg, 66-nylon, etc.), polycarbonate, polyacrylonitrile, polyimide, etc. Engineering plastics and the like. One of these resin materials can be used as the base material 1 alone or by blending two or more kinds into a film.
　プラスチック類のフィルムは、延伸、未延伸のどちらでもよく、十分な機械強度や寸法安定性を有するものが好ましい。特に、二軸方向に任意に延伸されたフィルムが好ましく用いられる。
　積層シート１０を包装材料に使用する場合、基材１としては、価格面、防湿性、充填適性、風合い、および廃棄性を考慮すると、ポリアミドフィルム、ポリエステルフィルムが好ましく、ポリエステルフィルムがより好ましい。
　基材１の表面に、基材１とガスバリア層３等との接着性の観点から、コロナ処理、火炎処理、プラズマ処理等の表面活性化処理が施されていてもよい。 The plastic film may be either stretched or unstretched, and preferably has sufficient mechanical strength and dimensional stability. In particular, a film arbitrarily stretched in the biaxial direction is preferably used.
When the laminated sheet 10 is used as a packaging material, the base material 1 is preferably a polyamide film or a polyester film, and more preferably a polyester film, in consideration of price, moisture resistance, filling suitability, texture, and discardability.
From the viewpoint of adhesion between the substrate 1 and the gas barrier layer 3 and the like, the surface of the substrate 1 may be subjected to a surface activation treatment such as corona treatment, flame treatment, and plasma treatment.
　基材１の厚さは、積層シート１０の用途に応じて適宜設定できる。例えば、積層シート１０を包装材料に使用する場合、特に制限を受けるものではないが、包装材料としての適性および加工性を考慮すると、実用的には３～２００μｍが好ましく、６～３０μｍがより好ましい。 The thickness of the substrate 1 can be appropriately set according to the use of the laminated sheet 10. For example, when the laminated sheet 10 is used as a packaging material, it is not particularly limited. However, in consideration of suitability as a packaging material and processability, it is preferably 3 to 200 μm and more preferably 6 to 30 μm. .
（ガスバリア層）
　ガスバリア層３は、無機材料から形成される。
　前記無機材料としては、積層シート１０に酸素バリア性、水蒸気バリア性等のガスバリア性を付与するための層を構成することができる無機材料が適宜選択され、例えば金属（例えばアルミニウム等）、無機酸化物（例えば酸化アルミニウム、酸化ケイ素、酸化マグネシウム、酸化錫等）等が挙げられる。
　ガスバリア層３としては、前記無機材料を蒸着法により基材１上に蒸着させた蒸着膜が好ましい。 (Gas barrier layer)
The gas barrier layer 3 is formed from an inorganic material.
As the inorganic material, an inorganic material capable of constituting a layer for imparting gas barrier properties such as oxygen barrier property and water vapor barrier property to the laminated sheet 10 is appropriately selected. For example, metal (for example, aluminum), inorganic oxidation (For example, aluminum oxide, silicon oxide, magnesium oxide, tin oxide, etc.).
The gas barrier layer 3 is preferably a deposited film obtained by depositing the inorganic material on the substrate 1 by a deposition method.
　酸化アルミニウムは、アルミニウム（Ａｌ）と酸素（Ｏ）との存在比が、Ａｌ：Ｏ＝１：１．５～１：２．０であることが好ましい。例えば酸化アルミニウム蒸着膜は、アルミニウムを蒸発材料にして、酸素ガスと、炭酸ガス等の不活性ガス等との混合ガスの存在下で薄膜形成を行う反応性蒸着、反応性スパッタリング、反応性イオンプレーティング等により形成することができる。この時、アルミニウムを酸素と反応させれば、化学量論的にはＡｌ２Ｏ３であることから、Ａｌ：Ｏ＝１：１．５であるはずである。しかし蒸着方法によって、一部アルミニウムのまま存在する場合や、または過酸化アルミニウムで存在する場合もある。そのため、Ｘ線光電子分光分析装置（ＸＰＳ）等を用いて蒸着膜の元素の存在比を測定すると、一概にＡｌ：Ｏ＝１：１．５とは言えないことがわかる。一般にＡｌ：Ｏ＝１：１．５より酸素が少なくアルミニウム量が多い場合は、級密な膜を形成するために良好なガスバリア性が得られるが、蒸着膜が黒く着色し、光線透過量が低くなる傾向がある。一方、Ａｌ：Ｏ＝１：２．０より酸素が多くアルミニウム量が少ない場合は、疎な膜を形成し、ガスバリア性は悪いが光線透過量は高く透明な膜が得られる。
　酸化ケイ素は、特に耐水性が必要とされる場合に好ましい。 The aluminum oxide preferably has an abundance ratio between aluminum (Al) and oxygen (O) of Al: O = 1: 1.5 to 1: 2.0. For example, an aluminum oxide vapor deposition film is a reactive vapor deposition, reactive sputtering, or reactive ion plate that forms a thin film in the presence of a mixed gas of oxygen gas and inert gas such as carbon dioxide gas using aluminum as an evaporation material. It can be formed by ting or the like. At this time, if aluminum is reacted with oxygen, it should be Al: O = 1: 1.5 because it is stoichiometrically Al 2 O 3 . However, depending on the vapor deposition method, some aluminum may exist as it is, or aluminum peroxide may exist. Therefore, when the abundance ratio of the elements in the deposited film is measured using an X-ray photoelectron spectrometer (XPS) or the like, it can be seen that Al: O = 1: 1.5 cannot be said. In general, when the amount of aluminum is less than Al: O = 1: 1.5 and the amount of aluminum is large, a good gas barrier property is obtained to form a dense film, but the deposited film is colored black, and the light transmission amount is high. Tend to be lower. On the other hand, when there is more oxygen than Al: O = 1: 2.0 and the amount of aluminum is small, a sparse film is formed, and a transparent film having a high light transmittance but a poor gas barrier property is obtained.
Silicon oxide is particularly preferred when water resistance is required.
　ガスバリア層３の厚さは、積層シート１０の用途や組成物（Ｉ）の層５の膜厚によっても異なるが、５～３００ｎｍであることが好ましく、１０～５０ｎｍがより好ましい。ガスバリア層３の厚さが前記範囲の下限値（５ｎｍ）未満であると、ガスバリア層３の連続性が損なわれるおそれがある。ガスバリア層３の厚さが前記範囲の上限値（３００ｎｍ）超であると、ガスバリア層３のフレキシビリティが低下し、成膜後に折り曲げ、引っ張りなどの外的要因により亀裂を生じるおそれがある。 The thickness of the gas barrier layer 3 varies depending on the use of the laminated sheet 10 and the film thickness of the layer 5 of the composition (I), but is preferably 5 to 300 nm, more preferably 10 to 50 nm. If the thickness of the gas barrier layer 3 is less than the lower limit (5 nm) of the above range, the continuity of the gas barrier layer 3 may be impaired. When the thickness of the gas barrier layer 3 exceeds the upper limit (300 nm) of the above range, the flexibility of the gas barrier layer 3 is lowered, and there is a possibility that cracking may occur due to external factors such as bending and pulling after film formation.
（組成物（Ｉ）の層）
　組成物（Ｉ）の層５は、組成物（Ｉ）から形成された層である。
　組成物（Ｉ）は、水酸基含有高分子化合物（Ａ）と、エポキシ基含有シランカップリング剤（Ｂ）と、前記エポキシ基含有シランカップリング剤（Ｂ）以外の他のケイ素化合物（Ｃ）とを含む。 (Layer of composition (I))
The layer 5 of the composition (I) is a layer formed from the composition (I).
The composition (I) comprises a hydroxyl group-containing polymer compound (A), an epoxy group-containing silane coupling agent (B), and another silicon compound (C) other than the epoxy group-containing silane coupling agent (B). including.
　水酸基含有高分子化合物（Ａ）としては、水酸基を有する高分子化合物であれば特に限定されない。
　水酸基含有高分子化合物（Ａ）としては、ガスバリア性の点から、ビニルアルコール系重合体が好ましい。ビニルアルコール系重合体とは、ビニルアルコール単位を含む重合体である。ビニルアルコール系重合体としては、ポリビニルアルコール（以下「ＰＶＡ」ともいう）、エチレン－ビニルアルコール共重合体、変性ビニルアルコール系重合体等が挙げられる。
　ビニルアルコール系重合体の重合度は、５００以上３０００以下であることが好ましく、１０００以上３０００以下がより好ましい。 The hydroxyl group-containing polymer compound (A) is not particularly limited as long as it is a polymer compound having a hydroxyl group.
The hydroxyl group-containing polymer compound (A) is preferably a vinyl alcohol polymer from the viewpoint of gas barrier properties. A vinyl alcohol polymer is a polymer containing vinyl alcohol units. Examples of the vinyl alcohol polymer include polyvinyl alcohol (hereinafter also referred to as “PVA”), an ethylene-vinyl alcohol copolymer, a modified vinyl alcohol polymer, and the like.
The degree of polymerization of the vinyl alcohol polymer is preferably 500 or more and 3000 or less, and more preferably 1000 or more and 3000 or less.
　ビニルアルコール系重合体の中でも特に、ＰＶＡが好ましい。高分子化合物（Ａ）がＰＶＡであると、ガスバリア性が特に優れる。
　ここで、ＰＶＡとは、一般にポリ酢酸ビニルをケン化して得られる材料である。ＰＶＡとしては、酢酸基が数％しか残存していない完全ケン化ＰＶＡでもよく、それよりも酢酸基の残存量が多い部分ケン化ＰＶＡでもよい。ケン化度が高い場合、組成物（Ｉ）の層５の耐水性が高いため好ましく、完全ケン化ＰＶＡが特に好ましい。
　ＰＶＡの重合度は３００～数千まで多種あり、どの重合度のＰＶＡを用いてもよいが、重合度が高いＰＶＡは耐水性が高いため好ましい。ＰＶＡの重合度は、５００以上３０００以下であることが好ましく、１０００以上３０００以下であることがより好ましい。 Among vinyl alcohol polymers, PVA is particularly preferable. When the polymer compound (A) is PVA, the gas barrier property is particularly excellent.
Here, PVA is a material generally obtained by saponifying polyvinyl acetate. The PVA may be completely saponified PVA in which only a few percent of acetate groups remain, or may be partially saponified PVA in which the remaining amount of acetate groups is larger than that. When the degree of saponification is high, it is preferable because the water resistance of the layer 5 of the composition (I) is high, and completely saponified PVA is particularly preferable.
There are various degrees of polymerization of PVA ranging from 300 to several thousand. PVA having any degree of polymerization may be used, but PVA having a high degree of polymerization is preferred because of its high water resistance. The degree of polymerization of PVA is preferably 500 or more and 3000 or less, and more preferably 1000 or more and 3000 or less.
　エポキシ基含有シランカップリング剤（Ｂ）としては、エポキシ基を有するシランカップリング剤であれば特に限定されず、例えば下記式（ｂ１）で表される化合物およびその加水分解物からなる群から選ばれる少なくとも１種の化合物（Ｂ１）、下記式（ｂ２）で表される化合物およびその加水分解物からなる群から選ばれる少なくとも１種の化合物（Ｂ２）等が挙げられる。これらの中でも化合物（Ｂ１）が好ましい。
　Ｒ３Ｓｉ（ＯＲ２）３　・・・（ｂ１）
　Ｒ３ＳｉＲ４（ＯＲ２）２　・・・（ｂ２）
（式中、Ｒ２は炭素数１～４のアルキル基または炭素数１～４のアルコキシアルキル基であり、式中の３つのＲ２は同じであっても異なっていてもよい。Ｒ３はエポキシ基を含む有機基であり、Ｒ４は炭素数１～５のアルキル基である。） The epoxy group-containing silane coupling agent (B) is not particularly limited as long as it is an silane coupling agent having an epoxy group, and is selected from the group consisting of a compound represented by the following formula (b1) and a hydrolyzate thereof, for example. And at least one compound (B2) selected from the group consisting of a compound represented by the following formula (b2) and a hydrolyzate thereof. Among these, the compound (B1) is preferable.
R 3 Si (OR 2 ) 3 (b1)
R 3 SiR 4 (OR 2 ) 2 (b2)
(In the formula, R 2 is an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl group having 1 to 4 carbon atoms, and three R 2 in the formula may be the same or different. R 3 is (It is an organic group containing an epoxy group, and R 4 is an alkyl group having 1 to 5 carbon atoms.)
　式（ｂ１）、（ｂ２）において、Ｒ２は、ＣＨ３、Ｃ２Ｈ５、またはＣ２Ｈ４ＯＣＨ３であることが好ましい。
　Ｒ３としては、例えば２－（３，４－エポキシシクロヘキシル）エチル基、３－グリシドキシプロピル基等が挙げられる。
　前記式（ｂ１）で表される化合物の具体例としては、２－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルトリエトキシシラン等が挙げられる。前記式（ｂ２）で表される化合物の具体例としては、３－グリシドキシプロピルメチルジメトキシシラン、３－グリシドキシプロピルエチルジエトキシシラン等が挙げられる。これらはいずれか１種を単独で又は２種以上組み合わせて使用できる。これらの中でも、柔軟性と耐熱湿性とを両立する観点で、３－グリシドキシプロピルトリメトキシシラン、３－グリシドキシプロピルトリエトキシシランが好ましく、３－グリシドキシプロピルトリメトキシシランがより好ましい。 In the formulas (b1) and (b2), R 2 is preferably CH 3 , C 2 H 5 , or C 2 H 4 OCH 3 .
Examples of R 3 include 2- (3,4-epoxycyclohexyl) ethyl group and 3-glycidoxypropyl group.
Specific examples of the compound represented by the formula (b1) include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropyltriethoxysilane. Etc. Specific examples of the compound represented by the formula (b2) include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethyldiethoxysilane, and the like. These can be used alone or in combination of two or more. Among these, 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane are preferable, and 3-glycidoxypropyltrimethoxysilane is more preferable from the viewpoint of achieving both flexibility and heat and humidity resistance. .
　式（ｂ１）または（ｂ２）で表される化合物を加水分解すると、ＯＲ２がＯＨとなる。
　式（ｂ１）または（ｂ２）で表される化合物の加水分解物は、公知の方法により得ることができる。式（ｂ１）または（ｂ２）で表される化合物の加水分解は、典型的には、酸またはアルカリ触媒とアルコールと水とを用いて行われる。加水分解が制御しやすい点では、酸触媒を用いることが好ましい。このとき、加水分解をさらに制御するために、一般的に知られている触媒等を添加してもよい。 When the compound represented by formula (b1) or (b2) is hydrolyzed, OR 2 becomes OH.
The hydrolyzate of the compound represented by the formula (b1) or (b2) can be obtained by a known method. The hydrolysis of the compound represented by the formula (b1) or (b2) is typically performed using an acid or alkali catalyst, alcohol and water. In view of easy control of hydrolysis, it is preferable to use an acid catalyst. At this time, in order to further control the hydrolysis, a generally known catalyst or the like may be added.
　ケイ素化合物（Ｃ）としては、例えば、下記式（ｃ１）で表される化合物およびその加水分解物からなる群から選ばれる少なくとも１種の化合物（Ｃ１）が挙げられる。
　Ｓｉ（ＯＲ１）４　・・・（ｃ１）
（式中、Ｒ１は炭素数１～４のアルキル基または炭素数１～４のアルコキシアルキル基であり、式中の４つのＲ１は同じであっても異なっていてもよい。） Examples of the silicon compound (C) include at least one compound (C1) selected from the group consisting of a compound represented by the following formula (c1) and a hydrolyzate thereof.
Si (OR 1 ) 4 (c1)
(In the formula, R 1 is an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl group having 1 to 4 carbon atoms, and four R 1 in the formula may be the same or different.)
　式（ｃ１）において、Ｒ１は、ＣＨ３、Ｃ２Ｈ５、またはＣ２Ｈ４ＯＣＨ３であることが好ましい。式（ｃ１）で表される化合物は１種を単独で又は２種以上組み合わせて使用できる。
　式（ｃ１）で表される化合物を加水分解すると、ＯＲ１がＯＨとなる。
　式（ｃ１）で表される化合物の加水分解物は、公知の方法により得ることができる。式（ｃ１）で表される化合物の加水分解は、典型的には、酸またはアルカリ触媒とアルコールと水とを用いて行われる。加水分解が制御しやすい点では、酸触媒を用いることが好ましい。このとき、加水分解をさらに制御するために、一般的に知られている触媒等を添加してもよい。 In the formula (c1), R 1 is preferably CH 3 , C 2 H 5 , or C 2 H 4 OCH 3 . The compounds represented by the formula (c1) can be used alone or in combination of two or more.
When the compound represented by the formula (c1) is hydrolyzed, OR 1 becomes OH.
The hydrolyzate of the compound represented by the formula (c1) can be obtained by a known method. The hydrolysis of the compound represented by the formula (c1) is typically performed using an acid or alkali catalyst, alcohol and water. In view of easy control of hydrolysis, it is preferable to use an acid catalyst. At this time, in order to further control the hydrolysis, a generally known catalyst or the like may be added.
　組成物（Ｉ）は、必要に応じて、ガスバリア性や耐熱湿性を損なわない範囲で、水酸基含有高分子化合物（Ａ）、エポキシ基含有シランカップリング剤（Ｂ）、およびケイ素化合物（Ｃ）以外の他の成分をさらに含んでもよい。
　他の成分としては、例えば、可塑剤、樹脂、分散剤、界面活性剤、柔軟剤、安定剤、アンチブロッキング剤、膜形成剤、粘着剤、酸素吸収剤、粘度鉱物等の添加剤が挙げられる。 The composition (I) may be used in addition to the hydroxyl group-containing polymer compound (A), the epoxy group-containing silane coupling agent (B), and the silicon compound (C) as long as the gas barrier property and heat and humidity resistance are not impaired. Other components may be further included.
Examples of other components include additives such as plasticizers, resins, dispersants, surfactants, softeners, stabilizers, antiblocking agents, film forming agents, pressure-sensitive adhesives, oxygen absorbers, and viscosity minerals. .
　組成物（Ｉ）において、水酸基含有高分子化合物（Ａ）の含有量は、水酸基含有高分子化合物（Ａ）の質量と、エポキシ基含有シランカップリング剤（Ｂ）の質量と、ケイ素化合物（Ｃ）のＳｉＯ２換算量との合計質量に対し、２５～３０質量％であり、２７～３０質量％であることが好ましい。つまり、水酸基含有高分子化合物（Ａ）の質量と、エポキシ基含有シランカップリング剤（Ｂ）の質量およびケイ素化合物（Ｃ）のＳｉＯ２換算量の合計と、の質量比（（Ａ）／［（Ｂ）＋（Ｃ）］）が、２５／７５～３０／７０の範囲内であることが好ましい。水酸基含有高分子化合物（Ａ）の含有量が前記範囲の下限値（２５質量％）以上であると、組成物（Ｉ）の層５のガスバリア性が優れる。また、組成物（Ｉ）の層５の柔軟性にも優れ、積層シート１０に折り曲げ、延伸等の物理的刺激（***）を加えたときに、積層シート１０のガスバリア性が損なわれにくい。水酸基含有高分子化合物（Ａ）の含有量が前記範囲の上限値（３０質量％）以下であると、組成物（Ｉ）の層５の耐熱湿性が優れ、高温高湿条件下でもガスバリア性が劣化しにくい。
　ケイ素化合物（Ｃ）のＳｉＯ２換算量とは、ケイ素化合物（Ｃ）に含まれるケイ素原子が全てＳｉＯ２になったと仮定した場合のＳｉＯ２の質量であり、ケイ素化合物（Ｃ）が有するケイ素原子の量から算出される。 In the composition (I), the content of the hydroxyl group-containing polymer compound (A) includes the mass of the hydroxyl group-containing polymer compound (A), the mass of the epoxy group-containing silane coupling agent (B), and the silicon compound (C). ) With respect to the total mass of SiO 2 equivalent to 25 to 30% by mass, preferably 27 to 30% by mass. That is, the mass ratio of the mass of the hydroxyl group-containing polymer compound (A) to the total mass of the epoxy group-containing silane coupling agent (B) and the silicon compound (C) in terms of SiO 2 ((A) / [ (B) + (C)]) is preferably in the range of 25/75 to 30/70. When the content of the hydroxyl group-containing polymer compound (A) is not less than the lower limit (25% by mass) of the above range, the gas barrier property of the layer 5 of the composition (I) is excellent. Moreover, it is excellent also in the softness | flexibility of the layer 5 of a composition (I), and when a physical stimulus (abuse), such as bending and extending | stretching, is added to the lamination sheet 10, the gas barrier property of the lamination sheet 10 is hard to be impaired. When the content of the hydroxyl group-containing polymer compound (A) is not more than the upper limit (30% by mass) of the above range, the heat and moisture resistance of the layer 5 of the composition (I) is excellent, and the gas barrier property is high even under high temperature and high humidity conditions. Hard to deteriorate.
The SiO 2 equivalent amount of the silicon compound (C), all the silicon atoms contained in the silicon compound (C) is a SiO 2 mass assuming that became SiO 2, silicon atoms having a silicon compound (C) It is calculated from the quantity.
　エポキシ基含有シランカップリング剤（Ｂ）の含有量は、水酸基含有高分子化合物（Ａ）の質量と、エポキシ基含有シランカップリング剤（Ｂ）の質量と、ケイ素化合物（Ｃ）のＳｉＯ２換算量との合計質量に対し、５～３０質量％であることが好ましく、５～２５質量％であることがより好ましく、１０～２０質量％であることがさらに好ましい。エポキシ基含有シランカップリング剤（Ｂ）の含有量が前記範囲内であると、組成物（Ｉ）の層５の柔軟性を損なわずに耐熱湿性を高めることができる。エポキシ基含有シランカップリング剤（Ｂ）の含有量が前記範囲の下限値（５質量％）未満であると、耐熱湿性が不十分になるおそれがあり、前記範囲の上限値（３０質量％）超であると、組成物（Ｉ）の層５の柔軟性が低下したり、エポキシ基含有シランカップリング剤（Ｂ）が有する官能基が孔となってガスバリア性が低下したりするおそれがある。
　エポキシ基含有シランカップリング剤（Ｂ）として、式（ｂ１）または（ｂ２）で表される化合物の加水分解物を用いる場合、エポキシ基含有シランカップリング剤（Ｂ）の含有量は、加水分解前の化合物の質量に基づいて算出される。また、ケイ素化合物（Ｃ）として、式（ｃ１）で表される化合物の加水分解物を用いる場合、ケイ素化合物（Ｃ）のＳｉＯ２換算量は、加水分解前の化合物の質量に基づいて算出される。 The content of the epoxy group-containing silane coupling agent (B) is the mass of the hydroxyl group-containing polymer compound (A), the mass of the epoxy group-containing silane coupling agent (B), and the silicon compound (C) in terms of SiO 2. The total mass with respect to the amount is preferably 5 to 30% by mass, more preferably 5 to 25% by mass, and still more preferably 10 to 20% by mass. When the content of the epoxy group-containing silane coupling agent (B) is within the above range, the heat and humidity resistance can be improved without impairing the flexibility of the layer 5 of the composition (I). If the content of the epoxy group-containing silane coupling agent (B) is less than the lower limit (5% by mass) of the above range, the heat and humidity resistance may be insufficient, and the upper limit (30% by mass) of the above range. If it is too high, the flexibility of the layer 5 of the composition (I) may be reduced, or the functional group of the epoxy group-containing silane coupling agent (B) may become pores and gas barrier properties may be reduced. .
When the hydrolyzate of the compound represented by the formula (b1) or (b2) is used as the epoxy group-containing silane coupling agent (B), the content of the epoxy group-containing silane coupling agent (B) is hydrolyzed. Calculated based on the mass of the previous compound. Further, as the silicon compound (C), when using a hydrolyzate of the compound represented by formula (c1), SiO 2 equivalent amount of the silicon compound (C) is calculated based on the weight of the unhydrolyzed compounds The
　組成物（Ｉ）中、水酸基含有高分子化合物（Ａ）の質量と、エポキシ基含有シランカップリング剤（Ｂ）の質量と、ケイ素化合物（Ｃ）のＳｉＯ２換算量との合計質量は、全固形分の質量に対し、７０質量％以上が好ましく、９０質量％以上がより好ましい。該含有量の上限は特に限定されず、１００質量％であってもよい。 In the composition (I), the total mass of the hydroxyl group-containing polymer compound (A), the epoxy group-containing silane coupling agent (B), and the silicon compound (C) in terms of SiO 2 is the total mass. 70 mass% or more is preferable with respect to the mass of solid content, and 90 mass% or more is more preferable. The upper limit of this content is not specifically limited, 100 mass% may be sufficient.
　組成物（Ｉ）の層５の厚さは、積層シート１０の用途によっても異なるが、５～３００ｎｍであることが好ましく、１０～５０ｎｍがより好ましい。
　組成物（Ｉ）の層５の厚さが前記下限値（５ｎｍ）以上であると、耐熱湿性に優れる。前記上限値（３００ｎｍ）以下であると、柔軟性に優れる。 The thickness of the layer 5 of the composition (I) varies depending on the use of the laminated sheet 10, but is preferably 5 to 300 nm, more preferably 10 to 50 nm.
When the thickness of the layer 5 of the composition (I) is not less than the lower limit (5 nm), the heat and humidity resistance is excellent. It is excellent in a softness | flexibility as it is below the said upper limit (300 nm).
（積層シートの製造方法）
　積層シート１０は、例えば、以下の（α１）および（α２）の工程を含む製造方法により製造できる。
　（α１）：基材１の一方の面上に、無機材料から構成されるガスバリア層３を形成する工程。
　（α２）：基材１のガスバリア層３が形成された側の面に、水酸基含有高分子化合物（Ａ）と、エポキシ基含有シランカップリング剤（Ｂ）と、ケイ素化合物（Ｃ）と、溶媒とを含むコーティング液（ａ）を塗工して前記コーティング剤（ａ）から構成される塗膜を形成し、前記塗膜を乾燥して組成物（Ｉ）の層５を形成する工程。 (Laminated sheet manufacturing method)
The laminated sheet 10 can be manufactured, for example, by a manufacturing method including the following steps (α1) and (α2).
(Α1): A step of forming the gas barrier layer 3 made of an inorganic material on one surface of the substrate 1.
(Α2): A hydroxyl group-containing polymer compound (A), an epoxy group-containing silane coupling agent (B), a silicon compound (C), and a solvent on the surface of the substrate 1 on which the gas barrier layer 3 is formed. The coating liquid (a) containing is formed, the coating film comprised from the said coating agent (a) is formed, the said coating film is dried, and the layer 5 of composition (I) is formed.
［工程（α１）］
　ガスバリア層３を形成する方法としては、公知の方法を用いることができる。例えばガスバリア層３が蒸着膜である場合、公知の蒸着方法を用いることができる。蒸着方法としては、例えば、真空蒸着法、スパッタリング法、イオンプレーティング法、化学気相成長法等が挙げられる。
　真空蒸着法による真空蒸着装置の加熱手段としては、電子線加熱方式、抵抗加熱方式、誘導加熱方式等が好ましい。蒸着膜の基材１への密着性および蒸着膜の緻密性を向上させるために、プラズマアシスト法やイオンビームアシスト法を用いることも可能である。また、蒸着膜の透明性を上げるために、蒸着の際、酸素ガス等を吹き込んだりする反応蒸着を行ってもよい。 [Step (α1)]
As a method for forming the gas barrier layer 3, a known method can be used. For example, when the gas barrier layer 3 is a vapor deposition film, a known vapor deposition method can be used. Examples of the vapor deposition method include a vacuum vapor deposition method, a sputtering method, an ion plating method, a chemical vapor deposition method, and the like.
As a heating means of the vacuum deposition apparatus by the vacuum deposition method, an electron beam heating method, a resistance heating method, an induction heating method, or the like is preferable. In order to improve the adhesion of the deposited film to the substrate 1 and the denseness of the deposited film, it is possible to use a plasma assist method or an ion beam assist method. In order to increase the transparency of the deposited film, reactive vapor deposition may be performed by blowing oxygen gas or the like at the time of vapor deposition.
［工程（α２）］
　コーティング液（ａ）は、溶媒を含むこと以外は、組成物（Ｉ）と同様である。
　コーティング液（ａ）の溶媒としては、水、または、水と有機溶媒との混合溶媒が好ましく、水と炭素数１～５の低級アルコールとの混合溶媒がより好ましい。 [Step (α2)]
The coating liquid (a) is the same as the composition (I) except that it contains a solvent.
As the solvent of the coating liquid (a), water or a mixed solvent of water and an organic solvent is preferable, and a mixed solvent of water and a lower alcohol having 1 to 5 carbon atoms is more preferable.
　コーティング液（ａ）の塗工方法としては、特に限定は無く、例えばキャスト法、ディッピング法、ロールコーティング法、グラビアコート法、スクリーン印刷法、リバースコート法、スプレーコート法、キットコート法、ダイコート法、メタリングバーコート法、チャンバードクター併用コート法、カーテンコート法等が挙げられる。 The coating method of the coating liquid (a) is not particularly limited. For example, casting method, dipping method, roll coating method, gravure coating method, screen printing method, reverse coating method, spray coating method, kit coating method, die coating method. , Metal ring bar coating method, chamber doctor combined coating method, curtain coating method and the like.
　塗膜の乾燥方法としては、特に限定は無く、例えば熱風乾燥法、熱ロール接触法、赤外線加熱法、マイクロ波加熱法等の方法が挙げられる。乾燥は、これらの方法のいずれかを単独または組み合わせて行ってもよい。乾燥温度としては特に限定は無いが、溶媒として上述した水や、水と有機溶媒との混合溶媒を用いる場合には、通常、５０～１６０℃が好ましい。また、乾燥の際の圧力は、通常は常圧または減圧下で行うことが好ましく、設備の簡便性の観点から常圧で行うことが好ましい。 The method for drying the coating film is not particularly limited, and examples thereof include a hot air drying method, a hot roll contact method, an infrared heating method, and a microwave heating method. Drying may be performed by any one of these methods alone or in combination. The drying temperature is not particularly limited, but when the above-mentioned water or a mixed solvent of water and an organic solvent is used as a solvent, it is usually preferably 50 to 160 ° C. In addition, the pressure during drying is usually preferably normal pressure or reduced pressure, and is preferably normal pressure from the viewpoint of facility simplicity.
　なお、組成物（Ｉ）の層５を２層以上積層する場合（例えば基材１の両面上に積層する場合）、各層を形成するためのコーティング液（ａ）の塗工および乾燥は、連続的に行ってもよく、巻取り工程や養生工程を経て、不連続的に行ってもよい。 In addition, when laminating | stacking two or more layers 5 of the composition (I) (for example, laminating | stacking on both surfaces of the base material 1), coating and drying of the coating liquid (a) for forming each layer are continuous. It may be performed continuously, or may be performed discontinuously through a winding process and a curing process.
（作用効果）
　積層シート１０は、基材１上に無機材料から形成されたガスバリア層３および組成物（Ｉ）の層５を備えるため、酸素バリア性、水蒸気バリア性等のガスバリア性に優れる。
　また、組成物（Ｉ）の層５は、柔軟性に優れる。そのため、積層シート１０の耐***性が高く、折り曲げ、延伸といった***後もガスバリア性が劣化しにくい。
　また、組成物（Ｉ）の層５は、耐熱湿性に優れる。そのため高温高湿下でも高いレベルでガスバリア性を発揮することができる。また、ボイル処理、レトルト処理等の熱水処理後においても高いレベルでガスバリア性を維持することができる。 (Function and effect)
Since the laminated sheet 10 includes the gas barrier layer 3 formed of an inorganic material and the layer 5 of the composition (I) on the substrate 1, the laminated sheet 10 is excellent in gas barrier properties such as oxygen barrier properties and water vapor barrier properties.
Further, the layer 5 of the composition (I) is excellent in flexibility. Therefore, the abuse resistance of the laminated sheet 10 is high, and the gas barrier property is not easily deteriorated even after abuse such as bending and stretching.
The layer 5 of the composition (I) is excellent in heat and humidity resistance. Therefore, the gas barrier property can be exhibited at a high level even under high temperature and high humidity. Further, the gas barrier property can be maintained at a high level even after hot water treatment such as boil treatment and retort treatment.
＜第二実施形態＞
　図２は、本発明の第二実施形態に係る積層シート２０を模式的に示す断面図である。なお、以下に示す実施形態において、前出の第一実施形態に対応する構成要素には同一の符号を付してその詳細な説明を省略する。
　積層シート２０は、基材１と、無機材料から形成されたガスバリア層３と、組成物（Ｉ）の層５と、以下の組成物（ＩＩ）から形成された層（以下「組成物（ＩＩ）の層」ともいう）７とを備える。組成物（ＩＩ）の層７は、ガスバリア層３と組成物（Ｉ）の層５との間に設けられている。
　組成物（ＩＩ）：水酸基含有高分子化合物（Ａ）と、エポキシ基含有シランカップリング剤（Ｂ）以外の他のケイ素化合物（Ｃ）とを含み、エポキシ基含有シランカップリング剤（Ｂ）を含まない組成物。なお、組成物（ＩＩ）はエポキシ基含有シランカップリング剤（Ｂ）を、水酸基含有高分子化合物（Ａ）の質量と、エポキシ基含有シランカップリング剤（Ｂ）の質量と、ケイ素化合物（Ｃ）のＳｉＯ２換算量との合計質量に対し、５質量％未満含んでいてもよい。
　積層シート２０は、組成物（ＩＩ）の層７をさらに備えること以外は第一実施形態と同様である。 <Second embodiment>
FIG. 2 is a cross-sectional view schematically showing a laminated sheet 20 according to the second embodiment of the present invention. In the embodiment described below, the same reference numerals are given to the components corresponding to the first embodiment, and the detailed description thereof is omitted.
The laminated sheet 20 includes a substrate 1, a gas barrier layer 3 formed of an inorganic material, a layer 5 of the composition (I), and a layer formed of the following composition (II) (hereinafter referred to as “composition (II). )) And 7). The layer 7 of the composition (II) is provided between the gas barrier layer 3 and the layer 5 of the composition (I).
Composition (II): A hydroxyl group-containing polymer compound (A) and a silicon compound (C) other than the epoxy group-containing silane coupling agent (B), and the epoxy group-containing silane coupling agent (B) No composition. The composition (II) comprises an epoxy group-containing silane coupling agent (B), a mass of the hydroxyl group-containing polymer compound (A), a mass of the epoxy group-containing silane coupling agent (B), and a silicon compound (C ) Less than 5% by mass with respect to the total mass with the SiO 2 equivalent.
The laminated sheet 20 is the same as that of the first embodiment except that the laminated sheet 20 further includes a layer 7 of the composition (II).
（組成物（ＩＩ）の層）
　組成物（ＩＩ）における水酸基含有高分子化合物（Ａ）、ケイ素化合物（Ｃ）はそれぞれ組成物（Ｉ）で挙げたものと同様であり、好ましい態様も同様である。
　組成物（ＩＩ）は、必要に応じて、水酸基含有高分子化合物（Ａ）、エポキシ基含有シランカップリング剤（Ｂ）およびケイ素化合物（Ｃ）以外の他の成分をさらに含んでもよい。他の成分としては、組成物（Ｉ）で挙げたものと同様のものが挙げられる。 (Layer of composition (II))
The hydroxyl group-containing polymer compound (A) and the silicon compound (C) in the composition (II) are the same as those described for the composition (I), and the preferred embodiments are also the same.
The composition (II) may further contain other components other than the hydroxyl group-containing polymer compound (A), the epoxy group-containing silane coupling agent (B), and the silicon compound (C) as necessary. Examples of the other components include the same as those mentioned for the composition (I).
　組成物（ＩＩ）において、水酸基含有高分子化合物（Ａ）の含有量は、水酸基含有高分子化合物（Ａ）とケイ素化合物（Ｃ）のＳｉＯ２換算量との合計に対し、２５～３０質量％であることが好ましく、２７～３０質量％であることがより好ましい。水酸基含有高分子化合物（Ａ）の含有量が前記範囲の下限値以上であると、組成物（ＩＩ）の層７のガスバリア性、柔軟性がより優れる。水酸基含有高分子化合物（Ａ）の含有量が前記範囲の上限値以下であると、組成物（ＩＩ）の層７の耐熱湿性がより優れる。 In the composition (II), the content of the hydroxyl group-containing polymer compound (A) is 25 to 30% by mass with respect to the total of the hydroxyl group-containing polymer compound (A) and the silicon compound (C) in terms of SiO 2. Preferably, the content is 27 to 30% by mass. When the content of the hydroxyl group-containing polymer compound (A) is not less than the lower limit of the above range, the gas barrier property and flexibility of the layer 7 of the composition (II) are more excellent. When the content of the hydroxyl group-containing polymer compound (A) is not more than the upper limit of the above range, the heat and humidity resistance of the layer 7 of the composition (II) is more excellent.
　組成物（ＩＩ）が、エポキシ基含有シランカップリング剤（Ｂ）を含有する場合、その含有量は、水酸基含有高分子化合物（Ａ）の質量と、エポキシ基含有シランカップリング剤（Ｂ）の質量と、ケイ素化合物（Ｃ）のＳｉＯ２換算量との合計質量に対し、５質量％未満が好ましく、３質量％未満がより好ましい。
　エポキシ基含有シランカップリング剤（Ｂ）の含有量が前記範囲内であると、ガスバリア性がより優れる。 When the composition (II) contains the epoxy group-containing silane coupling agent (B), the content of the hydroxyl group-containing polymer compound (A) and the epoxy group-containing silane coupling agent (B) The total mass of the mass and the SiO 2 equivalent of the silicon compound (C) is preferably less than 5% by mass, and more preferably less than 3% by mass.
When the content of the epoxy group-containing silane coupling agent (B) is within the above range, the gas barrier property is more excellent.
　組成物（ＩＩ）中、水酸基含有高分子化合物（Ａ）の質量とケイ素化合物（Ｃ）のＳｉＯ２換算量との合計質量は、全固形分に対し、７０質量％以上が好ましく、９０質量％以上がより好ましい。該含有量の上限は特に限定されず、１００質量％であってもよい。 In the composition (II), the total mass of the hydroxyl group-containing polymer compound (A) and the silicon compound (C) in terms of SiO 2 is preferably 70% by mass or more, and 90% by mass with respect to the total solid content. The above is more preferable. The upper limit of this content is not specifically limited, 100 mass% may be sufficient.
　組成物（ＩＩ）の層７の厚さは、積層シート１０の用途によっても異なるが、５～３００ｎｍであることが好ましく、１０～５０ｎｍがより好ましい。
　組成物（ＩＩ）の層７の厚さが前記下限値（５ｎｍ）以上であると、***を行っていない状態でのガスバリア性により優れる。前記上限値（３００ｎｍ）以下であると、柔軟性に優れる。 The thickness of the layer 7 of the composition (II) varies depending on the use of the laminated sheet 10, but is preferably 5 to 300 nm, more preferably 10 to 50 nm.
When the thickness of the layer 7 of the composition (II) is not less than the lower limit (5 nm), the gas barrier property in a state where abuse is not performed is excellent. It is excellent in a softness | flexibility as it is below the said upper limit (300 nm).
（積層シートの製造方法）
　積層シート２０は、例えば、以下の（β１）、（β２）および（β３）の工程を含む製造方法により製造できる。
　（β１）：基材１の一方の面上に、無機材料から構成されるガスバリア層３を形成する工程。
　（β２）：基材１のガスバリア層３が形成された側の面に、水酸基含有高分子化合物（Ａ）と、ケイ素化合物（Ｃ）と、溶媒とを含み、エポキシ基含有シランカップリング剤（Ｂ）を含まないコーティング液（ｂ）を塗工して前記コーティング剤（ｂ）から構成される塗膜を形成し、前記塗膜を乾燥して組成物（ＩＩ）の層７を形成する工程。
　（β３）：基材１のガスバリア層３および組成物（ＩＩ）の層７が形成された側の面に、水酸基含有高分子化合物（Ａ）と、エポキシ基含有シランカップリング剤（Ｂ）と、ケイ素化合物（Ｃ）と、溶媒とを含むコーティング液（ａ）を塗工して前記コーティング剤（ａ）から構成される塗膜を形成し、前記塗膜を乾燥して組成物（Ｉ）の層５を形成する工程。 (Laminated sheet manufacturing method)
The laminated sheet 20 can be manufactured, for example, by a manufacturing method including the following steps (β1), (β2), and (β3).
(Β1): A step of forming the gas barrier layer 3 made of an inorganic material on one surface of the substrate 1.
(Β2): The surface of the substrate 1 on which the gas barrier layer 3 is formed contains a hydroxyl group-containing polymer compound (A), a silicon compound (C), and a solvent, and an epoxy group-containing silane coupling agent ( A step of applying the coating liquid (b) not containing B) to form a coating film composed of the coating agent (b) and drying the coating film to form the layer 7 of the composition (II) .
(Β3): The hydroxyl group-containing polymer compound (A), the epoxy group-containing silane coupling agent (B), and the surface of the substrate 1 on the side where the gas barrier layer 3 and the layer 7 of the composition (II) are formed The coating liquid (a) containing the silicon compound (C) and the solvent is applied to form a coating film composed of the coating agent (a), and the coating film is dried to obtain the composition (I) Forming the layer 5.
［工程（β１）］
　工程（β１）は、前記工程（α１）と同様にして行うことができる。 [Step (β1)]
The step (β1) can be performed in the same manner as the step (α1).
［工程（β２）］
　工程（β２）は、コーティング液（ａ）の代わりにコーティング液（ｂ）を用いること以外は前記工程（α２）と同様にして行うことができる。
　コーティング液（ｂ）は、溶媒を含むこと以外は、組成物（ＩＩ）と同様である。
　コーティング液（ｂ）の溶媒としては、水、または、水と有機溶媒との混合溶媒が好ましく、水と炭素数１～５の低級アルコールとの混合溶媒がより好ましい。 [Step (β2)]
The step (β2) can be performed in the same manner as the step (α2) except that the coating solution (b) is used instead of the coating solution (a).
The coating liquid (b) is the same as the composition (II) except that it contains a solvent.
As the solvent of the coating liquid (b), water or a mixed solvent of water and an organic solvent is preferable, and a mixed solvent of water and a lower alcohol having 1 to 5 carbon atoms is more preferable.
［工程（β３）］
　工程（β３）は、前記工程（α２）と同様にして行うことができる。 [Step (β3)]
The step (β3) can be performed in the same manner as the step (α2).
（作用効果）
　積層シート２０にあっては、基材１上に無機材料から形成されるガスバリア層３および組成物（Ｉ）の層５を備えるため、第一実施形態と同様に、ガスバリア性に優れる。また、組成物（Ｉ）の層５は柔軟性、耐熱湿性に優れる。また、組成物（ＩＩ）の層７をさらに備えることで、***を行っていない状態でのガスバリア性がより優れる傾向がある。 (Function and effect)
Since the laminated sheet 20 includes the gas barrier layer 3 formed of an inorganic material and the layer 5 of the composition (I) on the substrate 1, it has excellent gas barrier properties as in the first embodiment. The layer 5 of the composition (I) is excellent in flexibility and heat and humidity resistance. Moreover, by further providing the layer 7 of the composition (II), there is a tendency that gas barrier properties in a state where abuse is not performed are more excellent.
＜第三実施形態＞
　図３は、本発明の第三実施形態に係る積層シート３０を模式的に示す断面図である。
　積層シート３０は、基材（第一の基材）１と、無機材料から形成されるガスバリア層３と、組成物（Ｉ）の層５と、他の基材（第二の基材）９とを備える。他の基材９は、組成物（Ｉ）の層５の上に、接着層１１を介して積層されている。
　積層シート３０は、他の基材９および接着層１１をさらに備えること以外は第一実施形態と同様である。
　積層シート３０は、ガスバリア層３と組成物（Ｉ）の層５との間に、組成物（ＩＩ）の層７をさらに備えてもよい。この場合、積層シート３０は、他の基材９および接着層１１をさらに備えること以外は第二実施形態と同様である。 <Third embodiment>
FIG. 3 is a cross-sectional view schematically showing a laminated sheet 30 according to the third embodiment of the present invention.
The laminated sheet 30 includes a base material (first base material) 1, a gas barrier layer 3 formed from an inorganic material, a layer 5 of the composition (I), and another base material (second base material) 9. With. The other base material 9 is laminated on the layer 5 of the composition (I) via an adhesive layer 11.
The laminated sheet 30 is the same as that of the first embodiment except that the laminated sheet 30 further includes another base material 9 and an adhesive layer 11.
The laminated sheet 30 may further include a layer 7 of the composition (II) between the gas barrier layer 3 and the layer 5 of the composition (I). In this case, the laminated sheet 30 is the same as that of the second embodiment except that the laminated sheet 30 further includes another base material 9 and an adhesive layer 11.
（他の基材）
　他の基材９は、強度付与、シール性やシール時の易開封性付与、意匠性付与、光遮断性付与等の目的で積層されている。
　他の基材９としては、目的に応じて適宜選択され、特に限定されないが、通常はプラスチックフィルム類や紙類が好ましい。プラスチックフィルム類や紙類は、１種を単独で用いても、２種以上を積層して用いてもよい。例えばプラスチックフィルム類と紙とを積層して用いてもよく、２種以上のプラスチックフィルム類を積層して用いてもよい。 (Other base materials)
The other base material 9 is laminated | stacked for the objectives, such as intensity | strength provision, sealing performance, easy opening provision at the time of sealing, design provision, and light-blocking provision.
The other base material 9 is appropriately selected depending on the purpose and is not particularly limited, but plastic films and papers are usually preferable. Plastic films and papers may be used alone or in combination of two or more. For example, plastic films and paper may be laminated and used, or two or more kinds of plastic films may be laminated and used.
　積層シート３０が、後述する縦製袋充填シール袋、真空包装袋、スパウト付パウチ、ラミネートチューブ容器、輸液バッグ、容器用蓋材、紙容器、真空断熱体等の成形品に用いられる場合、積層シート３０の最表層に、他の基材９として、ヒートシール可能な層が配置されることが好ましい。これにより、積層シート３０がヒートシール性を有する構成となり、成形品への加工が容易となる。
　ヒートシール可能な層としては、ポリオレフィン層が好ましい。ポリオレフィンとしては、ヒートシールに適した構成であれば特に限定されるものではなく、例えば、低密度ポリエチレン（ＬＤＰＥ）、無延伸ポリプロピレン（ＣＰＰ）等が挙げられる。
　ヒートシール可能な層の厚さは、特に限定されるものではないが、典型的には５～３００μｍの範囲内、好ましくは１０～１００μｍの範囲内で適宜設定することができる。 When the laminated sheet 30 is used in a molded product such as a vertical bag-filling sealing bag, a vacuum packaging bag, a pouch with a spout, a laminated tube container, an infusion bag, a container lid, a paper container, a vacuum insulator, etc. It is preferable that a heat-sealable layer is disposed as the other base material 9 on the outermost layer of the sheet 30. Thereby, the lamination sheet 30 becomes a structure which has heat-sealing property, and the process to a molded article becomes easy.
A polyolefin layer is preferred as the heat-sealable layer. The polyolefin is not particularly limited as long as it is a structure suitable for heat sealing, and examples thereof include low density polyethylene (LDPE) and unstretched polypropylene (CPP).
The thickness of the heat-sealable layer is not particularly limited, but typically can be appropriately set within a range of 5 to 300 μm, preferably within a range of 10 to 100 μm.
（接着層）
　接着層１１は、組成物（Ｉ）の層５と他の基材９とを接着する層である。
　接着層１１の材質としては、特に限定はなく、例えばドライラミネート法、ウェットラミネート法、押出しラミネート法等で用いられている公知の接着剤のなかから適宜選択できる。 (Adhesive layer)
The adhesive layer 11 is a layer that adheres the layer 5 of the composition (I) and another substrate 9.
The material of the adhesive layer 11 is not particularly limited, and can be appropriately selected from known adhesives used in, for example, a dry laminating method, a wet laminating method, and an extrusion laminating method.
（積層シートの製造方法）
　積層シート３０は、例えば、以下の（γ１）、（γ２）および（γ３）の工程を含む製造方法により製造できる。
　（γ１）：基材１の一方の面上に、無機材料から構成されるガスバリア層３を形成する工程。
　（γ２）：基材１のガスバリア層３が形成された側の面に、水酸基含有高分子化合物（Ａ）と、エポキシ基含有シランカップリング剤（Ｂ）と、ケイ素化合物（Ｃ）と、溶媒とを含むコーティング液（ａ）を塗工して前記コーティング剤（ａ）から構成される塗膜を形成し、前記塗膜を乾燥して組成物（Ｉ）の層５を形成する工程。
　（γ３）：基材１のガスバリア層３および組成物（Ｉ）の層５が形成された側の面に、接着層１１を介して他の基材９を積層する工程。 (Laminated sheet manufacturing method)
The laminated sheet 30 can be manufactured by, for example, a manufacturing method including the following steps (γ1), (γ2), and (γ3).
(Γ1): A step of forming the gas barrier layer 3 made of an inorganic material on one surface of the substrate 1.
(Γ2): A hydroxyl group-containing polymer compound (A), an epoxy group-containing silane coupling agent (B), a silicon compound (C), and a solvent on the surface of the substrate 1 on which the gas barrier layer 3 is formed. The coating liquid (a) containing is formed, the coating film comprised from the said coating agent (a) is formed, the said coating film is dried, and the layer 5 of composition (I) is formed.
(Γ3): A step of laminating another base material 9 via the adhesive layer 11 on the surface of the base material 1 on which the gas barrier layer 3 and the layer 5 of the composition (I) are formed.
［工程（γ１）］
　工程（γ１）は、前記工程（α１）と同様にして行うことができる。 [Step (γ1)]
The step (γ1) can be performed in the same manner as the step (α1).
［工程（γ２）］
　工程（γ２）は、前記工程（α２）と同様にして行うことができる。 [Process (γ2)]
The step (γ2) can be performed in the same manner as the step (α2).
［工程（γ３）］
　他の基材９の積層方法としては、接着剤を用いてラミネート法により積層する方法が挙げられる。具体的なラミネート法としては、ドライラミネート法、ウェットラミネート法、押出しラミネート法等が挙げられる。 [Process (γ3)]
As another method for laminating the base material 9, a method of laminating by an laminating method using an adhesive may be mentioned. Specific examples of the laminating method include a dry laminating method, a wet laminating method, and an extrusion laminating method.
（作用効果）
　積層シート３０にあっては、基材１上に無機材料から形成されるガスバリア層３および組成物（Ｉ）の層５を備えるため、第一実施形態と同様に、ガスバリア性に優れる。また、組成物（Ｉ）の層５は柔軟性、耐熱湿性に優れる。また、他の基材９によって、強度、シール性やシール時の易開封性、意匠性、光遮断性等の特性を付与することができる。 (Function and effect)
Since the laminated sheet 30 includes the gas barrier layer 3 formed of an inorganic material and the layer 5 of the composition (I) on the substrate 1, it has excellent gas barrier properties as in the first embodiment. The layer 5 of the composition (I) is excellent in flexibility and heat and humidity resistance. Further, the other base material 9 can impart properties such as strength, sealing properties, easy-opening properties at the time of sealing, design properties, and light blocking properties.
　以上、実施形態を示して本発明を説明したが、本発明は上記実施形態に限定されるものではない。上記実施形態における各構成およびそれらの組み合わせ等は一例であり、本発明の趣旨を逸脱しない範囲内で、構成の付加、省略、置換、およびその他の変更が可能である。 Although the present invention has been described with the embodiment, the present invention is not limited to the above embodiment. Each configuration in the above embodiment, a combination thereof, and the like are examples, and the addition, omission, replacement, and other modifications of the configuration can be made without departing from the spirit of the present invention.
　本発明の積層シートは、無機材料から形成されるガスバリア層３を有さなくてもよい。ガスバリア性、特に水蒸気バリア性、組成物（Ｉ）の層５を設けることの有用性の点では、ガスバリア層３を有することが好ましい。
　第一～第三実施形態では、基材１の一方の面上にガスバリア層３、組成物（Ｉ）の層５がこの順に積層した例を示したが、各層の配置はこれに限定されない。例えばガスバリア層３および組成物（Ｉ）の層５をそれぞれ基材１の両面に設けてもよく、基材１の一方の面上にガスバリア層３を設け、他方の面上に組成物（Ｉ）の層５を設けてもよい。耐***性の点では、基材１と組成物（Ｉ）の層５との間にガスバリア層３が設けられていることが好ましい。
　第二実施形態における組成物（ＩＩ）の層７や第三実施形態における他の基材９を、基材１の両面に設けてもよい。 The laminated sheet of this invention does not need to have the gas barrier layer 3 formed from an inorganic material. In view of gas barrier properties, particularly water vapor barrier properties, and usefulness of providing the layer 5 of the composition (I), it is preferable to have the gas barrier layer 3.
In the first to third embodiments, an example in which the gas barrier layer 3 and the layer 5 of the composition (I) are laminated in this order on one surface of the substrate 1 is shown, but the arrangement of each layer is not limited to this. For example, the gas barrier layer 3 and the layer 5 of the composition (I) may be provided on both surfaces of the substrate 1, respectively, the gas barrier layer 3 is provided on one surface of the substrate 1, and the composition (I ) Layer 5 may be provided. In terms of abuse resistance, it is preferable that a gas barrier layer 3 is provided between the substrate 1 and the layer 5 of the composition (I).
The layer 7 of the composition (II) in the second embodiment and the other substrate 9 in the third embodiment may be provided on both surfaces of the substrate 1.
　本発明の積層シートは、基材１とガスバリア層３との間に、それらの密着性を高める目的で、アンカーコート層をさらに有していてもよい。
　アンカーコート層を構成する材料としては、例えばウレタン系樹脂、エポキシ系樹脂、アクリル系樹脂、ポリエステル系樹脂等が挙げられる。また、用途に応じてこれらに硬化剤、シランカップリング剤等、他の添加物が添加されていてもよい。特にアクリルポリオールとイソシアネート化合物、シランカップリング剤の組み合わせが好ましい。この組み合わせから構成されるアンカーコート層を用いると、基材と蒸着層の間に、安定した高い密着性を得ることができる。 The laminated sheet of the present invention may further have an anchor coat layer between the base material 1 and the gas barrier layer 3 for the purpose of improving their adhesion.
Examples of the material constituting the anchor coat layer include urethane resins, epoxy resins, acrylic resins, and polyester resins. Further, other additives such as a curing agent and a silane coupling agent may be added to these depending on the application. In particular, a combination of an acrylic polyol, an isocyanate compound, and a silane coupling agent is preferable. When an anchor coat layer composed of this combination is used, stable and high adhesion can be obtained between the substrate and the vapor deposition layer.
　アンカーコート層の厚さは、基材１の面上における厚みが均一になる範囲であれば特に限定されないが、０．０１～２μｍであることが好ましく、０．０５～０．５μｍがより好ましい。アンカーコート層の厚さが前記範囲の下限値（０．０１μｍ）以上であれば、アンカーコート層の厚さの均一性が高く、基材１に対するガスバリア層３の密着性がより優れる。アンカーコート層の厚さが前記範囲の上限値（２μｍ）以下であれば、アンカーコート層が十分なフレキシビリティを保持し、***等の外的要因による亀裂が生じにくい。 The thickness of the anchor coat layer is not particularly limited as long as the thickness on the surface of the substrate 1 is uniform, but is preferably 0.01 to 2 μm, more preferably 0.05 to 0.5 μm. . When the thickness of the anchor coat layer is not less than the lower limit (0.01 μm) of the above range, the uniformity of the thickness of the anchor coat layer is high and the adhesion of the gas barrier layer 3 to the substrate 1 is more excellent. If the thickness of the anchor coat layer is less than or equal to the upper limit (2 μm) of the above range, the anchor coat layer retains sufficient flexibility and does not easily crack due to external factors such as abuse.
　本発明の積層シートは、ガスバリア層３と組成物（Ｉ）の層５との間に、組成物（ＩＩ）の層７以外の他の層を、組成物（ＩＩ）の層７に代えて、又は組成物（ＩＩ）の層７とともに、さらに有していてもよい。また、本発明の積層シートは、組成物（Ｉ）の層５の上（基材１側とは反対側）に、他の基材９および接着層１１以外の他の層をさらに有していてもよい。
　他の層としては、例えば、意匠性付与、光遮断性付与、防湿性付与等の目的で、印刷層や蒸着層を設けることができる。 In the laminated sheet of the present invention, a layer other than the layer 7 of the composition (II) is replaced with the layer 7 of the composition (II) between the gas barrier layer 3 and the layer 5 of the composition (I). Or may be further included with the layer 7 of the composition (II). Further, the laminated sheet of the present invention further has other layers other than the other substrate 9 and the adhesive layer 11 on the layer 5 of the composition (I) (on the side opposite to the substrate 1 side). May be.
As other layers, for example, a printing layer or a vapor deposition layer can be provided for the purpose of providing design properties, providing light blocking properties, providing moisture resistance, and the like.
＜用途＞
　本発明の積層シートの用途としては、包装材料が好ましい。本発明の積層シートは、上記のように、高温高湿下でも高いガスバリア性を発揮でき、ボイル処理、レトルト処理等の熱水処理後においても高いレベルでガスバリア性を維持することができる。また、***後もガスバリア性が劣化しにくいため、本発明の積層シートを用いて印刷工程やドライラミネート、溶融押し出しラミネート、熱圧着ラミネートなどの後加工を行い、食品、医薬品等の包装分野に用いられる実用範囲の広い包装材料を提供することが可能である。
　ただし本発明の積層シートの用途はこれに限定されるものではなく、包装材料以外の用途に用いることができる。包装材料以外の用途としては、例えばＬＣＤ用基板フィルム、有機ＥＬ用基板フィルム、電子ペーパー用基板フィルム、電子デバイス用封止フィルム、ＰＤＰ用フィルム、ＬＥＤ用フィルム、ＩＣタグ用フィルム、太陽電池用バックシート、太陽電池用保護フィルムなどの電子デバイス関連フィルム、光通信用部材、電子機器用フレキシブルフィルム、燃料電池用隔膜、燃料電池用封止フィルム、各種機能性フィルムの基板フィルム等が挙げられる。 <Application>
As a use of the laminated sheet of the present invention, a packaging material is preferable. As described above, the laminated sheet of the present invention can exhibit high gas barrier properties even under high temperature and high humidity, and can maintain gas barrier properties at a high level even after hot water treatment such as boil treatment and retort treatment. In addition, since gas barrier properties are unlikely to deteriorate even after abuse, post-processing such as printing process, dry lamination, melt extrusion lamination, thermocompression lamination using the laminated sheet of the present invention is used in the packaging field of foods, pharmaceuticals, etc. It is possible to provide a packaging material with a wide practical range.
However, the use of the laminated sheet of the present invention is not limited to this, and can be used for uses other than packaging materials. Applications other than packaging materials include, for example, LCD substrate films, organic EL substrate films, electronic paper substrate films, electronic device sealing films, PDP films, LED films, IC tag films, solar cell bags Sheets, films related to electronic devices such as protective films for solar cells, optical communication members, flexible films for electronic devices, diaphragms for fuel cells, sealing films for fuel cells, substrate films for various functional films, and the like.
≪包装材料≫
　本発明に係る包装材料は、前述の本発明の積層シートを含む。
　本発明の包装材料は、本発明の積層シートのみから構成されていてもよく、本発明の積層シートと他の材料とを含む構成であってもよい。他の材料としては、例えば熱可塑性樹脂フィルム、紙等が挙げられる。 ≪Packaging materials≫
The packaging material according to the present invention includes the above-described laminated sheet of the present invention.
The packaging material of this invention may be comprised only from the lamination sheet of this invention, and the structure containing the lamination sheet of this invention and another material may be sufficient as it. Examples of other materials include a thermoplastic resin film and paper.
　本発明の包装材料が適用される用途に特に限定はなく、様々な物品の包装材料として用いることができる。
　本発明の積層シートがガスバリア性を有する場合、本実施形態の包装材料は、酸素、水蒸気等の影響により劣化しやすい物品の包装材料として好ましく用いられ、なかでも、食品用包装材料として好ましく用いられる。食品用包装材料以外にも、非食品用、例えば農薬や医薬などの薬品、医療用具、機械部品、精密材料等のための包装材料として好ましく用いることができる。 The use to which the packaging material of the present invention is applied is not particularly limited and can be used as a packaging material for various articles.
When the laminated sheet of the present invention has gas barrier properties, the packaging material of this embodiment is preferably used as a packaging material for articles that are easily deteriorated by the influence of oxygen, water vapor, etc., and in particular, is preferably used as a packaging material for food. . In addition to food packaging materials, they can be preferably used as packaging materials for non-food products, for example, chemicals such as agricultural chemicals and pharmaceuticals, medical tools, machine parts, precision materials, and the like.
　本発明の積層シートは耐熱湿性に優れており、熱水処理を施したときに、ガスバリア性や層間密着性が劣化しにくい。そのため、本発明の包装材料は、熱水処理用包装材料として有用である。
　熱水処理としては、例えばボイル処理、レトルト処理等が挙げられる。 The laminated sheet of the present invention is excellent in heat and humidity resistance, and when subjected to hot water treatment, the gas barrier property and interlayer adhesion are not easily deteriorated. Therefore, the packaging material of the present invention is useful as a packaging material for hot water treatment.
Examples of the hot water treatment include boil treatment and retort treatment.
　ボイル処理は、食品等を保存するため湿熱で殺菌する方法である。ボイル処理としては、内容物にもよるが、食品等を包装した包装材料を６０～１００℃、大気圧下で、１０～１２０分の条件で殺菌処理を行う方法が挙げられる。
　ボイル処理は、熱水槽を用いて行うことが好ましく、一定温度の熱水槽の中に浸漬し、一定時間後に取り出すバッチ式と、熱水槽の中をトンネル式に通して殺菌する連続式がある。 The boil treatment is a method of sterilizing with wet heat to preserve foods and the like. Examples of the boil treatment include a method of sterilizing a packaging material in which foods and the like are packaged at 60 to 100 ° C. and atmospheric pressure for 10 to 120 minutes, depending on the contents.
The boil treatment is preferably carried out using a hot water tank, and there are a batch type in which it is immersed in a hot water tank at a constant temperature and taken out after a fixed time, and a continuous type in which the hot water tank is sterilized through a tunnel type.
　レトルト処理は、一般に食品等を保存するために、カビ、酵母、細菌などの微生物を加圧殺菌する方法である。レトルト処理としては、食品等を包装した包装材料を、１０５～１４０℃、０．１５～０．３ＭＰａで、１０～１２０分の条件で加圧殺菌処理する方法が挙げられる。
　レトルト処理に用いられるレトルト装置には、加熱蒸気を利用する蒸気式、加圧過熱水を利用する熱水式等があり、内容物となる食品等の殺菌条件に応じて適宜使い分けられる。 In general, retort treatment is a method of sterilizing microorganisms such as molds, yeasts, and bacteria in order to preserve foods and the like. Examples of the retort treatment include a method in which a packaging material in which food or the like is packaged is subjected to a pressure sterilization treatment at 105 to 140 ° C. and 0.15 to 0.3 MPa for 10 to 120 minutes.
The retort apparatus used for the retort treatment includes a steam type using heated steam, a hot water type using pressurized superheated water, and the like, which are properly used depending on the sterilization conditions of food or the like as the contents.
　熱水処理用包装材料で包装される内容物としては、特に限定されず、食品でも非食品でもよい。食品としては、例えばカレーや料理用調味ソース、食肉の加工品等が挙げられる。非食品としては、例えば輸液製剤等の医療品、半導体、精密材料等の産業品等が挙げられる。 The contents to be packaged with the hot water packaging material are not particularly limited, and may be food or non-food. Examples of the food include curry, cooking seasoning sauce, and processed meat products. Examples of non-food include medical products such as infusion preparations, and industrial products such as semiconductors and precision materials.
≪成形体≫
　本発明に係る成形品は、前述の本発明の包装材料を備える。
　成形品としては、例えば、容器、容器の一部を構成する部材等が挙げられ、具体例としては、縦製袋充填シール袋、真空包装袋、スパウト付パウチ、ラミネートチューブ容器、輸液バッグ、容器用蓋材、紙容器、真空断熱体等が挙げられる。 ≪Molded body≫
The molded product according to the present invention includes the packaging material of the present invention described above.
Examples of the molded article include a container, a member constituting a part of the container, and the like, and specific examples include a vertical bag filling and sealing bag, a vacuum packaging bag, a pouch with a spout, a laminate tube container, an infusion bag, and a container. Examples thereof include lid materials, paper containers, and vacuum insulators.
　本発明の成形品は、公知の方法により製造できる。例えば縦製袋充填シール袋、真空包装袋、スパウト付パウチ、ラミネートチューブ容器、輸液バッグ、容器用蓋材、紙容器、真空断熱体等の製造においては、通常、包装材料のヒートシールが行われる。そのため、これらの成形品を構成する包装材料としては、通常、一方または両方の最外層にヒートシール可能な層が配置されているものが好ましい。 The molded product of the present invention can be manufactured by a known method. For example, in the manufacture of vertical bag filling and sealing bags, vacuum packaging bags, spout pouches, laminated tube containers, infusion bags, container lids, paper containers, vacuum insulators, etc., heat sealing of packaging materials is usually performed. . Therefore, as a packaging material constituting these molded articles, one in which a heat-sealable layer is usually disposed on one or both outermost layers is preferable.
　以下、実施例および比較例に基づいて本発明を具体的に説明する。ただし、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be specifically described based on examples and comparative examples. However, the present invention is not limited to the following examples.
（調製例１）
　重合度２４００のＰＶＡ（クラレ製、ＰＶＡ１２４、完全ケン化ＰＶＡ）を固形分濃度が５質量％となるように水／メチルアルコール＝９０／１０（質量比）の混合溶媒にて希釈し、ＰＶＡ溶液を調製した。
　次に、テトラエトキシシラン（Ｓｉ（ＯＣ２Ｈ５）４、以下「ＴＥＯＳ」と称す。）に０．１Ｎ塩酸を加え、３０分間攪拌し加水分解させて固形分３質量％（ＳｉＯ２換算）のＴＥＯＳ加水分解溶液を調製した。
　別途、３－グリシドキシプロピルトリメトキシシラン（以下「ＧＰＴＭＳ」と称す。）に０．１Ｎ塩酸を加え、３０分間攪拌し加水分解させて固形分３質量％のＧＰＴＭＳ加水分解溶液を調製した。
　ＰＶＡ溶液とＧＰＴＭＳ加水分解溶液とＴＥＯＳ加水分解溶液とを、固形分質量比でＰＶＡ／ＧＰＴＭＳ／ＴＥＯＳ（ＳｉＯ２換算）が２５／５／７０となるように混合し、コーティング液（ａ１）を調製した。 (Preparation Example 1)
PVA solution with a polymerization degree of 2400 (manufactured by Kuraray, PVA124, completely saponified PVA) is diluted with a mixed solvent of water / methyl alcohol = 90/10 (mass ratio) so that the solid content concentration becomes 5% by mass, and the PVA solution Was prepared.
Next, 0.1N hydrochloric acid is added to tetraethoxysilane (Si (OC 2 H 5 ) 4 , hereinafter referred to as “TEOS”), and the mixture is stirred for 30 minutes to be hydrolyzed to a solid content of 3% by mass (in terms of SiO 2 ). A TEOS hydrolysis solution was prepared.
Separately, 0.1N hydrochloric acid was added to 3-glycidoxypropyltrimethoxysilane (hereinafter referred to as “GPTMS”), and the mixture was stirred for 30 minutes for hydrolysis to prepare a GPTMS hydrolysis solution having a solid content of 3% by mass.
A PVA solution, a GPTMS hydrolyzed solution, and a TEOS hydrolyzed solution are mixed so that PVA / GPTMS / TEOS (in terms of SiO 2 ) is 25/5/70 in terms of solid mass ratio to prepare a coating liquid (a1). did.
（調製例２）
　ＰＶＡ／ＧＰＴＭＳ／ＴＥＯＳ（ＳｉＯ２換算）を２５／１５／６０としたこと以外は調製例１と同様にしてコーティング液（ａ２）を調製した。 (Preparation Example 2)
A coating liquid (a2) was prepared in the same manner as in Preparation Example 1 except that PVA / GPTMS / TEOS (SiO 2 conversion) was 25/15/60.
（調製例３）
　ＰＶＡ／ＧＰＴＭＳ／ＴＥＯＳ（ＳｉＯ２換算）を２５／２５／５０としたこと以外は調製例１と同様にしてコーティング液（ａ３）を調製した。 (Preparation Example 3)
A coating solution (a3) was prepared in the same manner as in Preparation Example 1 except that PVA / GPTMS / TEOS (SiO 2 conversion) was 25/25/50.
（調製例４）
　ＰＶＡ／ＧＰＴＭＳ／ＴＥＯＳ（ＳｉＯ２換算）を２５／３０／４５としたこと以外は調製例１と同様にしてコーティング液（ａ４）を調製した。 (Preparation Example 4)
A coating liquid (a4) was prepared in the same manner as in Preparation Example 1 except that PVA / GPTMS / TEOS (SiO 2 conversion) was 25/30/45.
（調製例５）
　ＰＶＡ／ＧＰＴＭＳ／ＴＥＯＳ（ＳｉＯ２換算）を２７．５／５／６７．５としたこと以外は調製例１と同様にしてコーティング液（ａ５）を調製した。 (Preparation Example 5)
A coating liquid (a5) was prepared in the same manner as in Preparation Example 1, except that PVA / GPTMS / TEOS (SiO 2 conversion) was 27.5 / 5 / 67.5.
（調製例６）
　ＰＶＡ／ＧＰＴＭＳ／ＴＥＯＳ（ＳｉＯ２換算）を２７．５／７／６５．５としたこと以外は調製例１と同様にしてコーティング液（ａ６）を調製した。 (Preparation Example 6)
A coating liquid (a6) was prepared in the same manner as in Preparation Example 1, except that PVA / GPTMS / TEOS (SiO 2 equivalent) was 27.5 / 7 / 65.5.
（調製例７）
　ＰＶＡ／ＧＰＴＭＳ／ＴＥＯＳ（ＳｉＯ２換算）を２７．５／３０／４２．５としたこと以外は調製例１と同様にしてコーティング液（ａ７）を調製した。 (Preparation Example 7)
A coating solution (a7) was prepared in the same manner as in Preparation Example 1, except that PVA / GPTMS / TEOS (SiO 2 conversion) was 27.5 / 30 / 42.5.
（調製例８）
　ＰＶＡ／ＧＰＴＭＳ／ＴＥＯＳ（ＳｉＯ２換算）を３０／５／６５としたこと以外は調製例１と同様にしてコーティング液（ａ８）を調製した。 (Preparation Example 8)
A coating solution (a8) was prepared in the same manner as in Preparation Example 1, except that PVA / GPTMS / TEOS (SiO 2 conversion) was set to 30/5/65.
（調製例９）
　ＰＶＡ／ＧＰＴＭＳ／ＴＥＯＳ（ＳｉＯ２換算）を３０／１７．５／５２．５としたこと以外は調製例１と同様にしてコーティング液（ａ９）を調製した。 (Preparation Example 9)
A coating solution (a9) was prepared in the same manner as in Preparation Example 1, except that PVA / GPTMS / TEOS (SiO 2 equivalent) was 30 / 17.5 / 52.5.
（調製例１０）
　ＰＶＡ／ＧＰＴＭＳ／ＴＥＯＳ（ＳｉＯ２換算）を３０／３０／４０としたこと以外は調製例１と同様にしてコーティング液（ａ１０）を調製した。 (Preparation Example 10)
A coating solution (a10) was prepared in the same manner as in Preparation Example 1, except that PVA / GPTMS / TEOS (SiO 2 equivalent) was 30/30/40.
（調製例１１）
　ＧＰＴＭＳを３－グリシドキシプロピルトリエトキシシラン（以下「ＧＰＴＥＳ」と称す。）に変更したこと以外は調製例１と同様にしてコーティング液（ａ１１）を調製した。 (Preparation Example 11)
A coating solution (a11) was prepared in the same manner as in Preparation Example 1, except that GPTMS was changed to 3-glycidoxypropyltriethoxysilane (hereinafter referred to as “GPTES”).
（調製例１２）
　ＰＶＡ溶液とＴＥＯＳ加水分解溶液とを、固形分質量比でＰＶＡ／ＴＥＯＳ（ＳｉＯ２換算）が２５／７５となるように混合し、ＧＰＴＭＳ加水分解溶液を加えなかったこと以外は調製例１と同様にしてコーティング液（ｂ１）を調製した。 (Preparation Example 12)
The PVA solution and the TEOS hydrolysis solution were mixed so that the PVA / TEOS (SiO 2 conversion) was 25/75 in terms of solid content, and the same as in Preparation Example 1 except that the GPTMS hydrolysis solution was not added. Thus, a coating liquid (b1) was prepared.
（調製例１３）
　ＰＶＡ／ＧＰＴＭＳ／ＴＥＯＳ（ＳｉＯ２換算）を２０／１７．５／６２．５としたこと以外は調製例１と同様にしてコーティング液（ｂ２）を調製した。 (Preparation Example 13)
A coating solution (b2) was prepared in the same manner as in Preparation Example 1, except that PVA / GPTMS / TEOS (SiO 2 equivalent) was 20 / 17.5 / 62.5.
（調製例１４）
　ＰＶＡ／ＧＰＴＭＳ／ＴＥＯＳ（ＳｉＯ２換算）を３５／１７．５／４７．５としたこと以外は調製例１と同様にしてコーティング液（ｂ３）を調製した。 (Preparation Example 14)
A coating solution (b3) was prepared in the same manner as in Preparation Example 1, except that PVA / GPTMS / TEOS (SiO 2 equivalent) was 35 / 17.5 / 47.5.
（調製例１５）
　ＰＶＡ／ＧＰＴＭＳ／ＴＥＯＳ（ＳｉＯ２換算）を２７．５／３５／３７．５としたこと以外は調製例１と同様にしてコーティング液（ｂ４）を調製した。 (Preparation Example 15)
A coating liquid (b4) was prepared in the same manner as in Preparation Example 1 except that PVA / GPTMS / TEOS (SiO 2 equivalent) was 27.5 / 35 / 37.5.
（調製例１６）
　ＧＰＴＭＳを３－アミノプロピルトリメトキシシラン（以下「ＡＰＴＭＳ」と称す。）に変更したこと以外は調製例１と同様にしてコーティング液（ｂ５）を調製した。 (Preparation Example 16)
A coating solution (b5) was prepared in the same manner as in Preparation Example 1, except that GPTMS was changed to 3-aminopropyltrimethoxysilane (hereinafter referred to as “APTMS”).
（実施例１）
　２軸延伸ポリエチレンテレフタレートフィルム（ＰＥＴ：東レ製、ルミラー（登録商標）Ｐ６０、厚さ１２μｍ、内側コロナ処理）上に、電子線加熱方式による真空蒸着装置により、金属アルミニウムを蒸発させ、そこに酸素ガスを導入し、酸化アルミニウムを蒸着して厚さ２０ｎｍの蒸着膜（ガスバリア層）を形成した。 Example 1
On a biaxially stretched polyethylene terephthalate film (PET: manufactured by Toray, Lumirror (registered trademark) P60, thickness 12 μm, inner corona treatment), metal aluminum is evaporated by an electron beam heating vacuum deposition apparatus, and oxygen gas is present there. Then, aluminum oxide was vapor-deposited to form a vapor-deposited film (gas barrier layer) having a thickness of 20 nm.
　次に、このガスバリア層上に、コーティング液（ａ１）をバーコーターにより塗布し、乾燥機で１２０℃、１分間乾燥させ、膜厚約０．３μｍの被膜（層（ａ１））を形成し、［ＰＥＴ／ガスバリア層／層（ａ１）］の構成を有する積層シートを得た。 Next, a coating liquid (a1) is applied onto the gas barrier layer with a bar coater, and dried at 120 ° C. for 1 minute with a dryer to form a film (layer (a1)) having a film thickness of about 0.3 μm. A laminated sheet having the configuration of [PET / gas barrier layer / layer (a1)] was obtained.
（実施例２）
　コーティング液（ａ１）に換えてコーティング液（ａ２）を用いて被膜（層（ａ２））を形成したこと以外は、実施例１と同様の操作を行って［ＰＥＴ／ガスバリア層／層（ａ２）］の構成を有する積層シートを得た。 (Example 2)
[PET / gas barrier layer / layer (a2)] was performed in the same manner as in Example 1 except that the coating liquid (a2) was used instead of the coating liquid (a1) to form a film (layer (a2)). A laminated sheet having the structure is obtained.
（実施例３）
　コーティング液（ａ１）に換えてコーティング液（ａ３）を用いて被膜（層（ａ３））を形成したこと以外は、実施例１と同様の操作を行って［ＰＥＴ／ガスバリア層／層（ａ３）］の構成を有する積層シートを得た。 (Example 3)
[PET / gas barrier layer / layer (a3)] was performed in the same manner as in Example 1 except that the coating liquid (a3) was used instead of the coating liquid (a1) to form a film (layer (a3)). A laminated sheet having the structure is obtained.
（実施例４）
　コーティング液（ａ１）に換えてコーティング液（ａ４）を用いて被膜（層（ａ４））を形成したこと以外は、実施例１と同様の操作を行って［ＰＥＴ／ガスバリア層／層（ａ４）］の構成を有する積層シートを得た。 Example 4
[PET / gas barrier layer / layer (a4)] The same operation as in Example 1 was performed except that the coating liquid (a4) was used instead of the coating liquid (a1) to form a film (layer (a4)). A laminated sheet having the structure is obtained.
（実施例５）
　コーティング液（ａ１）に換えてコーティング液（ａ５）を用いて被膜（層（ａ５））を形成したこと以外は、実施例１と同様の操作を行って［ＰＥＴ／ガスバリア層／層（ａ５）］の構成を有する積層シートを得た。 (Example 5)
[PET / gas barrier layer / layer (a5)] was performed in the same manner as in Example 1 except that the coating liquid (a5) was used instead of the coating liquid (a1) to form a film (layer (a5)). A laminated sheet having the structure is obtained.
（実施例６）
　コーティング液（ａ１）に換えてコーティング液（ａ６）を用いて被膜（層（ａ６））を形成したこと以外は、実施例１と同様の操作を行って［ＰＥＴ／ガスバリア層／層（ａ６）］の構成を有する積層シートを得た。 (Example 6)
[PET / gas barrier layer / layer (a6)] was performed in the same manner as in Example 1 except that the coating liquid (a6) was used instead of the coating liquid (a1) to form a film (layer (a6)). A laminated sheet having the structure is obtained.
（実施例７）
　コーティング液（ａ１）に換えてコーティング液（ａ７）を用いて被膜（層（ａ７））を形成したこと以外は、実施例１と同様の操作を行って［ＰＥＴ／ガスバリア層／層（ａ７）］の構成を有する積層シートを得た。 (Example 7)
[PET / gas barrier layer / layer (a7)] The same operation as in Example 1 was performed except that the coating liquid (a7) was used instead of the coating liquid (a1) to form a film (layer (a7)). A laminated sheet having the structure is obtained.
（実施例８）
　コーティング液（ａ１）に換えてコーティング液（ａ８）を用いて被膜（層（ａ８））を形成したこと以外は、実施例１と同様の操作を行って［ＰＥＴ／ガスバリア層／層（ａ８）］の構成を有する積層シートを得た。 (Example 8)
[PET / gas barrier layer / layer (a8)] was performed in the same manner as in Example 1 except that the coating liquid (a8) was used instead of the coating liquid (a1) to form a film (layer (a8)). A laminated sheet having the structure is obtained.
（実施例９）
　コーティング液（ａ１）に換えてコーティング液（ａ９）を用いて被膜（層（ａ９））を形成したこと以外は、実施例１と同様の操作を行って［ＰＥＴ／ガスバリア層／層（ａ９）］の構成を有する積層シートを得た。 Example 9
[PET / gas barrier layer / layer (a9)] was performed in the same manner as in Example 1 except that the coating liquid (a9) was used instead of the coating liquid (a1) to form a film (layer (a9)). A laminated sheet having the structure is obtained.
（実施例１０）
　コーティング液（ａ１）に換えてコーティング液（ａ１０）を用いて被膜（層（ａ１０））を形成したこと以外は、実施例１と同様の操作を行って［ＰＥＴ／ガスバリア層／層（ａ１０）］の構成を有する積層シートを得た。 (Example 10)
[PET / gas barrier layer / layer (a10)] was performed in the same manner as in Example 1 except that the coating liquid (a10) was used instead of the coating liquid (a1) to form a film (layer (a10)). A laminated sheet having the structure is obtained.
（実施例１１）
　コーティング液（ａ１）に換えてコーティング液（ａ１１）を用いて被膜（層（ａ１１））を形成したこと以外は、実施例１と同様の操作を行って［ＰＥＴ／ガスバリア層／層（ａ１１）］の構成を有する積層シートを得た。 (Example 11)
[PET / gas barrier layer / layer (a11)] The same operation as in Example 1 was performed except that the coating liquid (a11) was used instead of the coating liquid (a1) to form a film (layer (a11)). A laminated sheet having the structure is obtained.
（実施例１２）
　コーティング液（ａ１）に換えてコーティング液（ｂ１）を用いて被膜（層（ｂ１））を形成したこと以外は、実施例１と同様の操作を行って［ＰＥＴ／ガスバリア層／層（ｂ１）］の構成を有する積層体を得た。
　次に、得られた積層体の層（ｂ１）上に、バーコーターによりコーティング液（ａ９）を塗布し、乾燥機で１２０℃、１分間乾燥させ、膜厚０．３μｍの被膜（層（ａ９））を形成し、［ＰＥＴフィルム／ガスバリア層／層（ｂ１）／層（ａ９）］の構成を有する積層シートを得た。 Example 12
[PET / gas barrier layer / layer (b1)] The same operation as in Example 1 was performed except that the coating liquid (b1) was used instead of the coating liquid (a1) to form a film (layer (b1)). The laminated body which has a structure of] was obtained.
Next, the coating liquid (a9) is applied onto the layer (b1) of the obtained laminate by a bar coater, and dried at 120 ° C. for 1 minute with a dryer to form a 0.3 μm-thick film (layer (a9 )) To form a laminated sheet having a structure of [PET film / gas barrier layer / layer (b1) / layer (a9)].
（比較例１）
　２軸延伸ポリエチレンテレフタレートフィルム（ＰＥＴ：東レ製、ルミラー（登録商標）Ｐ６０、厚さ１２μｍ、内側コロナ処理）上に、電子線加熱方式による真空蒸着装置により、金属アルミニウムを蒸発させ、そこに酸素ガスを導入し、酸化アルミニウムを蒸着して厚さ２０ｎｍの蒸着膜（ガスバリア層）を形成した。 (Comparative Example 1)
On a biaxially stretched polyethylene terephthalate film (PET: manufactured by Toray, Lumirror (registered trademark) P60, thickness 12 μm, inner corona treatment), metal aluminum is evaporated by an electron beam heating vacuum deposition apparatus, and oxygen gas is present there. Then, aluminum oxide was vapor-deposited to form a vapor-deposited film (gas barrier layer) having a thickness of 20 nm.
　次に、このガスバリア層上に、コーティング液（ｂ１）をバーコーターにより塗布し、乾燥機で１２０℃、１分間乾燥させ、膜厚約０．６μｍの被膜（層（ｂ１））を形成し、［ＰＥＴ／ガスバリア層／層（ｂ１）］の構成を有する積層シートを得た。 Next, the coating liquid (b1) is applied onto the gas barrier layer with a bar coater, and dried at 120 ° C. for 1 minute with a dryer to form a film (layer (b1)) having a film thickness of about 0.6 μm. A laminated sheet having the configuration of [PET / gas barrier layer / layer (b1)] was obtained.
（比較例２）
　コーティング液（ｂ１）に換えてコーティング液（ｂ２）を用いて被膜（層（ｂ２））を形成したこと以外は、比較例１と同様の操作を行って積層シートを得た。 (Comparative Example 2)
A laminated sheet was obtained in the same manner as in Comparative Example 1 except that the coating liquid (b2) was used instead of the coating liquid (b1) to form a film (layer (b2)).
（比較例３）
　コーティング液（ｂ１）に換えてコーティング液（ｂ３）を用いて被膜（層（ｂ３））を形成したこと以外は、比較例１と同様の操作を行って積層シートを得た。 (Comparative Example 3)
A laminated sheet was obtained in the same manner as in Comparative Example 1 except that the coating liquid (b3) was used instead of the coating liquid (b1) to form a film (layer (b3)).
（比較例４）
　コーティング液（ｂ１）に換えてコーティング液（ｂ４）を用いて被膜（層（ｂ４））を形成したこと以外は、比較例１と同様の操作を行って積層シートを得た。 (Comparative Example 4)
A laminated sheet was obtained in the same manner as in Comparative Example 1 except that the coating liquid (b4) was used instead of the coating liquid (b1) to form a film (layer (b4)).
（比較例５）
　コーティング液（ｂ１）に換えてコーティング液（ｂ５）を用いて被膜（層（ｂ５））を形成したこと以外は、比較例１と同様の操作を行って積層シートを得た。 (Comparative Example 5)
A laminated sheet was obtained by performing the same operation as in Comparative Example 1 except that the coating liquid (b5) was used instead of the coating liquid (b1) to form a film (layer (b5)).
（評価）
［１．ラミネートフィルムの作製］
　実施例１～１２および比較例１～５で得られた積層シートを用い、以下の手順で、ラミネートシートを作製した。
　積層シートの積層面に、Ｎｙ（延伸ナイロンフィルム）と、ＣＰＰ（ポリプロピレンフィルム）とを、接着剤を用いて、ＨＩＲＡＮＯ ＴＥＣＳＥＥＤ社製のマルチコーターＭＣ３５０により順次貼り合わせた。その後、４０℃にて３日間養生して、［積層シート／接着剤／Ｎｙ／接着剤／ＣＰＰ］の構成を有するラミネートシートを得た。
　別途、積層シートの積層面に、ＬＬＤＰＥ（直鎖状低密度ポリエチレン）を貼り合わせ、［積層シート／接着剤／ＬＬＤＰＥ］の構成を有するラミネートシートを得た。
　なお、積層面とは、ガスバリア層および被膜が積層された面である。 (Evaluation)
[1. Preparation of laminate film]
Using the laminated sheets obtained in Examples 1 to 12 and Comparative Examples 1 to 5, laminate sheets were produced by the following procedure.
Ny (stretched nylon film) and CPP (polypropylene film) were sequentially bonded to the laminated surface of the laminated sheet using a multi coater MC350 manufactured by HIRANO TECSEED, using an adhesive. Thereafter, the film was cured at 40 ° C. for 3 days to obtain a laminate sheet having a structure of [Laminated sheet / Adhesive / Ny / Adhesive / CPP].
Separately, LLDPE (linear low density polyethylene) was bonded to the laminated surface of the laminated sheet to obtain a laminated sheet having the configuration of [Laminated sheet / Adhesive / LLDPE].
The laminated surface is a surface on which a gas barrier layer and a film are laminated.
　接着剤としては、三井化学社製の２液硬化型接着剤、タケラックＡ５２５（主剤）／タケネートＡ５２（硬化剤）を用いた。
　Ｎｙとしては、ユニチカ社製の延伸ナイロンフィルム、エンブレムＯＮＭＢ（１５μｍ）を用いた。
　ＣＰＰとしては、東レフィルム加工社製のポリプロピレンフィルム、トレファンＺＫ９３ＦＭ（６０μｍ）を用いた。
　ＬＬＤＰＥとしては、三井化学東セロ社製の直鎖状低密度ポリエチレンフィルム、ＴＵＸ－ＴＣＳ（６０μｍ）を用いた。 As the adhesive, a two-component curable adhesive, Takelac A525 (main agent) / Takenate A52 (hardener) manufactured by Mitsui Chemicals, Inc. was used.
As Ny, a stretched nylon film, Emblem ONMB (15 μm) manufactured by Unitika Ltd. was used.
As the CPP, a polypropylene film manufactured by Toray Film Processing Co., Ltd., Treffan ZK93FM (60 μm) was used.
As LLDPE, a linear low-density polyethylene film, TUX-TCS (60 μm) manufactured by Mitsui Chemicals, Inc., Toro Cello Co., Ltd. was used.
　得られたラミネートシートについて、以下の評価を行った。結果を表１に示す。 The following evaluation was performed on the obtained laminate sheet. The results are shown in Table 1.
［２．ガスバリア性（***前）の評価］
　ラミネートフィルム（構成：積層シート／接着剤／ＬＬＤＰＥ）について、以下の手順で、酸素透過度および水蒸気透過度を測定した。各データは測定のバラつきを考慮し、Ｎ＝５で測定し、上下２点を除いた上で、Ｎ＝３にて平均値をとり、その値を採用した。測定結果を「原紙」の酸素透過度および水蒸気透過度として表１に示す。なお、「原紙」とは、後述する***試験及びレトルト滅菌処理に付されていないラミネートフィルムであることを意味する。 [2. Evaluation of gas barrier properties (before abuse)]
With respect to the laminate film (configuration: laminated sheet / adhesive / LLDPE), oxygen permeability and water vapor permeability were measured by the following procedure. Each data was measured at N = 5 in consideration of measurement variation, and after taking the upper and lower two points, an average value was taken at N = 3 and the value was adopted. The measurement results are shown in Table 1 as oxygen permeability and water vapor permeability of “base paper”. The “base paper” means a laminate film that has not been subjected to the abuse test and retort sterilization described later.
　「酸素透過度の測定」
　酸素透過試験器（ＯＸＴＲＡＮ２／２０、Ｍｏｄｅｒｎ　Ｃｏｎｔｒｏｌ社製）を用いて、温度３０℃、相対湿度７０％の条件で、サンプルの酸素透過度を測定した。測定方法は、ＪＩＳ　Ｋ－７１２６「Ｂ法（等圧法）」、および、ＡＳＴＭ　Ｄ３９８５－８１に準拠して、測定値を単位：ｃｍ３（ＳＴＰ）／（ｍ２・ｄａｙ・ＭＰａ）で表記した。ここで、（ＳＴＰ）は酸素の体積を規定するための標準条件（０℃、１気圧）を意味する。 "Measurement of oxygen permeability"
The oxygen permeability of the sample was measured under the conditions of a temperature of 30 ° C. and a relative humidity of 70% using an oxygen permeation tester (OXTRAN 2/20, manufactured by Modern Control). The measurement method was expressed in units of cm 3 (STP) / (m 2 · day · MPa) in accordance with JIS K-7126 “Method B (isobaric method)” and ASTM D3985-81. . Here, (STP) means standard conditions (0 ° C., 1 atm) for defining the volume of oxygen.
　「水蒸気透過度の測定」
　水蒸気透過試験器（ＰＥＲＭＡＴＲＡＮ３／３１、Ｍｏｄｅｒｎ　Ｃｏｎｔｒｏｌ社製）を用いて、温度４０℃、相対湿度９０％の条件で、サンプルの水素透過度を測定した。
　測定方法は、ＪＩＳ　Ｋ－７１２９、および、ＡＳＴＭ　Ｆ１２４９－９０に準拠して、測定値を単位：ｇ（ＳＴＰ）／（ｍ２・ｄａｙ）で表記した。 "Measurement of water vapor transmission rate"
Using a water vapor transmission tester (PERMATRAN 3/31, manufactured by Modern Control), the hydrogen permeability of the sample was measured under conditions of a temperature of 40 ° C. and a relative humidity of 90%.
The measurement method was expressed in units of g (STP) / (m 2 · day) in accordance with JIS K-7129 and ASTM F1249-90.
［３．柔軟性の評価］
　ラミネートフィルム（構成：積層シート／接着剤／ＬＬＤＰＥ）を縦２００ｍｍ×横１５０ｍｍの大きさに切り出してサンプルとした。該サンプルについて、以下の***試験を行った。
　サンプルを、東洋ボールドウィン社製のテンシロンを用いて、速度１００μｍ／秒で縦方向に５％延伸し、その延伸状態を１分間保持した後、同様の速度でフィルムを元の位置に戻し、延伸した。
　この***試験の後のサンプルについて、酸素透過度および水蒸気透過度を前記の測定方法により測定した。各データは測定のバラつきを考慮し、Ｎ＝５で測定し、上下２点を除いた上で、Ｎ＝３にて平均値をとり、その値を採用した。測定結果を「延伸後」の酸素透過度および水蒸気透過度として表１に示す。延伸後の値が原紙の値に近いほど、被膜の柔軟性が高く、延伸による積層シートのガスバリア性の劣化を抑制する効果が高いことを示す。 [3. Flexibility evaluation]
A laminate film (configuration: laminated sheet / adhesive / LLDPE) was cut into a size of 200 mm long × 150 mm wide to prepare a sample. The sample was subjected to the following abuse test.
The sample was stretched 5% in the machine direction at a speed of 100 μm / second using Tensilon manufactured by Toyo Baldwin, and the stretched state was maintained for 1 minute. Then, the film was returned to the original position at the same speed and stretched. .
About the sample after this abuse test, the oxygen permeability and the water vapor permeability were measured by the measurement method described above. Each data was measured at N = 5 in consideration of measurement variation, and after taking the upper and lower two points, an average value was taken at N = 3 and the value was adopted. The measurement results are shown in Table 1 as oxygen permeability and water vapor permeability “after stretching”. The closer the value after stretching to the value of the base paper, the higher the flexibility of the coating film, and the higher the effect of suppressing the deterioration of the gas barrier property of the laminated sheet due to stretching.
［４．耐熱湿性の評価］
　ラミネートフィルム（構成：積層シート／接着剤／Ｎｙ／接着剤／ＣＰＰ）を用いて、４辺をシール部とする縦２１０ｍｍ×横１５０ｍｍの大きさのパウチを作製し、内容物として水を充填した。その後、１２１℃、３０分間レトルト殺菌処理を行い、レトルト殺菌処理後の酸素および水蒸気透過度を測定した。その結果を「レトルト処理後」の酸素透過度および水蒸気透過度として表１に示す。レトルト処理後の値が原紙の値に近いほど、被膜の耐熱湿性が高く、高温高湿度条件下で被膜のガスバリア性が劣化しにくいことを示す。 [4. Evaluation of heat and humidity resistance]
Using a laminate film (configuration: laminate sheet / adhesive / Ny / adhesive / CPP), a pouch having a size of 210 mm in length and 150 mm in width with four sides as a seal portion was prepared and filled with water as the contents. . Thereafter, a retort sterilization treatment was performed at 121 ° C. for 30 minutes, and oxygen and water vapor permeability after the retort sterilization treatment were measured. The results are shown in Table 1 as oxygen permeability and water vapor permeability “after retort treatment”. The closer the value after retorting is to the value of the base paper, the higher the heat and humidity resistance of the coating, indicating that the gas barrier properties of the coating are less likely to deteriorate under high temperature and high humidity conditions.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１中、「（Ａ）成分」は水酸基含有高分子化合物（Ａ）、「Ｓｉ剤」はシランカップリング剤、「（Ｃ）成分」はケイ素化合物（Ｃ）を示す。 In Table 1, “(A) component” represents a hydroxyl group-containing polymer compound (A), “Si agent” represents a silane coupling agent, and “(C) component” represents a silicon compound (C).
　上記結果に示すとおり、実施例１～１２の積層シートは、原紙の状態で高いガスバリア性を有していた。また、原紙における酸素透過度および水蒸気透過度の値と、延伸後、レトルト処理後それぞれにおける酸素透過度および水蒸気透過度の値との差が小さく、被膜の柔軟性および耐熱湿性に優れていた。
　一方、被膜の形成に用いたコーティング液がエポキシ基含有シランカップリング剤（Ｂ）を含まない比較例１、高分子化合物（Ａ）とエポキシ基含有シランカップリング剤（Ｂ）とケイ素化合物（Ｃ）のＳｉＯ２換算量との合計に対する高分子化合物（Ａ）の割合が２５～３０質量％の範囲外である比較例２～３、前記合計に対するエポキシ基含有シランカップリング剤（Ｂ）の割合が５～３０質量％の範囲外である比較例４、エポキシ基を含有しないシランカップリング剤を用いた比較例５の積層シートは、原紙における酸素透過度および水蒸気透過度の値と、延伸後またはレトルト処理後における酸素透過度および水蒸気透過度の値との差が大きかった。 As shown in the above results, the laminated sheets of Examples 1 to 12 had high gas barrier properties in the state of the base paper. Further, the difference between the oxygen permeability and water vapor permeability of the base paper and the values of oxygen permeability and water vapor permeability after stretching and after retorting were small, and the film was excellent in flexibility and heat and humidity resistance.
On the other hand, the coating liquid used for forming the coating does not contain an epoxy group-containing silane coupling agent (B), Comparative Example 1, a polymer compound (A), an epoxy group-containing silane coupling agent (B), and a silicon compound (C ) Is a ratio of the polymer compound (A) to the total of the SiO 2 equivalent amount in Comparative Examples 2 to 3 outside the range of 25 to 30% by mass, the ratio of the epoxy group-containing silane coupling agent (B) to the total Is a laminated sheet of Comparative Example 4 using a silane coupling agent that does not contain an epoxy group, the values of oxygen permeability and water vapor permeability in the base paper, and after stretching Or the difference with the value of oxygen permeability and water vapor permeability after retort processing was large.
　本発明の積層シートは、高温高湿下でも高いガスバリア性を有し、ボイル処理、レトルト処理等の熱水処理後においても高いレベルでガスバリア性を維持することができる。また、折り曲げ、延伸といった***後もガスバリア性が劣化しにくい。
　そのため、本発明の積層シートを用いて、印刷工程やドライラミネート、溶融押し出しラミネート、熱圧着ラミネートなどの後加工を行い、食品、医薬品等の包装分野に用いられる実用範囲の広い包装材料を提供することが可能である。 The laminated sheet of the present invention has a high gas barrier property even under high temperature and high humidity, and can maintain the gas barrier property at a high level even after hot water treatment such as boil treatment and retort treatment. In addition, gas barrier properties are unlikely to deteriorate even after abuse such as bending or stretching.
Therefore, by using the laminated sheet of the present invention, post-processing such as a printing process, dry lamination, melt extrusion lamination, thermocompression lamination, etc. is provided to provide a packaging material with a wide practical range used in the packaging field of foods, pharmaceuticals, etc. It is possible.
　本発明の積層シートは、包装材料以外の用途にも用いることができる。包装材料以外の用途としては、例えばＬＣＤ用基板フィルム、有機ＥＬ用基板フィルム、電子ペーパー用基板フィルム、電子デバイス用封止フィルム、ＰＤＰ用フィルム、ＬＥＤ用フィルム、ＩＣタグ用フィルム、太陽電池用バックシート、太陽電池用保護フィルムなどの電子デバイス関連フィルム、光通信用部材、電子機器用フレキシブルフィルム、燃料電池用隔膜、燃料電池用封止フィルム、各種機能性フィルムの基板フィルム等が挙げられる。 The laminated sheet of the present invention can be used for applications other than packaging materials. Applications other than packaging materials include, for example, LCD substrate films, organic EL substrate films, electronic paper substrate films, electronic device sealing films, PDP films, LED films, IC tag films, solar cell bags Sheets, films related to electronic devices such as protective films for solar cells, optical communication members, flexible films for electronic devices, diaphragms for fuel cells, sealing films for fuel cells, substrate films for various functional films, and the like.
　１　基材
　３　ガスバリア層
　５　組成物（Ｉ）の層
　７　組成物（ＩＩ）の層
　９　他の基材
１０、２０、３０　積層シート
１１　接着層 DESCRIPTION OF SYMBOLS 1 Base material 3 Gas barrier layer 5 Layer of composition (I) 7 Layer of composition (II) 9 Other base materials 10, 20, 30 Laminated sheet 11 Adhesive layer

Claims (8)

  1. 　基材と、
    　水酸基含有高分子化合物（Ａ）と、エポキシ基含有シランカップリング剤（Ｂ）と、前記エポキシ基含有シランカップリング剤（Ｂ）以外の他のケイ素化合物（Ｃ）とを含む組成物から形成された層と、
    を備え、
    　前記水酸基含有高分子化合物（Ａ）の質量と、前記エポキシ基含有シランカップリング剤（Ｂ）の質量と、前記ケイ素化合物（Ｃ）のＳｉＯ２換算量との合計質量に対し、前記水酸基含有高分子化合物（Ａ）の割合が２５～３０質量％、前記エポキシ基含有シランカップリング剤化合物（Ｂ）の割合が５～３０質量％である、積層シート。     A substrate;
    It is formed from a composition containing a hydroxyl group-containing polymer compound (A), an epoxy group-containing silane coupling agent (B), and another silicon compound (C) other than the epoxy group-containing silane coupling agent (B). And the layer
    With
    With respect to the total mass of the mass of the hydroxyl group-containing polymer compound (A), the mass of the epoxy group-containing silane coupling agent (B), and the SiO 2 equivalent of the silicon compound (C), A laminated sheet in which the proportion of the molecular compound (A) is 25 to 30% by mass and the proportion of the epoxy group-containing silane coupling agent compound (B) is 5 to 30% by mass.
  2. 　前記ケイ素化合物（Ｃ）が、下記式（ｃ１）で表される化合物およびその加水分解物からなる群から選ばれる少なくとも１種の化合物（Ｃ１）を含む、請求項１に記載の積層シート。
    　Ｓｉ（ＯＲ１）４　・・・（ｃ１）
    （式中、Ｒ１は炭素数１～４のアルキル基または炭素数１～４のアルコキシアルキル基であり、式中の４つのＲ１は同じであっても異なっていてもよい。）     The laminated sheet according to claim 1, wherein the silicon compound (C) includes at least one compound (C1) selected from the group consisting of a compound represented by the following formula (c1) and a hydrolyzate thereof.
    Si (OR 1 ) 4 (c1)
    (In the formula, R 1 is an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl group having 1 to 4 carbon atoms, and four R 1 in the formula may be the same or different.)
  3. 　前記エポキシ基含有シランカップリング剤（Ｂ）が、下記式（ｂ１）で表される化合物およびその加水分解物からなる群から選ばれる少なくとも１種の化合物（Ｂ１）を含む、請求項１または２に記載の積層シート。
    　Ｒ３Ｓｉ（ＯＲ２）３　・・・（ｂ１）
    （式中、Ｒ２は炭素数１～４のアルキル基または炭素数１～４のアルコキシアルキル基であり、式中の３つのＲ２は同じであっても異なっていてもよく、Ｒ３はエポキシ基を含む有機基である。）     The epoxy group-containing silane coupling agent (B) contains at least one compound (B1) selected from the group consisting of a compound represented by the following formula (b1) and a hydrolyzate thereof. The laminated sheet according to 1.
    R 3 Si (OR 2 ) 3 (b1)
    (Wherein R 2 is an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl group having 1 to 4 carbon atoms, and three R 2 in the formula may be the same or different, and R 3 is An organic group containing an epoxy group.)
  4. 　無機材料から形成されるガスバリア層をさらに備える、請求項１～３のいずれか一項に記載の積層シート。 The laminated sheet according to any one of claims 1 to 3, further comprising a gas barrier layer formed of an inorganic material.
  5. 　請求項１～４のいずれか一項に記載の積層シートを含む包装材料。 A packaging material comprising the laminated sheet according to any one of claims 1 to 4.
  6. 　熱水処理用包装材料である、請求項５に記載の包装材料。 The packaging material according to claim 5, which is a packaging material for hot water treatment.
  7. 　請求項５または６に記載の包装材料を備える成形品。 A molded article comprising the packaging material according to claim 5 or 6.
  8. 　縦製袋充填シール袋、真空包装袋、スパウト付パウチ、ラミネートチューブ容器、輸液バッグ、容器用蓋材、紙容器または真空断熱体である、請求項７に記載の成形品。 The molded article according to claim 7, which is a vertical bag-filled sealing bag, a vacuum packaging bag, a pouch with a spout, a laminated tube container, an infusion bag, a container lid, a paper container, or a vacuum insulator.
PCT/JP2017/020039 2016-05-31 2017-05-30 Layered sheet, packaging material, and molded article WO2017209107A1 (en)

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