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WO2019039555A1 - Multilayered film, laminate, production method for laminate, and air bag - Google Patents

Multilayered film, laminate, production method for laminate, and air bag Download PDF

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Publication number
WO2019039555A1
WO2019039555A1 PCT/JP2018/031191 JP2018031191W WO2019039555A1 WO 2019039555 A1 WO2019039555 A1 WO 2019039555A1 JP 2018031191 W JP2018031191 W JP 2018031191W WO 2019039555 A1 WO2019039555 A1 WO 2019039555A1
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WO
WIPO (PCT)
Prior art keywords
multilayer film
layer
adhesive layer
base fabric
laminate
Prior art date
Application number
PCT/JP2018/031191
Other languages
French (fr)
Japanese (ja)
Inventor
洋佑 山田
徹 田上
ミヒャエル ルートヴィッヒ
Original Assignee
日東電工株式会社
ニットー スウィッツァーランド アーゲー
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Publication date
Application filed by 日東電工株式会社, ニットー スウィッツァーランド アーゲー filed Critical 日東電工株式会社
Publication of WO2019039555A1 publication Critical patent/WO2019039555A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/12Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/32Layered products comprising a layer of synthetic resin comprising polyolefins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/34Layered products comprising a layer of synthetic resin comprising polyamides
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/36Layered products comprising a layer of synthetic resin comprising polyesters
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/38Layered products comprising a layer of synthetic resin comprising epoxy resins
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02Physical, chemical or physicochemical properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B60VEHICLES IN GENERAL
    • B60RVEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
    • B60R21/00Arrangements or fittings on vehicles for protecting or preventing injuries to occupants or pedestrians in case of accidents or other traffic risks
    • B60R21/02Occupant safety arrangements or fittings, e.g. crash pads
    • B60R21/16Inflatable occupant restraints or confinements designed to inflate upon impact or impending impact, e.g. air bags
    • B60R21/23Inflatable members
    • B60R21/235Inflatable members characterised by their material

Definitions

  • the present invention relates to a multilayer film, a laminate, a method of manufacturing a laminate, and an air bag.
  • Patent Document 1 discloses a laminate used as a vehicle air bag, in which a film is dry-laminated on a woven fabric having warp yarns and weft yarns.
  • the above-mentioned laminate may be used in an environment where temperature or humidity or both are high. Therefore, in recent years, the laminated body is required to improve the durability under such a severe environment.
  • one form of the present invention makes it a subject to provide a multilayer film which enables manufacture of a layered product excellent in endurance under high temperature and / or a high humidity environment.
  • an embodiment of the present invention is a multilayer film used by bonding to a base fabric, and an adhesive layer to be bonded to the base fabric and the adhesive layer And the adhesive layer comprises an olefin-based polymer containing an epoxy group, and the melting point of the hermetic layer is higher than the melting point of the adhesive layer.
  • FIG. 1 is a schematic cross-sectional view of a multilayer film according to an aspect of the present invention.
  • 1 is a schematic cross-sectional view of a multilayer film according to an aspect of the present invention.
  • 1 is a schematic cross-sectional view of a multilayer film according to an aspect of the present invention. It is a typical sectional view of a layered product by one form of the present invention. It is a typical sectional view of a layered product by one form of the present invention.
  • FIG. 1 is a schematic view of an apparatus for manufacturing a laminate according to an aspect of the present invention. It is a schematic diagram explaining lamination
  • a multilayer film according to one aspect of the present invention is used by bonding to a base fabric, and has an adhesive layer on the side to be bonded to the base fabric and an airtight layer bonded to the adhesive layer.
  • the adhesive layer contains an olefin-based polymer containing an epoxy group, and the melting point of the hermetic layer is higher than the melting point of the adhesive layer.
  • the multilayer film 1 comprises a gas-tight layer 4 and an adhesive layer 2 bonded to the gas-tight layer 4, ie directly bonded to the gas-tight layer 4.
  • the multilayer film 1 can be used by being adhered to a base cloth, and in the case of adhesion, the adhesive layer 2 is the side to be adhered to the base cloth.
  • the adhesive layer 2 is directly laminated to the base fabric 8 and in the obtained laminate 10 It becomes an inner layer sandwiched between the cloth 8 and the airtight layer 4. Therefore, the adhesive layer 2 can be said to be a layer which bonds the airtight layer 4 and the base fabric 8.
  • the airtight layer is a layer having a function of preventing gas from flowing in and out of the layer (hereinafter, also referred to as an airtight function).
  • the adhesive layer is a layer exhibiting adhesion to the base fabric, and the adhesion is exhibited by softening or melting under predetermined conditions, for example, under conditions of increased temperature and / or pressure. It may be
  • the multilayer film has an adhesive layer containing an olefin-based polymer containing an epoxy group, whereby the multilayer film is adhered to a base fabric to produce a laminate; A laminate excellent in durability under the environment can be obtained.
  • high temperature refers to the temperature exceeding normal temperature
  • high humidity refers to the humidity exceeding normal humidity.
  • normal temperature refers to a temperature range of 5 to 35 ° C.
  • normal humidity refers to a range of relative humidity of 45 to 85%. Therefore, the multilayer film of the present embodiment can exhibit excellent durability even after being stored for a predetermined time under conditions of a temperature above 35 ° C. and / or a relative humidity above 85%.
  • the multilayer film of the present embodiment preferably has a temperature of 50 ° C. or more, more preferably 70 ° C. or more, and / or a humidity of 90% or more, more preferably 95% or more. Can also exhibit excellent durability. In addition, excellent durability can be exhibited even after storage under the above-described high temperature and high humidity conditions, for example, 84 hours or more, more preferably 168 hours or more, and still more preferably 408 hours or more.
  • the durability of the laminate is obtained, for example, by bonding a multilayer film and a base fabric to prepare a laminate, and storing the laminate under a high temperature and / or high humidity environment as described above for a predetermined time, It can be evaluated by measuring the delamination resistance (peel strength or breaking strength) between the multilayer film and the base fabric.
  • the evaluation of the delamination resistance can include the evaluation of the delamination resistance between layers in the multilayer film.
  • the multilayer film has a multilayer structure having at least two layers having an airtight layer and an adhesive layer.
  • each layer can separately have an adhesion function at the time of adhering the multilayer film to the base fabric and an airtight function in the obtained laminate. Therefore, when the multilayer film according to the present embodiment is used, a high-quality laminate that reliably exhibits both the adhesive function and the airtight function of the multilayer film is manufactured as compared to the case where the single layer film is adhered to the base fabric. be able to.
  • the melting point of the hermetic layer is higher than the melting point of the adhesive layer.
  • the adhesive layer can be softened or melted to a softness suitable for adhesion to the backing. As a result, even when the conditions of temperature and pressure at the time of production are changed, the laminate can be produced while achieving both the reliable adhesion to the base cloth and the maintenance of the airtightness of the multilayer film.
  • the adhesive layer can exhibit the adhesive function
  • the multilayer film can be favorably adhered to the base cloth without using an adhesive or the like separately.
  • the effort and cost by use of an adhesive agent can be reduced.
  • the melting point of a layer is the temperature at which the layer softens when the temperature of the layer is raised, and the molecules of the polymer in the layer begin to move relative to each other, causing the polymer to become fluid. Point to. Therefore, the melting point of the adhesive layer and the hermetic layer can be said to be the melting point of the polymer component (including the polymer alloy) in the adhesive layer and the hermetic layer, respectively.
  • the melting point of such a polymer can be the melting peak temperature measured by differential scanning calorimetry.
  • the adhesive layer is a layer on the side of the base fabric when the multilayer film is adhered to the base fabric, and is a layer showing adhesiveness to the base fabric under predetermined conditions. Furthermore, in the resulting laminate, the adhesive layer can also have an airtight function.
  • the adhesive layer contains an olefin-based polymer containing an epoxy group. Since the adhesive layer contains a polymer containing an epoxy group, it can improve the adhesion to a polyester-containing base fabric under high temperature and / or high humidity environments, so the base fabric and the adhesive layer Between the above and the other can hardly occur, and the durability can be improved.
  • the olefin-based polymer containing an epoxy group contained in the adhesive layer is preferably a copolymer containing a monomer unit containing an epoxy group and another monomer unit.
  • ⁇ -olefin / unsaturated carboxylic acid ester / epoxy It can be a terpolymer (terpolymer) of monomer units having a group.
  • ⁇ -olefins in terpolymers include ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-docosene, 1-tetracocene, 1-hexacocene, 1-octacocene, and 1-triaconcene It can be mentioned.
  • the above ⁇ -olefins may be contained singly or in combination of two or more in the terpolymer.
  • the unsaturated carboxylic acid ester in the terpolymer is preferably an alkyl (meth) acrylate.
  • (meth) acrylate refers to methacrylate and / or acrylate.
  • the alkyl (meth) acrylates include those in which the alkyl group has 1 to 24 carbon atoms. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
  • the acrylate may be contained singly or in combination of two or more in the olefin-based polymer containing an epoxy group.
  • the monomer unit having an epoxy group in the above terpolymer is preferably unsaturated epoxide.
  • Unsaturated epoxides include glycidyl esters and ethers of fatty acids, and esters and ethers of cycloaliphatic glycidyls and the like.
  • Glycidyl esters and ethers of fatty acids include, for example, allyl glycidyl ether, vinyl glycidyl ether, glycidyl maleate, glycidyl triconate, and glycidyl (meth) acrylate.
  • esters and ethers of alicyclic glycidyl for example, 2-cyclohexene-1-glycidyl ether, cyclohexene-4,5-diglycidyl dicarboxylate, cyclohexene-4-glycidyl carboxylate, 5-norbornene-2- Mention may be made of methyl 2-glycidyl carboxylate and diglycidyl endo-cis-bicyclo [2.2.1] -5-heptene-2,3-diglycidyl carboxylate.
  • glycidyl esters of fatty acids are preferable, and glycidyl methacrylate is more preferable, because the adhesion to a base fabric is good.
  • the unsaturated epoxide may be contained singly or in combination of two or more in the olefin-based polymer containing an epoxy group.
  • Olefin-based polymers containing epoxy groups can be obtained by radical polymerization of the monomers (ie ethylene, alkyl (meth) acrylates and unsaturated epoxides).
  • the olefin polymer may also be a copolymer obtained by grafting an unsaturated epoxide onto a copolymer of ethylene, an alkyl (meth) acrylate and an optionally used ⁇ -olefin, a vinyl ester, or a diene.
  • the grafting procedure itself can be performed by known methods.
  • the olefin-based polymer is not an unsaturated epoxide-grafted polymer but a random terpolymer of ethylene / alkyl (meth) acrylate / unsaturated epoxide obtained by copolymerization of the respective monomers.
  • it is a terpolymer of ethylene / (meth) acrylic ester / glycidyl (meth) acrylate, and even more preferable that it is a terpolymer of ethylene / acrylic ester / glycidyl methacrylate.
  • the olefin polymer contains a monomer unit other than the above monomer unit, for example, a vinyl ester of a saturated carboxylic acid such as vinyl acetate or vinyl propionate, or a diene such as 1,4-hexadiene. It is also good.
  • the content of ethylene contained in the above-mentioned olefin-based polymer in the adhesive layer is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 55% by mass with respect to 100% by mass of the olefin-based polymer (terpolymer).
  • the content may be at least parts by weight and / or preferably at most 94% by weight, more preferably at most 87% by weight, and even more preferably at most 75% by weight.
  • the content may be a range defined by any of the lower limit and the upper limit, and may be a range in which any of the lower limit and the upper limit is combined.
  • the content of the alkyl (meth) acrylate contained in the above-mentioned olefin-based polymer in the adhesive layer is preferably 5% by mass or more, more preferably 10% by mass or more, with respect to 100% by mass of the olefin-based polymer (terpolymer). More preferably, it may be 20% by mass or more and / or preferably 45% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less.
  • the content of unsaturated epoxide contained in the olefin polymer in the adhesive layer is preferably 1% by mass or more, more preferably 3% by mass or more, more preferably 100% by mass of the olefin polymer (terpolymer). May be 5% by weight or more and / or preferably 25% by weight or less, more preferably 20% by weight or less, and still more preferably 15% by weight or less.
  • the content of unsaturated epoxide contained in the above-mentioned olefin-based polymer in the adhesive layer is preferably 0.1% by mass or more, more preferably 1% by mass, and further preferably 100% by mass of the olefin-based polymer (terpolymer) It may be preferably 5% by mass or more and / or preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less.
  • content of the monomer which has an epoxy group into 0.1 mass% or more, adhesiveness with the base fabric under high temperature and high humidity can be improved.
  • the chemical stability of the adhesive layer can be secured by setting the content to 20% by mass or less.
  • the content of the epoxy group in the olefin polymer is preferably 0.05% by mass or more, more preferably 0.1% by mass or more and / or preferably 5% by mass or less, more preferably 3% by mass or less can do.
  • the melting point of the olefin polymer is preferably 50 ° C. or more, more preferably 55 ° C. or more, and / or preferably 150 ° C. or less, more preferably 130 ° C. or less.
  • the melting point of the adhesive layer is also preferably 50 ° C. or more, more preferably 55 ° C. or more, and / or preferably 150 ° C. or less, more preferably 130 ° C. or less.
  • the melting point of the adhesive layer is 50 ° C. or more, the mechanical strength of the multilayer film and the laminate at normal temperature can be secured, and by the melting point of the adhesive layer being 150 ° C. or less, the multilayer film and the laminate are laminated. Processability can be improved because processing can be performed at a relatively low temperature during manufacture of the body.
  • the adhesive layer can contain another polymer or copolymer other than the olefin-based polymer containing an epoxy group.
  • the other polymers that can be contained in the adhesive layer include olefin-based polymers or copolymers that do not contain an epoxy group, such as ethylene / alkyl (meth) acrylate copolymers.
  • additives may be added to the adhesive layer in addition to the components described above.
  • the additives include pigments, fillers, antioxidants, hydrolysis stabilizers, antiblocking agents, and the like.
  • the content of the olefin-based polymer containing an epoxy group in the adhesive layer is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, based on the total amount of the adhesive layer. Preferably it is 95 mass% or more, More preferably, it can be 99.5 mass% or more.
  • the polymer component contained in the adhesive layer is preferably made of an olefin-based polymer containing an epoxy group, and the adhesive layer is more preferably made of an olefin-based polymer containing an epoxy group.
  • the adhesive layer may be a single layer or two or more layers.
  • two or more adhesive layers for example, two layers of a layer to which a colorant such as a pigment is added and a layer to which a colorant is not added can be used. This makes it possible to reduce the amount of colorant used as compared to the configuration in which the colorant is added to the entire adhesive layer having the same thickness as a whole.
  • the total thickness of the adhesive layer is preferably 5 to 50 ⁇ m, more preferably 5 to 30 ⁇ m.
  • the hermetic layer is a layer having a hermetic function that does not allow gas to flow in and out of the layer. Therefore, for example, when the multilayer film and the laminate of the present embodiment are formed into a bag, when the air is stored inside the bag, the airtight layer has a function to reliably prevent the air from leaking out. Can.
  • the hermetic layer preferably contains a thermoplastic polymer.
  • the thermoplastic polymer contained in the hermetic layer is not particularly limited, but may be a thermoplastic elastomer or a thermoplastic resin, and is preferably a thermoplastic elastomer.
  • a thermoplastic elastomer 1 or more types can be used among an amide type elastomer, an ester type elastomer, an olefin type elastomer, a styrene type elastomer, a urethane type elastomer, and a thermoplastic rubber crosslinked body, for example.
  • it is preferable to use an amide-based elastomer because of its excellent low temperature properties and flexibility.
  • the amide-based elastomer preferably has polyamide as a hard segment, and polyester or polyether as a soft segment.
  • examples of the polyamide in the polyamide elastomer include nylon 6, nylon 6, 6, nylon 11, nylon 12 and the like, among which nylon 12 is preferable.
  • the polyamide-based elastomer may contain the above-mentioned polyamide alone or in combination as a hard segment.
  • the content of the hard segment in the thermoplastic elastomer in the hermetic layer is preferably 65% by mass or more, more preferably 75% by mass or more, with respect to 100% by mass of the thermoplastic elastomer, and / or It is preferable that it is 95 mass% or less, and it is more preferable that it is 85 mass% or less.
  • the content of the soft segment in the thermoplastic elastomer in the hermetic layer is preferably 5% by mass or more, more preferably 15% by mass or more, with respect to 100% by mass of the thermoplastic elastomer, and / or It is preferable that it is 35 mass% or less, and it is more preferable that it is 25 mass% or less.
  • the melting point of the thermoplastic elastomer contained in the hermetic layer is not particularly limited as long as the melting point of the hermetic layer is higher than the melting point of the adhesive layer, but is preferably 100 ° C. or more, more preferably 130 ° C. or more It is preferable that the temperature is 300 ° C. or less, and more preferably 210 ° C. or less.
  • the melting point of the hermetic layer is also preferably 100 ° C. or more, more preferably 130 ° C. or more, and / or preferably 300 ° C. or less, more preferably 210 ° C. or less.
  • the melting point of the hermetic layer is higher than the melting point of the adhesive layer, but the difference between the melting point of the hermetic layer and the melting point of the adhesive layer can be preferably 10 ° C. or more, more preferably
  • the temperature can be 30 ° C. or higher, and / or can be 150 ° C. or lower, more preferably 100 ° C. or lower.
  • the heating temperature at the time of manufacture may fluctuate somewhat by setting the difference between the melting point of the hermetic layer and the melting point of the adhesive layer in the above range. Even if it is, it is possible to secure the airtight function of the airtight layer and the adhesive function of the adhesive layer. As a result, the occurrence of defective products in which the air tightness is impaired due to failure of the adhesive layer to soften sufficiently and adhesion with the base cloth can not be made well or the air tight layer is deformed or deteriorated The production stability can be improved.
  • the airtight layer can be blended with a polymer that is not a thermoplastic elastomer, such as polyamide resin, polyester resin, polyolefin resin, polyvinyl chloride, polyurethane, acrylic resin, polycarbonate and the like.
  • a polymer that is not a thermoplastic elastomer such as polyamide resin, polyester resin, polyolefin resin, polyvinyl chloride, polyurethane, acrylic resin, polycarbonate and the like.
  • the content of the amide-based elastomer in the hermetic layer is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more based on the total amount of the hermetic layer. More preferably, it can be 99.5% by mass or more. It is preferable that the polymer component contained in the hermetic layer is made of an amide-based elastomer, and it is more preferable that the hermetic layer be made of an amide-based elastomer.
  • additives may be added to the hermetic layer.
  • the additives include pigments, fillers, antioxidants, hydrolysis stabilizers, antiblocking agents, and the like.
  • the hermetic layer may be a single layer or two or more layers.
  • the thickness of the entire hermetic layer is preferably 5 to 50 ⁇ m, and more preferably 5 to 30 ⁇ m.
  • an intermediate layer can be provided between the hermetic layer and the adhesive layer.
  • middle layer is shown with typical sectional drawing.
  • the multilayer film 1 is laminated in the order of the adhesive layer 2, the intermediate layer 3 and the airtight layer 4.
  • the intermediate layer is a layer having a function of bonding the hermetic layer and the adhesive layer.
  • the composition of the intermediate layer can be selected according to the composition and thickness of the hermetic layer and the adhesive layer, the application of the multilayer film, and the like.
  • the intermediate layer preferably contains a thermoplastic polymer, more preferably an olefin-based polymer, depending on the types of the gas tight layer and the adhesive layer used.
  • the intermediate layer more preferably contains an olefin-based resin or elastomer, and more preferably contains an olefin-based resin.
  • the olefin resin include polyethylene, polypropylene, ethylene-propylene copolymer, polybutylene, polymethylpentene and the like.
  • polyethylene include low density polyethylene (LPDE), high density polyethylene (HDPE), and linear low density polyethylene (L-LDPE).
  • the intermediate layer may contain the above-mentioned olefin-based polymer singly or in combination of two or more.
  • the olefin-based polymer may be a modified olefin-based polymer obtained by combining an unsaturated carboxylic acid or an anhydride thereof by an addition reaction, a grafting reaction or the like.
  • a modified olefin polymer maleic anhydride modified olefin resin or maleic anhydride modified olefin elastomer is mentioned.
  • maleic anhydride modified polyethylene, maleic anhydride modified polypropylene and the like can be mentioned.
  • the intermediate layer may contain the above modified olefin-based polymer singly or in combination of two or more.
  • the intermediate layer preferably contains a maleic anhydride-modified olefin-based polymer as described above, because the adhesion to the polyamide is good, and the maleic anhydride-modified polyethylene Is more preferable, and it is further preferable to contain maleic anhydride modified low density polyethylene.
  • the adhesive layer contains an olefin-based polymer containing an epoxy group
  • the intermediate layer preferably contains polyethylene which is not maleic anhydride modified, and more preferably contains polyethylene which is not modified, It is further preferred to include high density polyethylene which is not maleic anhydride modified.
  • the melting point of the olefin-based polymer contained in the intermediate layer is preferably 50 ° C. or more, more preferably 60 ° C. or more, and / or preferably 200 ° C. or less, more preferably 180 ° C. or less.
  • the melting point of the intermediate layer is preferably 50 ° C. or more, more preferably 60 ° C. or less, and / or preferably 200 ° C. or less, more preferably 180 ° C. or less.
  • the middle layer may be two or more layers.
  • the composition of each layer may be the same or different.
  • the number of intermediate layers is two or more, by selecting the material of each intermediate layer so as to improve the adhesion between each layer in the multilayer film, the bond between the respective layers can be further strengthened, thereby And delamination in the multilayer film can be prevented.
  • FIG. 3 An example of a multilayer film provided with two intermediate layers is shown in FIG. 3 in a schematic cross-sectional view.
  • the multilayer film 1 is laminated in the order of the adhesive layer 2, the first intermediate layer 3 a, the second intermediate layer 3 b, and the airtight layer 4.
  • the first intermediate layer 3 a is directly bonded to the adhesive layer 2
  • the second intermediate layer 3 b is directly bonded to the adhesive layer 4.
  • the second interlayer directly bonded to the gas-tight layer is preferably a maleic anhydride-modified olefinic system. It may comprise a polymer, more preferably maleic anhydride modified low density polyethylene. Also, the first intermediate layer directly bonded to the adhesive layer is preferably non-maleic anhydride modified polyethylene, more preferably non-modified polyethylene, still more preferably non-maleic anhydride modified high density polyethylene Can be included.
  • the thickness of the entire intermediate layer can be preferably 5 to 50 ⁇ m, more preferably 5 to 30 ⁇ m.
  • additives may be added to each layer of the intermediate layer.
  • the additives include pigments, fillers, antioxidants, hydrolysis stabilizers, antiblocking agents, and the like.
  • a multilayer film can be produced by directly bonding the adhesive layer and the hermetic layer.
  • the multilayer film has an intermediate layer, it can be produced by directly bonding the adhesive layer and the intermediate layer, and directly bonding the intermediate layer and the hermetic layer.
  • the adhesive layer, the airtight layer, and, if necessary, the intermediate layer may be formed as separate sheets by extrusion or the like, and may be bonded and integrated.
  • the materials for the adhesive layer, the airtight layer, and the intermediate layer as needed may be brought into a molten state and simultaneously extruded (co-extrusion) and molded using an inflation method, a T-die method or the like.
  • an inflation method which can be enlarged and has excellent productivity.
  • the multilayer film produced can be cut into the desired shape and size depending on the application.
  • the multilayer film may be wound around a reel or the like, and may be unwound at the time of use.
  • a release sheet may be provided at least on the adhesive layer side, whereby the adhesive layer can be protected until immediately before use.
  • the multilayer film according to the present embodiment can be used by adhering to a base fabric.
  • the base fabric is a sheet-like structure that functions as a support for securing the mechanical strength of the laminate obtained by laminating the multilayer film and the base fabric.
  • the sheet shape includes, in addition to a planar shape, a shape formed in a tubular shape, a bag shape, or a balloon shape when viewed as a whole.
  • the base fabric preferably contains fibers.
  • the base fabric may be a woven fabric, a knitted fabric, a non-woven fabric, and may be fully or partially sewn.
  • a woven fabric is preferable because of high mechanical strength, and a biaxial structure in which a plurality of warps and a plurality of wefts are combined is preferable, and a plurality of warps, a plurality of wefts, and a plurality of diagonals are combined.
  • a three-axis structure can also be used.
  • the weave is not limited, and may be plain weave, twill weave, satin weave, and the like.
  • the base fabric is more preferably a plain weave fabric because of its strength and ease of manufacture.
  • the base cloth is not a flat base cloth, but OPW (One Piece Woven) woven into a cylindrical or bag shape without a seam so that it can have a curved surface according to the shape of the target product Is also included.
  • the above-mentioned OPW can be used in a state of being inflated and storing air therein, and can be suitably used in applications such as vehicle air bags.
  • the OPW used for a curtain airbag has a complex curved surface in which a plurality of rooms are formed, and can have a structure having unevenness when inflated.
  • peeling is more likely to occur between the base fabric and the film than when the film is adhered to an uneven base fabric.
  • the multilayer film according to the present embodiment the multilayer film can be adhered well even if it is an OPW having irregularities, and the delamination can be prevented.
  • the fibers contained in the base fabric may be synthetic fibers, natural fibers, regenerated fibers, semi-synthetic fibers, inorganic fibers, and combinations thereof (including blended yarns and mixed weaves).
  • synthetic fibers particularly polymer fibers
  • composite fibers such as core-sheath fibers, side-by-side fibers, and split-type fibers can also be used.
  • homopolyester such as polyalkylene terephthalate such as polyethylene terephthalate and polybutylene terephthalate
  • aliphatic dicarboxylic acid such as isophthalic acid, 5-sodium sulfoisophthalic acid or adipic acid as an acid component constituting the repeating unit of polyester Polyester fiber copolymerized with acid, etc., nylon 6, 6 nylon 6, nylon 12, nylon 4 6 and nylon 6 and nylon 6 6 copolymer, nylon with polyalkylene glycol, dicarboxylic acid, amines etc.
  • Sulfur such as aramid fiber represented by polymerized polyamide fiber, copolymerization with paraphenylene terephthalamide and aromatic ether, rayon fiber, ultra high molecular weight polyethylene fiber, paraphenylene sulfone, polysulfone and the like Down fibers, polyether ketone fibers and the like.
  • the base fabric may contain two or more fibers.
  • the backing is a fabric
  • different types of fibers can be used as the fibers used for yarns extending in different directions. More specifically, in the case of having a biaxial structure including a warp and a weft, the warp and the weft can be fibers of different types. In this case, at least one of the warp yarn and the weft yarn can be made of polyester fiber.
  • the backing can comprise polyester.
  • the base fabric can include fibers made of polyester or fibers containing polyester. That is, the base fabric may contain polyester fibers mixed with other fibers by mixing, etc., or may contain a blended fiber of polyester and a material other than polyester, or polyester and polyester The core-sheath type, the side-by-side type, and the split type composite fibers made of other materials may be included.
  • the base fabric contains polyester, the laminate can be manufactured relatively inexpensively while securing the mechanical strength and the weather resistance of the laminate.
  • the base fabric is made of polyester fibers, the above-mentioned effect is further exhibited.
  • polyester contained in a base fabric polyalkylene terephthalate or polyalkylene naphthalate is preferable.
  • the polyester include homopolyesters such as polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), and polyesters
  • the acid component constituting the unit include copolymers obtained by copolymerizing aliphatic dicarboxylic acids such as isophthalic acid, 5-sodium sulfoisophthalic acid and adipic acid.
  • the above polyesters can be used alone or in combination of two or more in the form of mixed weave, blend, composite fiber, or polymer blend.
  • Fibers other than polyester fibers that may be included in the base fabric may be one or more of synthetic fibers made of materials other than polyester, natural fibers, regenerated fibers, semi-synthetic fibers, and inorganic fibers. Further, as materials other than polyester, polyamide, polyolefin, aramid, acrylic, vinylon, polyurethane and the like can be mentioned.
  • the backing when the backing is a textile, the backing may comprise two or more different fibers, in which case, for example, the fibers or yarns extending in different directions can be of different types.
  • the fibers or yarns extending in different directions can be of different types.
  • the warp and the weft can be different types of fibers.
  • at least one of the warp yarn and the weft yarn can be made of polyester fiber.
  • the yarn contained in the backing may be monofilament or multifilament.
  • the yarn is a multifilament, it is preferable that the total fineness of the yarn (single yarn fineness ⁇ multiple yarn number) is 100 to 700 dtex.
  • the single yarn fineness of the fibers used in the base fabric is preferably 1 to 10 dtex.
  • the weave density is preferably 5 to 30 yarns / cm 2 for each of the warp yarns and weft yarns.
  • the base fabric may be closed, or may have an opening because the resulting laminate can be made lighter.
  • a multilayer film formed in advance is laminated on the base fabric to form a laminate. Therefore, even if a base fabric having an opening is used as a base fabric to be adhered to the multilayer film of the present embodiment, sufficient mechanical properties are prevented without causing disadvantages such as penetration of a polymer composition having a relatively low viscosity. A laminate having strength and air tightness can be obtained.
  • FIG. 4 shows a schematic cross-sectional view of a laminate according to an embodiment of the present invention.
  • the laminate 10 is configured by bonding the multilayer film 1 provided with the above-mentioned airtight layer 4 and the adhesive layer 2 and the base fabric 8.
  • the multilayer film 1 is disposed on one surface of the base fabric 8, but the multilayer film of the present embodiment can also be provided on both sides of the base fabric 8.
  • the multilayer films 1A and 1B are respectively from above and below on the surface of the OPW 9 (base fabric 8) in a state where the air of the bag is extracted and folded. It may be laminated.
  • the laminate of the form shown in FIG. 5 can be used as an air bag or the like because it can store air inside.
  • the multilayer films 1, 1A, 1B do not have an intermediate layer, but the multilayer film of each example may have one or more of the above-mentioned intermediate layers. .
  • the laminate can be adhered to the backing by heating and / or pressing the above-mentioned multilayer film. At that time, it is considered that the epoxy group contained in the olefin-based polymer in the adhesive layer irreversibly reacts with the polyester in the base fabric to form a bond. Such bonding can improve the durability of the laminate under high temperature and / or high humidity.
  • One embodiment of the present invention is a method for producing a laminate having the above-described multilayer film and a base fabric, and by pressing the multilayer film and the base fabric while heating at a temperature at which the hermetic layer does not melt, Bonding the multilayer film to the base fabric.
  • the "film” means a flexible thin film, and the state of temperature, hardness and the like does not matter. That is, the multilayer film to be supplied may be at normal temperature or lower, or may have a temperature higher than normal temperature. In addition, it may be softened to be able to at least partially exhibit an adhesive function. Therefore, the laminate according to the present embodiment can be manufactured, for example, by bonding a multilayer film supplied at normal temperature or less to a base fabric while heating it at a temperature below the melting point of the hermetic layer using a heating means. Also, for example, it can be produced by bonding a polymer, which is heated by an extruder and extruded into a film, to a base cloth.
  • FIG. 6 schematically shows a laminate manufacturing apparatus 100 for carrying out the method of manufacturing a laminate according to the present embodiment.
  • stacked on both surfaces of the base fabric 8 is demonstrated.
  • the layered product manufacturing apparatus 100 includes a heating unit 102 and a cooling unit 104.
  • the base fabric 8 and the multilayer films 1A and 1B previously wound up in a reel or the like are respectively unwound, and both sides of the base fabric 8 (upper surface And the lower surface) of the multilayer films 1A and 1B, respectively.
  • the multilayer film 1A, the base fabric 8 and the multilayer film 1B, which are superimposed, are sent to the heating unit 102, and pressure is applied while heating in the heating unit 102.
  • the heating unit 102 includes, for example, a pressing unit including a pair of opposing rolls (such as nip rolls) or a pair of opposing belts as in the example of FIG.
  • a pressing unit including a pair of opposing rolls (such as nip rolls) or a pair of opposing belts as in the example of FIG.
  • the heating temperature is set to a temperature at which the adhesive layer softens or melts and the hermetic layer does not melt (melt).
  • the adhesive layer can be pressed against the base fabric in a state where the adhesive layer is sufficiently softened or melted while securing the function of the hermetic layer. Then, the softened or melted adhesive layer can also penetrate into the concavities and convexities of the surface of the base fabric, so that the adhesive layer can be tightly adhered to the base fabric.
  • multilayer film 1A, 1B can be each adhere
  • the heating temperature can be set, for example, to a temperature lower than the melting point of the hermetic layer, whereby the function of the hermetic layer can be ensured more reliably. Further, the heating temperature may be a temperature at which the hermetic layer does not lose its hermetic function under the influence of heat.
  • the stacked body 10 that has passed through the heating unit 102 is transported to the cooling unit 104.
  • the temperature of the laminate 10 can be lowered preferably to room temperature. That is, the method for manufacturing a laminate according to the present embodiment may further include a cooling step.
  • the cooling unit 104 may include a cooling unit including a cooling medium, an intake unit, and the like. Further, as in the example of FIG. 6, the cooling unit 104 may be pressurized using a pressing unit including a pair of opposing belts, but the pressing is not necessarily required.
  • the laminate 10 is wound on a reel as needed, as shown in FIG.
  • either of the multilayer films 1A and 1B can be abbreviate
  • surface of the base fabric 8 can be manufactured.
  • the base fabric 8 it is also possible to use a tubular or bag-like OPW 9 woven without a seam. Thereby, a laminate as shown in FIG. 5 can be manufactured.
  • the base fabric 8 is OPW
  • air is removed from the inside of the OPW to flatten it, and the one previously wound on a reel or the like is used. Similar to the above-described example, the OPW is unwound before being superimposed, and the multilayer films 1A and 1B are respectively superimposed on the upper surface and the lower surface.
  • FIG. 7 schematically shows a state in which the multilayer films 1A and 1B are respectively superimposed on the upper surface and the lower surface of the OPW 9 (base fabric 8) loaded into the laminate manufacturing apparatus 100 in a flat state.
  • the multilayer film 1A, the OPW 9 (base fabric 8), and the multilayer film 1B stacked together are pressed from both sides by a pair of pressing means in the pressing unit 102.
  • multilayer films 1A and 1B are bonded to the upper and lower surfaces of OPW 9 (base fabric 8), respectively, and the edges of multilayer films 1A and 1B are bonded to each other by heating and pressing or by an adhesive or the like.
  • a laminate 10 as shown in FIG. 5 can be obtained.
  • the adhesive layers 2A and 2B can be adhered so as to cover the entire edge of the OPW 9 (base fabric 8). Also, the extra edge of the laminate 10 can be removed by cutting or the like. In this manner, it is possible to manufacture a laminate in which the base fabric is formed in a bag shape, and the multilayer film is formed on the entire surface of the OPW 9 (base fabric 8). The laminate thus obtained can be used as an air bag.
  • the heating temperature at the time of manufacturing a laminated body will not be specifically limited if it is the temperature which an airtight layer does not melt
  • the heating temperature may be a temperature below the melting point of the hermetic layer and a temperature at which the adhesive layer softens.
  • the heating temperature and pressure depend on the configuration of the multilayer film and the base fabric, the heating temperature is preferably 100 ° C. or more, more preferably 120 ° C. or more, and / or 250 ° C. or less C. or less, more preferably 200.degree. C. or less.
  • the pressurizing pressure is preferable to be 5N / cm 2 or more, it can be 10 N / cm 2 or more, and / or preferable to be 700 N / cm 2 or less, to 500 N / cm 2 or less Can. Furthermore, it can be 5 to 50 N / cm 2 according to the operating conditions at the time of manufacturing the laminate.
  • the multilayer film and the laminate according to the present embodiment are suitably used in vehicle airbags, outdoor products, packaging applications and the like, and particularly suitably used in the manufacture of vehicle airbags, particularly curtain airbags.
  • the curtain airbag is attached to a roof line or the like in the upper portion of the side window, and refers to an airbag that is deployed in a curtain shape vertically downward along the side window when a high load is applied in a collision or the like.
  • the material of the curtain airbag is required to have pressure resistance, specifically, Mechanical strength such as strength and tear strength is required.
  • the curtain airbag is often stored in a casing or the like in a folded or rolled state for a long time before deployment, flexibility is also required.
  • when stored it is often exposed to high temperature and high humidity environments.
  • the multilayer film and the laminate according to the present embodiment can be suitably used even in such applications.
  • security is requested
  • the standards for safety are set in each country, but the standards tend to be strict.
  • temperature and humidity conditions in the conventional high temperature and high humidity adhesion test are temperature What was 40.degree. C. and 92% relative humidity becomes more severe as 70.degree. C. temperature and 95% relative humidity. Therefore, there has been a demand for an air bag material that can withstand such severe high temperature and high humidity environment.
  • the multilayer film and the laminate according to the present embodiment are unlikely to cause delamination even after being stored under such severe high temperature and high humidity, and can exhibit excellent durability.
  • a multilayer film was formed, and the multilayer film was further adhered to a base fabric to produce a laminate, which was evaluated.
  • a 100 ⁇ m-thick polyethylene terephthalate film is attached to the airtight layer side of the multilayer film through an adhesive. It reinforced and used.
  • Example 1 (Preparation of multilayer film) In an inflation extrusion apparatus (manufactured by Collin) having four extruders, terpolymers of ethylene, acrylic ester, and glycidyl methacrylate (“LOTADER® AX 8900” manufactured by Arkema, content of glycidyl methacrylate: 8% by mass, Melting point: 65 ° C), high density polyethylene (“HMA014" manufactured by Exxonmobile, melting point: 134 ° C), and low density polyethylene modified with maleic anhydride (“Plexar PX800” manufactured by Lyondell Basell, melting point 117 ° C to 125 ° C) A polyamide (“Vestamid (registered trademark)” manufactured by Evonik, melting point 170 ° C.) was frequently added, and melted at a temperature higher than the melting point of each resin to prepare a four-layer film by an inflation method. The extrusion rate of each layer was 10 g / m 2 .
  • the obtained four-layer film is a terpolymer of ethylene, acrylic ester and glycidyl methacrylate as an adhesive layer, high density polyethylene as a first intermediate layer, low density polyethylene modified with maleic anhydride as a second intermediate layer, and polyamide as an airtight layer. Were stacked in the order described.
  • Example 1 shows the outstanding high temperature high humidity adhesiveness.
  • the adhesive layer comprises an olefin-based polymer containing an epoxy group
  • the multilayer film wherein the melting point of the hermetic layer is higher than the melting point of the adhesive layer.
  • the multilayer film according to claim 1 wherein the content of epoxy group of the olefin-based polymer is 0.05 to 5% by mass with respect to the total amount of the olefin-based polymer.
  • the intermediate layer has a first intermediate layer and a second intermediate layer, the first intermediate layer is bonded to the adhesive layer, and the second intermediate layer is bonded to the air tight layer.
  • Appendix 9 A laminate, wherein the multilayer film according to any one of appendices 1 to 8 and a base fabric containing polyester are adhered.
  • a method for producing a laminate comprising a base fabric and a multilayer film,
  • the base fabric comprises polyester and
  • the multilayer film is a multilayer film having an adhesive layer containing an olefin-based polymer containing an epoxy group, and an airtight layer bonded to the adhesive layer, having a melting point higher than that of the adhesive layer, and containing a polymer.
  • a method for producing a laminate comprising the step of adhering the multilayer film and the base fabric by pressing the multilayer film and the base fabric while heating at a temperature at which the hermetic layer does not melt.
  • the heating temperature is 130 to 200 ° C.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Air Bags (AREA)

Abstract

A multilayered film to be bonded to fabric, the multilayered film comprising an adhesive layer to be bonded to the fabric and an airtight layer bonded to the adhesive layer, wherein the adhesive layer comprises an olefin-based polymer containing epoxy groups and the airtight layer has a higher melting point than the adhesive layer.

Description

多層フィルム、積層体、積層体の製造方法、及びエアバッグMultilayer film, laminate, method of producing laminate, and airbag
 本発明は、多層フィルム、積層体、積層体の製造方法、及びエアバッグに関する。 The present invention relates to a multilayer film, a laminate, a method of manufacturing a laminate, and an air bag.
 従来、基布とその上に積層されたフィルムとを備えた積層体が知られている。例えば、特許文献1には、車両用エアバッグとして使用される積層体であって、経糸及び緯糸を有する織物にフィルムがドライラミネートされてなるものが開示されている。 Conventionally, a laminate having a base fabric and a film laminated thereon is known. For example, Patent Document 1 discloses a laminate used as a vehicle air bag, in which a film is dry-laminated on a woven fabric having warp yarns and weft yarns.
国際公開第2015/065273号International Publication No. 2015/065273
 ところで、上記のような積層体は、温度若しくは湿度、又はその両方が高い環境で使用されることがある。そのため、近年、積層体には、そのような厳しい環境下での耐久性の向上が求められている。 By the way, the above-mentioned laminate may be used in an environment where temperature or humidity or both are high. Therefore, in recent years, the laminated body is required to improve the durability under such a severe environment.
 しかしながら、特許文献1に記載の発明では、高温及び/又は高湿での積層体の耐久性については、何ら検討されていない。 However, in the invention described in Patent Document 1, the durability of the laminate at high temperature and / or high humidity is not studied at all.
 上記の点に鑑みて、本発明の一形態は、高温及び/又は高湿の環境下での耐久性に優れた積層体の製造を可能にする多層フィルムを提供することを課題とする。 In view of the above-mentioned point, one form of the present invention makes it a subject to provide a multilayer film which enables manufacture of a layered product excellent in endurance under high temperature and / or a high humidity environment.
 上記課題を解決するために、本発明の一形態は、基布に接着して使用される多層フィルムであって、前記基布に接着される側となる接着層と、当該接着層に結合されている気密層とを有し、前記接着層は、エポキシ基を含有するオレフィン系ポリマーを含み、前記気密層の融点は前記接着層の融点よりも高い。 In order to solve the above problems, an embodiment of the present invention is a multilayer film used by bonding to a base fabric, and an adhesive layer to be bonded to the base fabric and the adhesive layer And the adhesive layer comprises an olefin-based polymer containing an epoxy group, and the melting point of the hermetic layer is higher than the melting point of the adhesive layer.
 本発明の一形態によれば、高温及び/又は高湿の環境下での耐久性に優れた積層体の製造を可能にする多層フィルムを提供することができる。 According to one aspect of the present invention, it is possible to provide a multilayer film that enables the production of a laminate excellent in durability under high temperature and / or high humidity environments.
本発明の一形態による多層フィルムの模式的な断面図である。1 is a schematic cross-sectional view of a multilayer film according to an aspect of the present invention. 本発明の一形態による多層フィルムの模式的な断面図である。1 is a schematic cross-sectional view of a multilayer film according to an aspect of the present invention. 本発明の一形態による多層フィルムの模式的な断面図である。1 is a schematic cross-sectional view of a multilayer film according to an aspect of the present invention. 本発明の一形態による積層体の模式的な断面図である。It is a typical sectional view of a layered product by one form of the present invention. 本発明の一形態による積層体の模式的な断面図である。It is a typical sectional view of a layered product by one form of the present invention. 本発明の一形態による積層体を製造するための装置の模式図である。FIG. 1 is a schematic view of an apparatus for manufacturing a laminate according to an aspect of the present invention. 本発明の一形態による積層体の製造工程における基布と多層フィルムとの積層について説明する模式図である。It is a schematic diagram explaining lamination | stacking with the base fabric and multilayer film in the manufacturing process of the laminated body by one form of this invention.
 (多層フィルム)
 本発明の一形態による多層フィルムは、基布に接着して使用されるものであって、基布に接着される側となる接着層と、接着層に結合されている気密層とを有し、接着層は、エポキシ基を含有するオレフィン系ポリマーを含み、気密層の融点は接着層の融点よりも高い。
(Multilayer film)
A multilayer film according to one aspect of the present invention is used by bonding to a base fabric, and has an adhesive layer on the side to be bonded to the base fabric and an airtight layer bonded to the adhesive layer. The adhesive layer contains an olefin-based polymer containing an epoxy group, and the melting point of the hermetic layer is higher than the melting point of the adhesive layer.
 図1に、多層フィルムの一例を模式的な断面図で示す。図1の例では、多層フィルム1は、気密層4と、この気密層4に接合されている、すなわち気密層4に直接的に結合されている接着層2とを有する。多層フィルム1は、基布に接着させて使用することができ、接着の際には、接着層2は、基布に接着される側となる。多層フィルム1が基布に接着されて図4に示すような積層体10が形成される場合、接着層2は、基布8に直接的に積層され、得られた積層体10中では、基布8と気密層4との間に挟まれた内部の層となる。よって、接着層2は、気密層4と基布8とを結合させる層ともいえる。 In FIG. 1, an example of a multilayer film is shown by typical sectional drawing. In the example of FIG. 1, the multilayer film 1 comprises a gas-tight layer 4 and an adhesive layer 2 bonded to the gas-tight layer 4, ie directly bonded to the gas-tight layer 4. The multilayer film 1 can be used by being adhered to a base cloth, and in the case of adhesion, the adhesive layer 2 is the side to be adhered to the base cloth. When the multilayer film 1 is adhered to the base fabric to form a laminate 10 as shown in FIG. 4, the adhesive layer 2 is directly laminated to the base fabric 8 and in the obtained laminate 10 It becomes an inner layer sandwiched between the cloth 8 and the airtight layer 4. Therefore, the adhesive layer 2 can be said to be a layer which bonds the airtight layer 4 and the base fabric 8.
 本明細書において、気密層とは、当該層の内外で気体を流通させない機能(以下、気密機能ともいう)を有する層である。また、接着層とは、基布に対する接着性を示す層であり、この接着性は、所定の条件下、例えば温度及び/又は圧力を上昇させた条件下で軟化又は融解させることにより発現されるものであってよい。 In the present specification, the airtight layer is a layer having a function of preventing gas from flowing in and out of the layer (hereinafter, also referred to as an airtight function). The adhesive layer is a layer exhibiting adhesion to the base fabric, and the adhesion is exhibited by softening or melting under predetermined conditions, for example, under conditions of increased temperature and / or pressure. It may be
 本形態では、多層フィルムが、エポキシ基を含有するオレフィン系ポリマーを含む接着層を有することによって、多層フィルムを、基布に接着させて積層体を作製した場合に、高温及び/又は高湿の環境下での耐久性に優れた積層体を得ることができる。なお、本明細書では、高温とは、常温を超える温度を指し、高湿とは、常湿を超える湿度を指す。ここで、常温とは、5~35℃の温度範囲を指し、常湿とは、45~85%の相対湿度の範囲を指す。よって、本形態の多層フィルムは、35℃を超える温度及び/又は85%を超える相対湿度の条件下で所定時間保存された後であっても、優れた耐久性を示すことができる。また、本形態の多層フィルムは、好ましくは50℃以上、より好ましくは70℃以上の温度条件であっても、且つ/又は好ましくは90%以上、より好ましくは95%以上の湿度条件であっても、優れた耐久性を示すことができる。また、上記の高温及び高湿条件下で、例えば、84時間以上、より好ましくは168時間以上、さらに好ましくは408時間以上で保存した後であっても優れた耐久性を示すことができる。 In this embodiment, the multilayer film has an adhesive layer containing an olefin-based polymer containing an epoxy group, whereby the multilayer film is adhered to a base fabric to produce a laminate; A laminate excellent in durability under the environment can be obtained. In addition, in this specification, high temperature refers to the temperature exceeding normal temperature, and high humidity refers to the humidity exceeding normal humidity. Here, normal temperature refers to a temperature range of 5 to 35 ° C., and normal humidity refers to a range of relative humidity of 45 to 85%. Therefore, the multilayer film of the present embodiment can exhibit excellent durability even after being stored for a predetermined time under conditions of a temperature above 35 ° C. and / or a relative humidity above 85%. In addition, the multilayer film of the present embodiment preferably has a temperature of 50 ° C. or more, more preferably 70 ° C. or more, and / or a humidity of 90% or more, more preferably 95% or more. Can also exhibit excellent durability. In addition, excellent durability can be exhibited even after storage under the above-described high temperature and high humidity conditions, for example, 84 hours or more, more preferably 168 hours or more, and still more preferably 408 hours or more.
 積層体の耐久性は、例えば、多層フィルムと基布とを接着させて積層体を作製し、その積層体を、上述のような高温及び/又は高湿の環境下で所定時間保存した後、多層フィルムと基布との間での耐層間剥離性(剥離強度又は破壊強度)を測定することによって評価することができる。この耐層間剥離性の評価には、多層フィルム内の各層間での耐層間剥離性の評価を含めることができる。 The durability of the laminate is obtained, for example, by bonding a multilayer film and a base fabric to prepare a laminate, and storing the laminate under a high temperature and / or high humidity environment as described above for a predetermined time, It can be evaluated by measuring the delamination resistance (peel strength or breaking strength) between the multilayer film and the base fabric. The evaluation of the delamination resistance can include the evaluation of the delamination resistance between layers in the multilayer film.
 多層フィルムは、気密層と接着層とを有する少なくとも2層を有する多層構造となっている。これにより、多層フィルムを基布へ接着させる際の接着機能と、得られる積層体における気密機能とを各層に別個に持たせることができる。そのため、本形態による多層フィルムを用いた場合、単層フィルムを基布に接着させる場合と比べて、多層フィルムの接着機能と気密機能との両方を確実に発揮する高品質の積層体を製造することができる。 The multilayer film has a multilayer structure having at least two layers having an airtight layer and an adhesive layer. Thereby, each layer can separately have an adhesion function at the time of adhering the multilayer film to the base fabric and an airtight function in the obtained laminate. Therefore, when the multilayer film according to the present embodiment is used, a high-quality laminate that reliably exhibits both the adhesive function and the airtight function of the multilayer film is manufactured as compared to the case where the single layer film is adhered to the base fabric. be able to.
 また、気密層の融点は、接着層の融点よりも高くなっている。このように、本形態では、気密層及び接着層の各層に、熱に対する挙動が異なる材料を用いているため、多層フィルムを加熱して基布に接着させる場合、気密層の軟化を抑えつつ、接着層を、基布との接着に適した柔らかさに軟化又は融解させることができる。これにより、製造時の温度や圧力の条件の変動があっても、基布への確実な接着と多層フィルムの気密性の維持とを両立させて積層体を製造することができる。 In addition, the melting point of the hermetic layer is higher than the melting point of the adhesive layer. As described above, in the present embodiment, since materials having different heat behavior are used for each of the airtight layer and the adhesive layer, when the multilayer film is heated and adhered to the base fabric, the softening of the airtight layer is suppressed. The adhesive layer can be softened or melted to a softness suitable for adhesion to the backing. As a result, even when the conditions of temperature and pressure at the time of production are changed, the laminate can be produced while achieving both the reliable adhesion to the base cloth and the maintenance of the airtightness of the multilayer film.
 上述のように接着層が接着機能を発揮できるため、多層フィルムは、別途接着剤等を用いることなく、基布に良好に接着させることができる。これにより、接着剤の使用による手間やコストを低減することができる。また、長期間使用する場合や高温高湿の環境下で使用する場合等に、接着剤の変質によって積層体が柔軟性を失ったり、層間剥離が生じたりすることを防止できる。 As described above, since the adhesive layer can exhibit the adhesive function, the multilayer film can be favorably adhered to the base cloth without using an adhesive or the like separately. Thereby, the effort and cost by use of an adhesive agent can be reduced. Further, when used for a long time or under a high temperature and high humidity environment, it is possible to prevent the laminate from losing its flexibility or causing delamination due to the deterioration of the adhesive.
 本明細書において、層の融点とは、層の温度を上昇させた場合に層が軟化して、層中のポリマーの分子同士が相対運動を始め、ポリマーが流動性を示すようになる温度を指す。よって、接着層及び気密層の融点は、それぞれ接着層及び気密層中のポリマー成分(ポリマーアロイを含む)の融点ということができる。このようなポリマーの融点は、示差走査熱量計で測定された融解ピーク温度とすることができる。 As used herein, the melting point of a layer is the temperature at which the layer softens when the temperature of the layer is raised, and the molecules of the polymer in the layer begin to move relative to each other, causing the polymer to become fluid. Point to. Therefore, the melting point of the adhesive layer and the hermetic layer can be said to be the melting point of the polymer component (including the polymer alloy) in the adhesive layer and the hermetic layer, respectively. The melting point of such a polymer can be the melting peak temperature measured by differential scanning calorimetry.
 (接着層)
 上述のように、接着層は、多層フィルムを基布に接着させる際に、基布側となる層であり、所定条件下で基布に対する接着性を示す層である。さらに、得られる積層体においては、接着層は気密機能を有することもできる。
(Adhesive layer)
As described above, the adhesive layer is a layer on the side of the base fabric when the multilayer film is adhered to the base fabric, and is a layer showing adhesiveness to the base fabric under predetermined conditions. Furthermore, in the resulting laminate, the adhesive layer can also have an airtight function.
 本形態では、接着層は、エポキシ基を含有するオレフィン系ポリマーを含む。接着層が、エポキシ基を含むポリマーを含んでいることで、ポリエステルを含む基布に対し、高温及び/又は高湿の環境下での接着性を向上させることができるため、基布と接着層との間で剥離が生じにくくなり、耐久性を向上させることができる。 In the present embodiment, the adhesive layer contains an olefin-based polymer containing an epoxy group. Since the adhesive layer contains a polymer containing an epoxy group, it can improve the adhesion to a polyester-containing base fabric under high temperature and / or high humidity environments, so the base fabric and the adhesive layer Between the above and the other can hardly occur, and the durability can be improved.
 接着層に含まれるエポキシ基を含有するオレフィン系ポリマーは、エポキシ基を含有するモノマー単位と、別のモノマー単位とを含むコポリマーであると好ましく、例えば、α-オレフィン/不飽和カルボン酸エステル/エポキシ基を有するモノマー単位のターポリマー(三元共重合体)とすることができる。 The olefin-based polymer containing an epoxy group contained in the adhesive layer is preferably a copolymer containing a monomer unit containing an epoxy group and another monomer unit. For example, α-olefin / unsaturated carboxylic acid ester / epoxy It can be a terpolymer (terpolymer) of monomer units having a group.
 ターポリマー中のα-オレフィンとしては、エチレン、プロピレン、1-ブテン、1-ペンテン、3-メチル-1-ブテン、1-ヘキセン、4-メチル-1-ペンテン、3-メチル-1-ペンテン、1-オクテン、1-デセン、1-ドデセン、1-テトラデセン、1-ヘキサデセン、1-オクタデセン、1-エイコセン、1-ドコセン、1-テトラコセン、1-ヘキサコセン、1-オクタコセン、及び1-トリアコンテンが挙げられる。上記のα-オレフィンは、ターポリマー中に単独で又は2種以上含まれていてよい。 Examples of α-olefins in terpolymers include ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, 1-docosene, 1-tetracocene, 1-hexacocene, 1-octacocene, and 1-triaconcene It can be mentioned. The above α-olefins may be contained singly or in combination of two or more in the terpolymer.
 上記ターポリマーにおける不飽和カルボン酸エステルは、アルキル(メタ)アクリレートであると好ましい。本明細書においては、「(メタ)アクリレート」とは、メタクリレート及び/又はアクリレートを指す。アルキル(メタ)アクリレートとしては、アルキル基が1~24個の炭素原子を有するものが挙げられる。具体例としては、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n-ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、及び2-エチルへキシル(メタ)アクリレートが挙げられ、これらのアルキル(メタ)アクリレートは、エポキシ基を含有するオレフィン系ポリマー中に単独で又は2種以上含まれていてよい。 The unsaturated carboxylic acid ester in the terpolymer is preferably an alkyl (meth) acrylate. As used herein, "(meth) acrylate" refers to methacrylate and / or acrylate. The alkyl (meth) acrylates include those in which the alkyl group has 1 to 24 carbon atoms. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. The acrylate may be contained singly or in combination of two or more in the olefin-based polymer containing an epoxy group.
 上記ターポリマーにおけるエポキシ基を有するモノマー単位は、不飽和エポキシドであると好ましい。不飽和エポキシドとしては、脂肪酸のグリシジルエステル及びエーテル、並びに脂環式グリシジルのエステル及びエーテル等が挙げられる。脂肪酸のグリシジルエステル及びエーテルとしては、例えばアリルグリシジルエーテル、ビニルグリシジルエーテル、グリシジルマレエート、グリシジルイタコネート、グリシジル(メタ)アクリレートが挙げられる。また、脂環式グリシジルのエステル及びエーテルとしては、例えば、2-シクロヘキセン-1-グリシジルエーテル、シクロヘキセン-4,5-ジグリシジルジカルボキシレート、シクロヘキセン-4-グリシジルカルボキシレート、5-ノルボルネン-2-メチル-2-グリシジルカルボキシレート、及びジグリシジルエンド-シス-ビシクロ[2.2.1]-5-ヘプテン-2,3-ジグリシジルカルボキシレートが挙げられる。上記のうち、基布に対する接着性が良好であることから、脂肪酸のグリシジルエステルが好ましく、グリシジルメタクリレートがより好ましい。上記不飽和エポキシドは、エポキシ基を含有するオレフィン系ポリマー中に単独で又は2種以上含まれていてよい。 The monomer unit having an epoxy group in the above terpolymer is preferably unsaturated epoxide. Unsaturated epoxides include glycidyl esters and ethers of fatty acids, and esters and ethers of cycloaliphatic glycidyls and the like. Glycidyl esters and ethers of fatty acids include, for example, allyl glycidyl ether, vinyl glycidyl ether, glycidyl maleate, glycidyl triconate, and glycidyl (meth) acrylate. Further, as esters and ethers of alicyclic glycidyl, for example, 2-cyclohexene-1-glycidyl ether, cyclohexene-4,5-diglycidyl dicarboxylate, cyclohexene-4-glycidyl carboxylate, 5-norbornene-2- Mention may be made of methyl 2-glycidyl carboxylate and diglycidyl endo-cis-bicyclo [2.2.1] -5-heptene-2,3-diglycidyl carboxylate. Among the above, glycidyl esters of fatty acids are preferable, and glycidyl methacrylate is more preferable, because the adhesion to a base fabric is good. The unsaturated epoxide may be contained singly or in combination of two or more in the olefin-based polymer containing an epoxy group.
 エポキシ基を含有するオレフィン系ポリマーは、モノマー(すなわち、エチレン、アルキル(メタ)アクリレート、及び不飽和エポキシド)のラジカル重合で得ることができる。 Olefin-based polymers containing epoxy groups can be obtained by radical polymerization of the monomers (ie ethylene, alkyl (meth) acrylates and unsaturated epoxides).
 また、上記オレフィン系ポリマーは、エチレンと、アルキル(メタ)アクリレートと、任意に用いられるα-オレフィン、ビニルエステル、又はジエンとのコポリマーに、不飽和エポキシドをグラフトしたコポリマーであってもよい。グラフト操作自体は周知の方法によって行うことができる。しかし、オレフィン系ポリマーは、不飽和エポキシドをグラフトさせたポリマーではなく、各モノマーの共重合で得られたエチレン/アルキル(メタ)アクリレート/不飽和エポキシドのランダムターポリマーであると好ましい。エチレン/(メタ)アクリルエステル/グリシジル(メタ)アクリレートのターポリマーであるとより好ましく、エチレン/アクリルエステル/グリシジルメタクリレートのターポリマーであるとさらに好ましい。 The olefin polymer may also be a copolymer obtained by grafting an unsaturated epoxide onto a copolymer of ethylene, an alkyl (meth) acrylate and an optionally used α-olefin, a vinyl ester, or a diene. The grafting procedure itself can be performed by known methods. However, it is preferable that the olefin-based polymer is not an unsaturated epoxide-grafted polymer but a random terpolymer of ethylene / alkyl (meth) acrylate / unsaturated epoxide obtained by copolymerization of the respective monomers. It is more preferable that it is a terpolymer of ethylene / (meth) acrylic ester / glycidyl (meth) acrylate, and even more preferable that it is a terpolymer of ethylene / acrylic ester / glycidyl methacrylate.
 なお、上記オレフィン系ポリマーは、上記のモノマー単位以外のモノマー単位、例えば、飽和カルボン酸のビニルエステル、例えば酢酸ビニル又はプロピオン酸ビニル、ジエン、例えば1,4-ヘキサジエン等のモノマー単位を含んでいてもよい。 The olefin polymer contains a monomer unit other than the above monomer unit, for example, a vinyl ester of a saturated carboxylic acid such as vinyl acetate or vinyl propionate, or a diene such as 1,4-hexadiene. It is also good.
 接着層中の上記オレフィン系ポリマーに含まれるエチレンの含有量は、オレフィン系ポリマー(ターポリマー)100質量%に対して、好ましくは30質量%以上、より好ましくは40質量%以上、さらに好ましくは55質量部%以上、そして/あるいは、好ましくは94質量%以下、より好ましくは87質量%以下、さらに好ましくは75質量%以下であってよい。上記含有量は、上記下限値及び上限値のいずれかで規定される範囲であってよく、上記下限値及び上限値のいずれを組み合わせた範囲であってもよい。以下、他の成分及び条件についても同様である。 The content of ethylene contained in the above-mentioned olefin-based polymer in the adhesive layer is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 55% by mass with respect to 100% by mass of the olefin-based polymer (terpolymer). The content may be at least parts by weight and / or preferably at most 94% by weight, more preferably at most 87% by weight, and even more preferably at most 75% by weight. The content may be a range defined by any of the lower limit and the upper limit, and may be a range in which any of the lower limit and the upper limit is combined. Hereinafter, the same applies to other components and conditions.
 接着層中の上記オレフィン系ポリマーに含まれるアルキル(メタ)アクリレートの含有量は、オレフィン系ポリマー(ターポリマー)100質量%に対して、好ましくは5質量%以上、より好ましくは10質量%以上、さらに好ましくは20質量%以上、そして/あるいは、好ましくは45質量%以下、より好ましくは40質量%以下、さらに好ましくは30質量%以下であってよい。 The content of the alkyl (meth) acrylate contained in the above-mentioned olefin-based polymer in the adhesive layer is preferably 5% by mass or more, more preferably 10% by mass or more, with respect to 100% by mass of the olefin-based polymer (terpolymer). More preferably, it may be 20% by mass or more and / or preferably 45% by mass or less, more preferably 40% by mass or less, and still more preferably 30% by mass or less.
 接着層中の上記オレフィン系ポリマーに含まれる不飽和エポキシドの含有量は、オレフィン系ポリマー(ターポリマー)100質量%に対して、好ましくは1質量%以上、より好ましくは3質量%以上、さらに好ましくは5質量%以上、そして/あるいは、好ましくは25質量以下、より好ましくは20質量%以下、さらに好ましくは15質量%以下であってよい。不飽和エポキシドの含有量を1質量%以上とすることで、接着層とポリエステルを含む基布との接着性を向上させることができ、25質量%以下とすることで、オレフィン系ポリマーのゲル化を防止することができる。 The content of unsaturated epoxide contained in the olefin polymer in the adhesive layer is preferably 1% by mass or more, more preferably 3% by mass or more, more preferably 100% by mass of the olefin polymer (terpolymer). May be 5% by weight or more and / or preferably 25% by weight or less, more preferably 20% by weight or less, and still more preferably 15% by weight or less. By setting the content of unsaturated epoxide to 1% by mass or more, the adhesion between the adhesive layer and the base fabric containing polyester can be improved, and by setting the content to 25% by mass or less, gelling of the olefin-based polymer Can be prevented.
 接着層中の上記オレフィン系ポリマーに含まれる不飽和エポキシドの含有量は、オレフィン系ポリマー(ターポリマー)100質量%に対して、好ましくは0.1質量%以上、より好ましくは1質量%、さらに好ましくは5質量%以上、そして/あるいは、好ましくは20質量%以下、より好ましくは15質量%以下、さらに好ましくは10質量%以下とすることができる。エポキシ基を有するモノマーの含有量を0.1質量%以上とすることで、高温・高湿下での基布との接着性を向上させることができる。また、20質量%以下とすることで、接着層の化学的な安定性を確保することができる。 The content of unsaturated epoxide contained in the above-mentioned olefin-based polymer in the adhesive layer is preferably 0.1% by mass or more, more preferably 1% by mass, and further preferably 100% by mass of the olefin-based polymer (terpolymer) It may be preferably 5% by mass or more and / or preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less. By making content of the monomer which has an epoxy group into 0.1 mass% or more, adhesiveness with the base fabric under high temperature and high humidity can be improved. Moreover, the chemical stability of the adhesive layer can be secured by setting the content to 20% by mass or less.
 オレフィン系ポリマー中のエポキシ基の含有率は、好ましくは0.05質量%以上、より好ましくは0.1質量%以上、そして/あるいは、好ましくは5質量%以下、より好ましくは3質量%以下にすることができる。 The content of the epoxy group in the olefin polymer is preferably 0.05% by mass or more, more preferably 0.1% by mass or more and / or preferably 5% by mass or less, more preferably 3% by mass or less can do.
 また、上記オレフィン系ポリマーの融点は、50℃以上であると好ましく、55℃以上であるとより好ましく、そして/あるいは、150℃以下であると好ましく、130℃以下であるとより好ましい。そして、接着層の融点も、50℃以上であると好ましく、55℃以上であるとより好ましく、そして/あるいは、150℃以下であると好ましく、130℃以下であるとより好ましい。接着層の融点が50℃以上であることで、多層フィルム及び積層体の常温での機械的強度を確保することができ、また接着層の融点が150℃以下であることで、多層フィルム及び積層体の製造の際に比較的低い温度で加工が可能となるので、加工性を向上させることができる。 The melting point of the olefin polymer is preferably 50 ° C. or more, more preferably 55 ° C. or more, and / or preferably 150 ° C. or less, more preferably 130 ° C. or less. The melting point of the adhesive layer is also preferably 50 ° C. or more, more preferably 55 ° C. or more, and / or preferably 150 ° C. or less, more preferably 130 ° C. or less. When the melting point of the adhesive layer is 50 ° C. or more, the mechanical strength of the multilayer film and the laminate at normal temperature can be secured, and by the melting point of the adhesive layer being 150 ° C. or less, the multilayer film and the laminate are laminated. Processability can be improved because processing can be performed at a relatively low temperature during manufacture of the body.
 接着層には、エポキシ基を含有するオレフィン系ポリマー以外の他のポリマー又はコポリマーを含有させることができる。接着層に含有させることのできる上記他のポリマーとしては、エポキシ基を含有しないオレフィン系ポリマー又はコポリマー、例えば、エチレン/アルキル(メタ)アクリレートのコポリマー等が挙げられる。 The adhesive layer can contain another polymer or copolymer other than the olefin-based polymer containing an epoxy group. Examples of the other polymers that can be contained in the adhesive layer include olefin-based polymers or copolymers that do not contain an epoxy group, such as ethylene / alkyl (meth) acrylate copolymers.
 接着層には、上述した成分以外に添加剤が添加されていてよい。添加剤としては、顔料、充填材、酸化防止剤、加水分解安定剤、アンチブロッキング剤等が挙げられる。 Additives may be added to the adhesive layer in addition to the components described above. The additives include pigments, fillers, antioxidants, hydrolysis stabilizers, antiblocking agents, and the like.
 接着層中の、エポキシ基を含有するオレフィン系ポリマーの含有量は、接着層の全量に対して、好ましくは50質量%以上、より好ましくは70質量%以上、さらに好ましくは90質量%以上、さらに好ましくは95質量%以上、さらに好ましくは99.5質量%以上とすることができる。また、接着層に含まれるポリマー成分が、エポキシ基を含有するオレフィン系ポリマーからなると好ましく、接着層が、エポキシ基を含有するオレフィン系ポリマーからなるとより好ましい。 The content of the olefin-based polymer containing an epoxy group in the adhesive layer is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, based on the total amount of the adhesive layer. Preferably it is 95 mass% or more, More preferably, it can be 99.5 mass% or more. In addition, the polymer component contained in the adhesive layer is preferably made of an olefin-based polymer containing an epoxy group, and the adhesive layer is more preferably made of an olefin-based polymer containing an epoxy group.
 接着層は、1層であってもよいし、2層以上であってもよい。接着層が2層以上ある場合、例えば、顔料等の着色剤を添加した層と、着色剤を添加しない層との2層とすることができる。これにより、全体として同じ厚みの接着層全体に着色剤を添加した構成に比べ、使用される着色剤の量を少なくすることができる。接着層全体の厚さは、5~50μmであると好ましく、5~30μmであるとより好ましい。 The adhesive layer may be a single layer or two or more layers. When there are two or more adhesive layers, for example, two layers of a layer to which a colorant such as a pigment is added and a layer to which a colorant is not added can be used. This makes it possible to reduce the amount of colorant used as compared to the configuration in which the colorant is added to the entire adhesive layer having the same thickness as a whole. The total thickness of the adhesive layer is preferably 5 to 50 μm, more preferably 5 to 30 μm.
 (気密層)
 気密層は、上述のように、当該層の内外で気体を流通させない気密機能を有する層である。よって、例えば、本形態の多層フィルム及び積層体を袋状に形成した場合、袋の内部に空気を貯め込んだ場合、その空気が外へ漏れることを確実に防止する働きを気密層が担うことができる。
(Airtight layer)
As described above, the hermetic layer is a layer having a hermetic function that does not allow gas to flow in and out of the layer. Therefore, for example, when the multilayer film and the laminate of the present embodiment are formed into a bag, when the air is stored inside the bag, the airtight layer has a function to reliably prevent the air from leaking out. Can.
 気密層は、熱可塑性ポリマーを含むことが好ましい。気密層に含まれる熱可塑性ポリマーは、特に限定されないが、熱可塑性エラストマー又は熱可塑性樹脂であってよく、熱可塑性エラストマーであると好ましい。熱可塑性エラストマーとしては、例えば、アミド系エラストマー、エステル系エラストマー、オレフィン系エラストマー、スチレン系エラストマー、ウレタン系エラストマー、熱可塑性ゴム架橋体のうち1種以上を用いることができる。中でも、低温特性、柔軟性に優れていることからアミド系エラストマーを用いることが好ましい。 The hermetic layer preferably contains a thermoplastic polymer. The thermoplastic polymer contained in the hermetic layer is not particularly limited, but may be a thermoplastic elastomer or a thermoplastic resin, and is preferably a thermoplastic elastomer. As a thermoplastic elastomer, 1 or more types can be used among an amide type elastomer, an ester type elastomer, an olefin type elastomer, a styrene type elastomer, a urethane type elastomer, and a thermoplastic rubber crosslinked body, for example. Among them, it is preferable to use an amide-based elastomer because of its excellent low temperature properties and flexibility.
 上記アミド系エラストマーは、ハードセグメントとしてポリアミドを有し、ソフトセグメントとしてポリエステル又はポリエーテルを有するものが好ましい。ポリアミド系エラストマー中のポリアミドとしては、ナイロン6、ナイロン6,6、ナイロン11、ナイロン12等が挙げられ、中でもナイロン12が好ましい。ポリアミド系エラストマーは、ハードセグメントとして、上述のポリアミドを単独で又は2種以上含んでいてよい。 The amide-based elastomer preferably has polyamide as a hard segment, and polyester or polyether as a soft segment. Examples of the polyamide in the polyamide elastomer include nylon 6, nylon 6, 6, nylon 11, nylon 12 and the like, among which nylon 12 is preferable. The polyamide-based elastomer may contain the above-mentioned polyamide alone or in combination as a hard segment.
 なお、気密層における熱可塑性エラストマー中のハードセグメントの含有量は、熱可塑性エラストマー100質量%に対して、65質量%以上であると好ましく、75質量%以上であるとより好ましく、そして/あるいは、95質量%以下であると好ましく、85質量%以下であるとより好ましい。また、気密層における熱可塑性エラストマー中のソフトセグメントの含有量は、熱可塑性エラストマー100質量%に対して、5質量%以上であると好ましく、15質量%以上であるとより好ましく、そして/あるいは、35質量%以下であると好ましく、25質量%以下であるとより好ましい。 The content of the hard segment in the thermoplastic elastomer in the hermetic layer is preferably 65% by mass or more, more preferably 75% by mass or more, with respect to 100% by mass of the thermoplastic elastomer, and / or It is preferable that it is 95 mass% or less, and it is more preferable that it is 85 mass% or less. In addition, the content of the soft segment in the thermoplastic elastomer in the hermetic layer is preferably 5% by mass or more, more preferably 15% by mass or more, with respect to 100% by mass of the thermoplastic elastomer, and / or It is preferable that it is 35 mass% or less, and it is more preferable that it is 25 mass% or less.
 気密層に含まれる熱可塑性エラストマーの融点は、気密層の融点が接着層の融点より高い温度となるのであれば、特に限定されないが、100℃以上であると好ましく、130℃以上であるとより好ましく、そして/あるいは、300℃以下であると好ましく、210℃以下であるとより好ましい。そして、気密層の融点も、100℃以上であると好ましく、130℃以上であるとより好ましく、そして/あるいは、300℃以下であると好ましく、210℃以下であるとより好ましい。 The melting point of the thermoplastic elastomer contained in the hermetic layer is not particularly limited as long as the melting point of the hermetic layer is higher than the melting point of the adhesive layer, but is preferably 100 ° C. or more, more preferably 130 ° C. or more It is preferable that the temperature is 300 ° C. or less, and more preferably 210 ° C. or less. The melting point of the hermetic layer is also preferably 100 ° C. or more, more preferably 130 ° C. or more, and / or preferably 300 ° C. or less, more preferably 210 ° C. or less.
 上述のように、気密層の融点は接着層の融点よりも高くなっているが、気密層の融点と接着層の融点との差は、好ましくは10℃以上とすることができ、より好ましくは30℃以上とすることができ、そして/あるいは、150℃以下とすることができ、より好ましくは100℃以下とすることができる。多層フィルムを、熱を利用して基布に接着させる際には、気密層の融点と接着層の融点との差を上記の範囲とすることで、製造時の加熱温度が多少変動することがあっても、気密層の気密機能及び接着層の接着機能を確保することができる。そのため、接着層が十分に軟化せずに基布との接着が良好にできなかったり、或いは気密層が変形又は変質したりする等して気密性が損なわれた不良品が発生することを低減でき、生産安定性を向上させることができる。 As described above, the melting point of the hermetic layer is higher than the melting point of the adhesive layer, but the difference between the melting point of the hermetic layer and the melting point of the adhesive layer can be preferably 10 ° C. or more, more preferably The temperature can be 30 ° C. or higher, and / or can be 150 ° C. or lower, more preferably 100 ° C. or lower. When bonding a multilayer film to a base fabric using heat, the heating temperature at the time of manufacture may fluctuate somewhat by setting the difference between the melting point of the hermetic layer and the melting point of the adhesive layer in the above range. Even if it is, it is possible to secure the airtight function of the airtight layer and the adhesive function of the adhesive layer. As a result, the occurrence of defective products in which the air tightness is impaired due to failure of the adhesive layer to soften sufficiently and adhesion with the base cloth can not be made well or the air tight layer is deformed or deteriorated The production stability can be improved.
 気密層には、熱可塑性エラストマーでないポリマー、例えばポリアミド樹脂、ポリエステル樹脂、ポリオレフィン樹脂、ポリ塩化ビニル、ポリウレタン、アクリル樹脂、ポリカーボネート等を配合することができる。 The airtight layer can be blended with a polymer that is not a thermoplastic elastomer, such as polyamide resin, polyester resin, polyolefin resin, polyvinyl chloride, polyurethane, acrylic resin, polycarbonate and the like.
 気密層中のアミド系エラストマーの含有量は、気密層の全量に対して、好ましくは50質量%以上、より好ましくは70質量%以上、さらに好ましくは90質量%以上、さらに好ましくは95質量%以上、さらに好ましくは99.5質量%以上とすることができる。気密層に含まれるポリマー成分が、アミド系エラストマーからなると好ましく、気密層が、アミド系エラストマーからなるとより好ましい。 The content of the amide-based elastomer in the hermetic layer is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more based on the total amount of the hermetic layer. More preferably, it can be 99.5% by mass or more. It is preferable that the polymer component contained in the hermetic layer is made of an amide-based elastomer, and it is more preferable that the hermetic layer be made of an amide-based elastomer.
 また、気密層には、上述した成分以外に添加剤が添加されていてよい。添加剤としては、顔料、充填材、酸化防止剤、加水分解安定剤、アンチブロッキング剤等が挙げられる。 In addition to the components described above, additives may be added to the hermetic layer. The additives include pigments, fillers, antioxidants, hydrolysis stabilizers, antiblocking agents, and the like.
 気密層は、1層であってもよいし、2層以上であってもよい。気密層全体の厚さは、5~50μmであると好ましく、5~30μmであるとさらに好ましい。 The hermetic layer may be a single layer or two or more layers. The thickness of the entire hermetic layer is preferably 5 to 50 μm, and more preferably 5 to 30 μm.
 (中間層)
 本形態による多層フィルムでは、気密層と接着層との間に中間層を設けることができる。図2に、中間層を備えた多層フィルムの一例を模式的な断面図で示す。図2に示すように、多層フィルム1は、接着層2、中間層3、及び気密層4の順に積層されている。
(Intermediate layer)
In the multilayer film according to the present embodiment, an intermediate layer can be provided between the hermetic layer and the adhesive layer. In FIG. 2, an example of the multilayer film provided with the intermediate | middle layer is shown with typical sectional drawing. As shown in FIG. 2, the multilayer film 1 is laminated in the order of the adhesive layer 2, the intermediate layer 3 and the airtight layer 4.
 中間層は、気密層と接着層とを結合させる機能を有する層である。中間層の組成は、気密層及び接着層の組成や厚さ、多層フィルムの用途等に応じて選択することができる。中間層を設けることで、気密層と接着層との結合力を強化することができ、これにより、多層フィルム内の層間剥離を防止することができる。また、中間層を設けることで、機械的強度等の特性を向上させることもできる。 The intermediate layer is a layer having a function of bonding the hermetic layer and the adhesive layer. The composition of the intermediate layer can be selected according to the composition and thickness of the hermetic layer and the adhesive layer, the application of the multilayer film, and the like. By providing the intermediate layer, the bonding strength between the hermetic layer and the adhesive layer can be enhanced, whereby the delamination in the multilayer film can be prevented. In addition, by providing the intermediate layer, characteristics such as mechanical strength can be improved.
 中間層は、用いられる気密層及び接着層の種類にもよるが、熱可塑性ポリマーを含むことが好ましく、オレフィン系ポリマーであることがより好ましい。特に、中間層は、オレフィン系の樹脂又はエラストマーを含むことがより好ましく、オレフィン系樹脂を含むことがより好ましい。オレフィン系樹脂としては、ポリエチレン、ポリプロピレン、エチレン-プロピレン共重合体、ポリブチレン、ポリメチルペンテン等が挙げられる。ポリエチレンとしては、低密度ポリエチレン(LPDE)、高密度ポリエチレン(HDPE)、直鎖状低密度ポリエチレン(L-LDPE)が挙げられる。中間層は、上記オレフィン系ポリマーを、単独で又は2種以上含んでいてよい。 The intermediate layer preferably contains a thermoplastic polymer, more preferably an olefin-based polymer, depending on the types of the gas tight layer and the adhesive layer used. In particular, the intermediate layer more preferably contains an olefin-based resin or elastomer, and more preferably contains an olefin-based resin. Examples of the olefin resin include polyethylene, polypropylene, ethylene-propylene copolymer, polybutylene, polymethylpentene and the like. Examples of polyethylene include low density polyethylene (LPDE), high density polyethylene (HDPE), and linear low density polyethylene (L-LDPE). The intermediate layer may contain the above-mentioned olefin-based polymer singly or in combination of two or more.
 上記オレフィン系ポリマーは、不飽和カルボン酸又はその無水物が付加反応やグラフト反応等により結合させて得られる変性オレフィン系ポリマーであってもよい。そのような変性オレフィン系ポリマーとしては、無水マレイン酸変性オレフィン系樹脂又は無水マレイン酸変性オレフィン系エラストマーが挙げられる。具体的には、無水マレイン酸変性ポリエチレン、無水マレイン酸変性ポリプロピレン等が挙げられる。中間層は、上記変性オレフィン系ポリマーを単独で又は2種以上含んでいてよい。 The olefin-based polymer may be a modified olefin-based polymer obtained by combining an unsaturated carboxylic acid or an anhydride thereof by an addition reaction, a grafting reaction or the like. As such a modified olefin polymer, maleic anhydride modified olefin resin or maleic anhydride modified olefin elastomer is mentioned. Specifically, maleic anhydride modified polyethylene, maleic anhydride modified polypropylene and the like can be mentioned. The intermediate layer may contain the above modified olefin-based polymer singly or in combination of two or more.
 気密層がポリアミドを含む場合には、中間層は、ポリアミドとの接着性が良好であることから、上述のような無水マレイン酸変性されたオレフィン系ポリマーを含むことが好ましく、無水マレイン酸変性ポリエチレンを含むことがより好ましく、無水マレイン酸変性低密度ポリエチレンを含むことがさらに好ましい。また、接着層が、エポキシ基を含有するオレフィン系ポリマーを含む場合には、中間層は、無水マレイン酸変性されていないポリエチレンを含むことが好ましく、変性されていないポリエチレンを含むことがより好ましく、無水マレイン酸変性されていない高密度ポリエチレンを含むことがさらに好ましい。 When the airtight layer contains a polyamide, the intermediate layer preferably contains a maleic anhydride-modified olefin-based polymer as described above, because the adhesion to the polyamide is good, and the maleic anhydride-modified polyethylene Is more preferable, and it is further preferable to contain maleic anhydride modified low density polyethylene. When the adhesive layer contains an olefin-based polymer containing an epoxy group, the intermediate layer preferably contains polyethylene which is not maleic anhydride modified, and more preferably contains polyethylene which is not modified, It is further preferred to include high density polyethylene which is not maleic anhydride modified.
 中間層に含まれるオレフィン系ポリマーの融点は、50℃以上であると好ましく、60℃以上であるとより好ましく、そして/あるいは、200℃以下であると好ましく、180℃以下であるとより好ましい。そして、中間層の融点は、50℃以上であると好ましく、60℃以下であるとより好ましく、そして/あるいは、200℃以下であると好ましく、180℃以下であるとより好ましい。 The melting point of the olefin-based polymer contained in the intermediate layer is preferably 50 ° C. or more, more preferably 60 ° C. or more, and / or preferably 200 ° C. or less, more preferably 180 ° C. or less. The melting point of the intermediate layer is preferably 50 ° C. or more, more preferably 60 ° C. or less, and / or preferably 200 ° C. or less, more preferably 180 ° C. or less.
 中間層は、2層以上であってもよい。中間層が2層以上である場合、各層の組成は、同じであってもよいし異なっていてもよい。中間層を2層以上とした場合、多層フィルムにおける各層間の接着性が向上するように、各中間層の材料を選択することで、各層間の結合をより強固にすることができ、これにより、多層フィルム内の層間剥離を防止することができる。 The middle layer may be two or more layers. When the intermediate layer is two or more layers, the composition of each layer may be the same or different. When the number of intermediate layers is two or more, by selecting the material of each intermediate layer so as to improve the adhesion between each layer in the multilayer film, the bond between the respective layers can be further strengthened, thereby And delamination in the multilayer film can be prevented.
 図3に、2層の中間層を備えた多層フィルムの一例を模式的な断面図で示す。図3に示すように、多層フィルム1は、接着層2、第1中間層3a、第2中間層3b、及び気密層4の順に積層されている。第1中間層3aは接着層2と直接結合しており、第2中間層3bは接着層4と直接結合している。 An example of a multilayer film provided with two intermediate layers is shown in FIG. 3 in a schematic cross-sectional view. As shown in FIG. 3, the multilayer film 1 is laminated in the order of the adhesive layer 2, the first intermediate layer 3 a, the second intermediate layer 3 b, and the airtight layer 4. The first intermediate layer 3 a is directly bonded to the adhesive layer 2, and the second intermediate layer 3 b is directly bonded to the adhesive layer 4.
 気密層がポリアミドを含み、且つ接着層が、エポキシ基を含有するオレフィン系ポリマーを含む場合には、気密層と直接結合している第2中間層は、好ましくは無水マレイン酸変性されたオレフィン系ポリマー、より好ましくは無水マレイン酸変性低密度ポリエチレンを含むことができる。また、接着層と直接結合している第1中間層は、好ましくは無水マレイン酸変性されていないポリエチレン、より好ましくは変性されていないポリエチレン、さらに好ましくは無水マレイン酸変性されていない高密度ポリエチレンを含むことができる。 If the gas-tight layer comprises a polyamide and the adhesive layer comprises an olefin-based polymer containing epoxy groups, the second interlayer directly bonded to the gas-tight layer is preferably a maleic anhydride-modified olefinic system. It may comprise a polymer, more preferably maleic anhydride modified low density polyethylene. Also, the first intermediate layer directly bonded to the adhesive layer is preferably non-maleic anhydride modified polyethylene, more preferably non-modified polyethylene, still more preferably non-maleic anhydride modified high density polyethylene Can be included.
 中間層全体の厚さは、好ましくは5~50μm、より好ましくは5~30μmとすることができる。 The thickness of the entire intermediate layer can be preferably 5 to 50 μm, more preferably 5 to 30 μm.
 中間層の各層には、上述した成分以外に添加剤が添加されていてよい。添加剤としては、顔料、充填材、酸化防止剤、加水分解安定剤、アンチブロッキング剤等が挙げられる。 In addition to the components described above, additives may be added to each layer of the intermediate layer. The additives include pigments, fillers, antioxidants, hydrolysis stabilizers, antiblocking agents, and the like.
 (多層フィルムの製造)
 多層フィルムは、接着層と気密層とを直接的に結合させることによって製造することができる。また、多層フィルムが中間層を有する場合には、接着層と中間層とを直接的に結合させ、且つ中間層と気密層とを直接的に結合させることによって製造することができる。その場合、予め、接着層、気密層、及び必要に応じて中間層をそれぞれ別個のシートとして押出成形等により成形しておき、互いを接合させて一体化させることができる。例えば、各シートを重ねて熱プレス又は熱ロールによって溶融圧着する方法、成形されたシート上に溶融した材料を押し出す押出ラミネート法等が挙げられる。
(Manufacture of multilayer film)
A multilayer film can be produced by directly bonding the adhesive layer and the hermetic layer. In addition, when the multilayer film has an intermediate layer, it can be produced by directly bonding the adhesive layer and the intermediate layer, and directly bonding the intermediate layer and the hermetic layer. In that case, the adhesive layer, the airtight layer, and, if necessary, the intermediate layer may be formed as separate sheets by extrusion or the like, and may be bonded and integrated. For example, there is a method in which the respective sheets are stacked and melt-pressed by a heat press or a heat roll, and an extrusion laminating method in which the molten material is extruded on a formed sheet.
 また、接着層、気密層、及び必要に応じて中間層の材料をそれぞれ溶融状態にして、同時に押出成形し(共押出し)、インフレーション法、Tダイ法等を用いて成形することができる。このうち、大面積化が可能であり生産性に優れるインフレーション法を用いることが好ましい。 In addition, the materials for the adhesive layer, the airtight layer, and the intermediate layer as needed may be brought into a molten state and simultaneously extruded (co-extrusion) and molded using an inflation method, a T-die method or the like. Among these, it is preferable to use an inflation method which can be enlarged and has excellent productivity.
 製造された多層フィルムは、用途に応じて、所望の形状及び大きさに切断することができる。また、多層フィルムは、リール等に巻き付けられていてよく、使用時に巻き解かれるようにしてもよい。さらに、多層フィルムには、少なくとも接着層側に剥離シートが設けられていてよく、これにより、使用直前まで接着層を保護することができる。 The multilayer film produced can be cut into the desired shape and size depending on the application. The multilayer film may be wound around a reel or the like, and may be unwound at the time of use. Furthermore, in the multilayer film, a release sheet may be provided at least on the adhesive layer side, whereby the adhesive layer can be protected until immediately before use.
 (基布)
 本形態による多層フィルムは、基布に接着させて使用することができる。本明細書において、基布とは、多層フィルムと基布との積層により得られる積層体の機械的強度を確保するための支持体として機能するシート状の構造体である。ここで、シート状とは、平面状の他、全体として見た場合に筒状、袋状、風船状に形成されている形状も含む。
(Base cloth)
The multilayer film according to the present embodiment can be used by adhering to a base fabric. In the present specification, the base fabric is a sheet-like structure that functions as a support for securing the mechanical strength of the laminate obtained by laminating the multilayer film and the base fabric. Here, the sheet shape includes, in addition to a planar shape, a shape formed in a tubular shape, a bag shape, or a balloon shape when viewed as a whole.
 基布は、繊維を含むものが好ましい。基布は、織物、編物、不織布であってよく、全体にわたり又は部分的に縫製が施されたものであってもよい。中でも、機械的強度が高いことから織物が好ましく、複数の経糸と複数の緯糸とを組み合わせた2軸構造であると好ましく、複数の経糸と、複数の緯糸と、複数の斜糸とを組み合わせた3軸構造とすることもできる。2軸構造の基布である場合、織り方は限定されず、平織、綾織、繻子織等であってよい。強度及び製造の容易性から、基布は、平織された織物であるとより好ましい。また、基布には、平面状の基布ではなく、目的とする製品の形状に合わせて、湾曲面を有することができるよう、縫い目なく筒状又は袋状に織り上げられたOPW(One Piece Woven)も含まれる。 The base fabric preferably contains fibers. The base fabric may be a woven fabric, a knitted fabric, a non-woven fabric, and may be fully or partially sewn. Among them, a woven fabric is preferable because of high mechanical strength, and a biaxial structure in which a plurality of warps and a plurality of wefts are combined is preferable, and a plurality of warps, a plurality of wefts, and a plurality of diagonals are combined. A three-axis structure can also be used. When it is a base fabric of a biaxial structure, the weave is not limited, and may be plain weave, twill weave, satin weave, and the like. The base fabric is more preferably a plain weave fabric because of its strength and ease of manufacture. In addition, the base cloth is not a flat base cloth, but OPW (One Piece Woven) woven into a cylindrical or bag shape without a seam so that it can have a curved surface according to the shape of the target product Is also included.
 上記OPWは、膨らませて内部に空気を貯めた状態で使用することができ、車両用エアバッグ等の用途で好適に用いることができる。このうち、カーテンエアバッグのために利用されるOPWは、複数の部屋が形成された複雑な曲面を有しており、膨らませた時に凹凸を有する構造を有し得る。通常、このような凹凸のある構造を有する基布にフィルムを接着させた場合、凹凸のない基布にフィルムを接着させるのに比べて、基布とフィルムとの間で剥離が生じやすい。しかしながら、本形態による多層フィルムを用いることで、凹凸のあるOPWであっても、多層フィルムを良好に接着することができ、層間剥離を防止することができる。 The above-mentioned OPW can be used in a state of being inflated and storing air therein, and can be suitably used in applications such as vehicle air bags. Among these, the OPW used for a curtain airbag has a complex curved surface in which a plurality of rooms are formed, and can have a structure having unevenness when inflated. In general, when a film is adhered to a base fabric having such an uneven structure, peeling is more likely to occur between the base fabric and the film than when the film is adhered to an uneven base fabric. However, by using the multilayer film according to the present embodiment, the multilayer film can be adhered well even if it is an OPW having irregularities, and the delamination can be prevented.
 基布に含まれる繊維は、合成繊維、天然繊維、再生繊維、半合成繊維、無機繊維、及びこれらの組合せ(混紡、混織を含む)であってよい。中でも、合成繊維、特にポリマー繊維であると好ましい。繊維としては、芯鞘型繊維、サイドバイサイド型繊維、分割型繊維等の複合繊維を用いることもできる。 The fibers contained in the base fabric may be synthetic fibers, natural fibers, regenerated fibers, semi-synthetic fibers, inorganic fibers, and combinations thereof (including blended yarns and mixed weaves). Among them, synthetic fibers, particularly polymer fibers, are preferred. As the fibers, composite fibers such as core-sheath fibers, side-by-side fibers, and split-type fibers can also be used.
 繊維を構成するポリマーとしては、ポリエチレンテレフタレート、ポリブチレンテレフタレートといったポリアルキレンテレフタレート等のホモポリエステル、ポリエステルの繰り返し単位を構成する酸成分にイソフタル酸、5-ナトリウムスルホイソフタル酸又はアジピン酸等の脂肪族ジカルボン酸等を共重合したポリエステル繊維、ナイロン6・6、ナイロン6,ナイロン12、ナイロン4・6及びナイロン6とナイロン6・6共重合体、ナイロンにポリアルキレングリコール、ジカルボン酸やアミン類等を共重合したポリアミド繊維、パラフェニレンテレフタルアミド及び芳香族エーテルとの共重合等に代表されるアラミド繊維、レーヨン繊維、超高分子量ポリエチレン繊維、パラフェニレンサルフォン、ポリサルフォン等のサルフォン系繊維、ポリエーテルケトン繊維等が挙げられる。 As a polymer constituting the fiber, homopolyester such as polyalkylene terephthalate such as polyethylene terephthalate and polybutylene terephthalate, aliphatic dicarboxylic acid such as isophthalic acid, 5-sodium sulfoisophthalic acid or adipic acid as an acid component constituting the repeating unit of polyester Polyester fiber copolymerized with acid, etc., nylon 6, 6 nylon 6, nylon 12, nylon 4 6 and nylon 6 and nylon 6 6 copolymer, nylon with polyalkylene glycol, dicarboxylic acid, amines etc. Sulfur such as aramid fiber represented by polymerized polyamide fiber, copolymerization with paraphenylene terephthalamide and aromatic ether, rayon fiber, ultra high molecular weight polyethylene fiber, paraphenylene sulfone, polysulfone and the like Down fibers, polyether ketone fibers and the like.
 なお、基布は2以上の繊維を含んでいてよい。例えば基布が織物である場合、異なる方向に延在する糸に用いられる繊維として、異なる種類の繊維を使用することができる。より具体的には、経糸と緯糸とを含む2軸構造を有する場合、経糸と緯糸とを異なる種類の繊維とすることができる。この場合、経糸及び緯糸の少なくとも一方をポリエステル繊維とすることができる。 The base fabric may contain two or more fibers. For example, if the backing is a fabric, different types of fibers can be used as the fibers used for yarns extending in different directions. More specifically, in the case of having a biaxial structure including a warp and a weft, the warp and the weft can be fibers of different types. In this case, at least one of the warp yarn and the weft yarn can be made of polyester fiber.
 本形態では、基布はポリエステルを含むことができる。ポリエステルを含む基布と、上述の多層フィルムとによって、高温及び/又は高湿の環境下での耐久性により一層優れた積層体を得ることができる。より具体的には、基布は、ポリエステルからなる繊維又はポリエステルを含む繊維を含むことができる。すなわち、基布は、ポリエステル製繊維を、混織等により他の繊維と混合して含んでいてよいし、ポリエステルとポリエステル以外の材料との混紡繊維を含んでいてもよいし、或いはポリエステルとポリエステル以外の材料とからなる、芯鞘型、サイドバイサイド型、分割型等の複合繊維を含んでいてもよい。基布がポリエステルを含むことで、積層体の機械的強度、耐候性を確保しつつ、積層体を比較的安価に製造することができる。また、基布がポリエステル製の繊維からなっている場合には、上記効果がより一層発揮される。 In the present form, the backing can comprise polyester. By the base fabric containing polyester and the above-mentioned multilayer film, it is possible to obtain a laminate which is more excellent in durability under high temperature and / or high humidity environment. More specifically, the base fabric can include fibers made of polyester or fibers containing polyester. That is, the base fabric may contain polyester fibers mixed with other fibers by mixing, etc., or may contain a blended fiber of polyester and a material other than polyester, or polyester and polyester The core-sheath type, the side-by-side type, and the split type composite fibers made of other materials may be included. When the base fabric contains polyester, the laminate can be manufactured relatively inexpensively while securing the mechanical strength and the weather resistance of the laminate. In addition, when the base fabric is made of polyester fibers, the above-mentioned effect is further exhibited.
 基布に含まれるポリエステルとしては、ポリアルキレンテレフタレート又はポリアルキレンンナフタレートが好ましい。ポリエステルの具体例としては、ポリエチレンテレフタレート(PET)、ポリトリメチレンテレフタレート(PTT)、ポリブチレンテレフタレート(PBT)、ポリエチレンナフタレート(PEN)、ポリブチレンナフタレート(PBN)等のホモポリエステル、ポリエステルの繰り返し単位を構成する酸成分にイソフタル酸、5-ナトリウムスルホイソフタル酸、アジピン酸等の脂肪族ジカルボン酸等を共重合したコポリマーが挙げられる。上記ポリエステルは、単独で、又は混織、混紡、複合繊維、又はポリマーブレンドの形態で2種以上組み合わせて用いることができる。 As polyester contained in a base fabric, polyalkylene terephthalate or polyalkylene naphthalate is preferable. Specific examples of the polyester include homopolyesters such as polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), and polyesters Examples of the acid component constituting the unit include copolymers obtained by copolymerizing aliphatic dicarboxylic acids such as isophthalic acid, 5-sodium sulfoisophthalic acid and adipic acid. The above polyesters can be used alone or in combination of two or more in the form of mixed weave, blend, composite fiber, or polymer blend.
 基布に含み得る、ポリエステル繊維以外の繊維としては、ポリエステル以外の材料からなる合成繊維、天然繊維、再生繊維、半合成繊維、無機繊維の1種以上であってよい。また、ポリエステル以外の材料としては、ポリアミド、ポリオレフィン、アラミド、アクリル、ビニロン、ポリウレタン等が挙げられる。 Fibers other than polyester fibers that may be included in the base fabric may be one or more of synthetic fibers made of materials other than polyester, natural fibers, regenerated fibers, semi-synthetic fibers, and inorganic fibers. Further, as materials other than polyester, polyamide, polyolefin, aramid, acrylic, vinylon, polyurethane and the like can be mentioned.
 基布が織物である場合、基布は2種以上の異なる繊維を含んでいてよく、その場合、例えば、異なる方向に延在する繊維又は糸を、互いに異なる種類とすることができる。例えば、経糸と緯糸とを含む2軸構造を有する場合、経糸と緯糸とを異なる種類の繊維とすることができる。この場合、経糸及び緯糸の少なくとも一方をポリエステル製繊維とすることができる。 When the backing is a textile, the backing may comprise two or more different fibers, in which case, for example, the fibers or yarns extending in different directions can be of different types. For example, if it has a biaxial structure including a warp and a weft, the warp and the weft can be different types of fibers. In this case, at least one of the warp yarn and the weft yarn can be made of polyester fiber.
 基布に含まれる糸は、モノフィラメントであってもよいし、マルチフィラメントであってもよい。糸がマルチフィラメントである場合、糸の総繊度(単糸繊度×合糸数)が100~700dtexであることが好ましい。また、基布に用いられている繊維の単糸繊度は、1~10dtexであると好ましい。また、基布が平織の織物である場合、織り密度としては、経糸及び緯糸がそれぞれ、5~30本/cmであることが好ましい。 The yarn contained in the backing may be monofilament or multifilament. When the yarn is a multifilament, it is preferable that the total fineness of the yarn (single yarn fineness × multiple yarn number) is 100 to 700 dtex. The single yarn fineness of the fibers used in the base fabric is preferably 1 to 10 dtex. When the base fabric is a plain weave fabric, the weave density is preferably 5 to 30 yarns / cm 2 for each of the warp yarns and weft yarns.
 基布の目付(1m当たり質量)は、積層体(最終製品)の収納性やコストを考慮して、300g/m以下、より好ましくは200g/m以下、さらに好ましくは190g/m以下、さらに好ましくは150g/m以下、100g/m以下とすることができる。また、機械的強度を確保する観点から、好ましくは30g/m以上、より好ましくは50g/m以上、さらに好ましくは70g/m以上とすることができる。 Weight per unit area of the base fabric (1 m 2 per mass), taking into account the storage and cost of the laminate (final product), 300 g / m 2 or less, more preferably 200 g / m 2 or less, more preferably 190 g / m 2 Hereinafter, more preferably, it can be 150 g / m 2 or less and 100 g / m 2 or less. Further, from the viewpoint of securing mechanical strength, it is preferably 30 g / m 2 or more, more preferably 50 g / m 2 or more, and still more preferably 70 g / m 2 or more.
 なお、基布は、目の詰まったものであってもよいし、得られる積層体をより軽量にできることから、開口を有するものであってもよい。本形態では、基布にポリマー組成物をコーティングすることによって層を形成するのではなく、予め形成しておいた多層フィルムを基布に積層させて積層体とする。そのため、本形態の多層フィルムに接着させる基布として、開口を有する基布を用いたとしても、粘度が比較的低いポリマー組成物が裏抜けする等の不都合が発生することなく、十分な機械的強度や気密性を有する積層体を得ることができる。 The base fabric may be closed, or may have an opening because the resulting laminate can be made lighter. In this embodiment, instead of forming a layer by coating the base fabric with the polymer composition, a multilayer film formed in advance is laminated on the base fabric to form a laminate. Therefore, even if a base fabric having an opening is used as a base fabric to be adhered to the multilayer film of the present embodiment, sufficient mechanical properties are prevented without causing disadvantages such as penetration of a polymer composition having a relatively low viscosity. A laminate having strength and air tightness can be obtained.
 (積層体)
 図4に、本発明の一形態による積層体の模式的な断面図を示す。積層体10は、上述した気密層4と接着層2とを備えた多層フィルム1と、基布8とが接着されて構成されている。
(Laminate)
FIG. 4 shows a schematic cross-sectional view of a laminate according to an embodiment of the present invention. The laminate 10 is configured by bonding the multilayer film 1 provided with the above-mentioned airtight layer 4 and the adhesive layer 2 and the base fabric 8.
 図4の例では、基布8の一方の面に多層フィルム1が配置されているが、本形態の多層フィルムは、基布8の両面に設けることもできる。また、基布8としてOPWを用いた場合、図5に示すように、袋の空気を抜き畳んだ状態で、OPW9(基布8)の表面に、上方及び下方からそれぞれ多層フィルム1A、1Bが積層されたものであってもよい。図5に示す形態の積層体は、内側に空気を貯めることができるため、エアバッグ等に使用することができる。 In the example of FIG. 4, the multilayer film 1 is disposed on one surface of the base fabric 8, but the multilayer film of the present embodiment can also be provided on both sides of the base fabric 8. When OPW is used as the base fabric 8, as shown in FIG. 5, the multilayer films 1A and 1B are respectively from above and below on the surface of the OPW 9 (base fabric 8) in a state where the air of the bag is extracted and folded. It may be laminated. The laminate of the form shown in FIG. 5 can be used as an air bag or the like because it can store air inside.
 また、図4、5の例では、多層フィルム1、1A、1Bは、中間層を備えていないが、各例の多層フィルムは、1層又は2層以上の上述の中間層を備えていてよい。 Also, in the examples of FIGS. 4 and 5, the multilayer films 1, 1A, 1B do not have an intermediate layer, but the multilayer film of each example may have one or more of the above-mentioned intermediate layers. .
 積層体の製造においては、製品の低コスト化が常に求められている。特に車両用エアバッグの分野では、基布の材料として従来、ナイロン等のポリアミドが用いられることが多かったが、近年では、比較的安価なポリエステル製の基布が使用されるようになっている。そのため、ポリエステル製糸を含む基布に対しても接着性の高いフィルム材料が求められていた。しかしながら、従来のフィルムでは、ポリエステル製糸を含む基布に対する接着性が十分でない場合があった。これに対し、エポキシ基を含有するオレフィン系ポリマーを含む接着層を備えた上述の多層フィルムを、ポリエステルを含む基布に接着させて積層体を製造した場合、高温及び/又は高湿の条件下の条件において多層フィルムと基布との間での層間剥離が生じにくく、優れた耐久性を示す。 In the manufacture of laminates, cost reduction of products is always required. Particularly in the field of vehicle airbags, conventionally, polyamides such as nylon have often been used as the material of the base cloth, but in recent years relatively cheap polyester base cloth has come to be used . Therefore, a film material having high adhesiveness to a base fabric containing polyester yarn has been required. However, conventional films may not have sufficient adhesion to the base fabric containing polyester yarn. On the other hand, when the above-mentioned multilayer film provided with an adhesive layer containing an olefin-based polymer containing an epoxy group is adhered to a base cloth containing polyester to produce a laminate, conditions of high temperature and / or high humidity In the conditions of 3, it is difficult to cause delamination between the multilayer film and the base fabric, and show excellent durability.
 積層体は、上述の多層フィルムを、加熱及び/又は加圧することによって、基布に接着させることができる。その際、接着層中のオレフィン系ポリマーに含まれるエポキシ基が、基布中のポリエステルと不可逆的に反応し、結合が形成されると考えられる。このような結合によって、積層体の高温及び/又は高湿下での耐久性を向上させることができる。 The laminate can be adhered to the backing by heating and / or pressing the above-mentioned multilayer film. At that time, it is considered that the epoxy group contained in the olefin-based polymer in the adhesive layer irreversibly reacts with the polyester in the base fabric to form a bond. Such bonding can improve the durability of the laminate under high temperature and / or high humidity.
 (積層体の製造方法)
 本発明の一形態は、上述の多層フィルムと、基布とを有する積層体の製造方法であって、気密層が融解しない温度で加熱しながら、多層フィルムと基布とを加圧することにより、多層フィルムと前記基布とを接着させる工程を含む。
(Method of manufacturing laminate)
One embodiment of the present invention is a method for producing a laminate having the above-described multilayer film and a base fabric, and by pressing the multilayer film and the base fabric while heating at a temperature at which the hermetic layer does not melt, Bonding the multilayer film to the base fabric.
 ここで、本形態による積層体において、「フィルム」とは、可撓性の薄膜を意味し、その温度、硬さ等の状態は問わない。つまり、供給される多層フィルムは、常温以下であってもよいし、常温より高い温度のものであってもよい。また、軟化されて少なくとも部分的に接着機能を発揮できる状態にあるものであってもよい。よって、本形態による積層体は、例えば、常温以下で供給された多層フィルムを、加熱手段を用いて気密層の融点を下回る温度で加熱しながら基布に接着させることによって製造することもできるし、また例えば、押出機で加熱されてフィルム状に押し出されたポリマーを、基布と接着させることによって製造することができる。 Here, in the laminate according to the present embodiment, the "film" means a flexible thin film, and the state of temperature, hardness and the like does not matter. That is, the multilayer film to be supplied may be at normal temperature or lower, or may have a temperature higher than normal temperature. In addition, it may be softened to be able to at least partially exhibit an adhesive function. Therefore, the laminate according to the present embodiment can be manufactured, for example, by bonding a multilayer film supplied at normal temperature or less to a base fabric while heating it at a temperature below the melting point of the hermetic layer using a heating means. Also, for example, it can be produced by bonding a polymer, which is heated by an extruder and extruded into a film, to a base cloth.
 図6に、本形態による積層体の製造方法を実施するための積層体製造装置100を模式的に示す。図6では、基布8の両面に多層フィルムが積層された積層体を製造するための装置について説明する。積層体製造装置100は、加熱部102及び冷却部104を備えている。 FIG. 6 schematically shows a laminate manufacturing apparatus 100 for carrying out the method of manufacturing a laminate according to the present embodiment. In FIG. 6, the apparatus for manufacturing the laminated body by which the multilayer film was laminated | stacked on both surfaces of the base fabric 8 is demonstrated. The layered product manufacturing apparatus 100 includes a heating unit 102 and a cooling unit 104.
 図6の積層体製造装置100を用いた製造方法においては、まず、予めリール等に巻き取られていた基布8、及び多層フィルム1A、1Bをそれぞれ巻き解いて、基布8の両面(上面及び下面)に多層フィルム1A、1Bをそれぞれ重ね合せる。重ね合された多層フィルム1A、基布8、及び多層フィルム1Bを、加熱部102に送り、加熱部102において加熱しながら加圧する。 In the manufacturing method using the laminate manufacturing apparatus 100 of FIG. 6, first, the base fabric 8 and the multilayer films 1A and 1B previously wound up in a reel or the like are respectively unwound, and both sides of the base fabric 8 (upper surface And the lower surface) of the multilayer films 1A and 1B, respectively. The multilayer film 1A, the base fabric 8 and the multilayer film 1B, which are superimposed, are sent to the heating unit 102, and pressure is applied while heating in the heating unit 102.
 加熱部102は、例えば、一対の対向するロール(ニップロール等)、又は図6の例のような一対の対向するベルトからなる加圧手段を備えている。このような加圧手段の一対のロール又はベルトの少なくとも一方を加熱し、この加圧手段の間に、重ね合わせられた多層フィルム1A、基布8、及び多層フィルム1Bを通すことで、加熱及び加圧を行うことができる。ここで、多層フィルムの接着層の融点は気密層の融点よりも低いので、例えば、加熱温度を、接着層が軟化又は融解する温度であって気密層が融解(溶融)しない温度としておくことで、気密層の機能を確保しつつ、接着層が十分に軟化又は融解した状態で接着層を基布へと押し付けることができる。そして、軟化又は融解した接着層は、基布の表面の凹凸の凹部にも入り込み、接着層を基布に密に接着させることができる。これにより、図示の形態では、多層フィルム1A、1Bを基布8へそれぞれ接着させることができ、多層フィルム1A、基布8、及び多層フィルム1Bを備えた積層体10が形成され、搬送される。上記加熱温度は、例えば、気密層の融点未満の温度とすることができ、これにより、気密層の機能をより確実に確保することができる。また、加熱温度は、気密層が熱の影響によりその気密機能を失わない温度であればよい。 The heating unit 102 includes, for example, a pressing unit including a pair of opposing rolls (such as nip rolls) or a pair of opposing belts as in the example of FIG. By heating at least one of the pair of rolls or belts of such pressing means and passing the laminated multilayer film 1A, the base cloth 8 and the multilayer film 1B between the pressing means, heating and It can be pressurized. Here, since the melting point of the adhesive layer of the multilayer film is lower than the melting point of the hermetic layer, for example, the heating temperature is set to a temperature at which the adhesive layer softens or melts and the hermetic layer does not melt (melt). The adhesive layer can be pressed against the base fabric in a state where the adhesive layer is sufficiently softened or melted while securing the function of the hermetic layer. Then, the softened or melted adhesive layer can also penetrate into the concavities and convexities of the surface of the base fabric, so that the adhesive layer can be tightly adhered to the base fabric. Thereby, in the form of illustration, multilayer film 1A, 1B can be each adhere | attached on the base fabric 8, and the laminated body 10 provided with the multilayer film 1A, the base fabric 8, and the multilayer film 1B is formed and conveyed. . The heating temperature can be set, for example, to a temperature lower than the melting point of the hermetic layer, whereby the function of the hermetic layer can be ensured more reliably. Further, the heating temperature may be a temperature at which the hermetic layer does not lose its hermetic function under the influence of heat.
 加熱部102を通過した積層体10は、冷却部104へと搬送される。冷却部104においては、積層体10の温度を、好ましくは常温にまで下げることができる。つまり、本形態による積層体の製造方法は、冷却工程をさらに有していてよい。冷却部104は、冷却媒体を含む冷却手段や、吸気手段等を備えていてよい。また、冷却部104において、図6の例のように、一対の対向するベルトからなる加圧手段を用いて加圧されてもよいが、加圧は必ずしも必要ではない。積層体10は、図6に示すように、必要に応じてリールに巻かれる。 The stacked body 10 that has passed through the heating unit 102 is transported to the cooling unit 104. In the cooling unit 104, the temperature of the laminate 10 can be lowered preferably to room temperature. That is, the method for manufacturing a laminate according to the present embodiment may further include a cooling step. The cooling unit 104 may include a cooling unit including a cooling medium, an intake unit, and the like. Further, as in the example of FIG. 6, the cooling unit 104 may be pressurized using a pressing unit including a pair of opposing belts, but the pressing is not necessarily required. The laminate 10 is wound on a reel as needed, as shown in FIG.
 なお、図6の積層体製造装置100においては、多層フィルム1A及び1Bのいずれかを省略することができる。その場合、図4に示すような、基布8の片面に多層フィルム1が積層された積層体10を製造することができる。 In addition, in the laminated body manufacturing apparatus 100 of FIG. 6, either of the multilayer films 1A and 1B can be abbreviate | omitted. In that case, as shown in FIG. 4, the laminated body 10 by which the multilayer film 1 was laminated | stacked on the single side | surface of the base fabric 8 can be manufactured.
 また、基布8として、縫い目なく織られた筒状又は袋状のOPW9を用いることもできる。これにより、図5に示すような積層体を製造することができる。図6に示す装置において、基布8をOPWとする場合には、OPWの内部から空気が抜かれて平らにされ、予めリール等に巻かれたものを使用する。上述の例と同様に、OPWも、重ね合される前に巻き解かれ、その上面及び下面に、多層フィルム1A及び1Bがそれぞれ重ね合せられる。 Further, as the base fabric 8, it is also possible to use a tubular or bag-like OPW 9 woven without a seam. Thereby, a laminate as shown in FIG. 5 can be manufactured. In the apparatus shown in FIG. 6, in the case where the base fabric 8 is OPW, air is removed from the inside of the OPW to flatten it, and the one previously wound on a reel or the like is used. Similar to the above-described example, the OPW is unwound before being superimposed, and the multilayer films 1A and 1B are respectively superimposed on the upper surface and the lower surface.
 図7に、平らにされた状態で積層体製造装置100に投入されたOPW9(基布8)の上面及び下面に、多層フィルム1A及び1Bがそれぞれ重ね合された状態の図を模式的に示す。図7に示すように重ね合わされた多層フィルム1A、OPW9(基布8)、及び多層フィルム1Bは、加圧部102において、一対の加圧手段によって両面から加圧される。これにより、多層フィルム1A及び1Bが、OPW9(基布8)の上面及び下面にそれぞれ接合され、また多層フィルム1A及び1Bの縁部が、加熱及び加圧により又は接着剤等により互いに接合されることで、図5に示すような積層体10を得ることができる。この際、接着層2A、2Bは、OPW9(基布8)の縁部全体を覆うように接着させることができる。また、積層体10の余分な縁部は、切断等により除去することができる。このようにして、基布が袋状に形成されており、OPW9(基布8)の表面全体に多層フィルムが形成されている積層体を製造することができる。このようにして得られた積層体は、エアバッグとして使用することができる。 FIG. 7 schematically shows a state in which the multilayer films 1A and 1B are respectively superimposed on the upper surface and the lower surface of the OPW 9 (base fabric 8) loaded into the laminate manufacturing apparatus 100 in a flat state. . As shown in FIG. 7, the multilayer film 1A, the OPW 9 (base fabric 8), and the multilayer film 1B stacked together are pressed from both sides by a pair of pressing means in the pressing unit 102. Thereby, multilayer films 1A and 1B are bonded to the upper and lower surfaces of OPW 9 (base fabric 8), respectively, and the edges of multilayer films 1A and 1B are bonded to each other by heating and pressing or by an adhesive or the like. Thus, a laminate 10 as shown in FIG. 5 can be obtained. At this time, the adhesive layers 2A and 2B can be adhered so as to cover the entire edge of the OPW 9 (base fabric 8). Also, the extra edge of the laminate 10 can be removed by cutting or the like. In this manner, it is possible to manufacture a laminate in which the base fabric is formed in a bag shape, and the multilayer film is formed on the entire surface of the OPW 9 (base fabric 8). The laminate thus obtained can be used as an air bag.
 積層体を製造する際の加熱温度は、気密層が融解しない温度であり、且つ接着層が軟化又は融解する温度であれば、特に限定されない。加熱温度は、気密層の融点未満の温度で、且つ接着層が軟化する温度とすることができる。加熱温度及び加圧圧力は、多層フィルム及び基布の構成にもよるが、加熱温度は、100℃以上であると好ましく、120℃以上であるとより好ましく、そして/あるいは、250℃以下であると好ましく、200℃以下であるとより好ましい。また、加圧圧力は、5N/cm以上であると好ましく、10N/cm以上とすることができ、そして/あるいは、700N/cm以下であると好ましく、500N/cm以下とすることができる。さらに、積層体製造時の運転条件に応じて5~50N/cmとすることができる。 The heating temperature at the time of manufacturing a laminated body will not be specifically limited if it is the temperature which an airtight layer does not melt | dissolve, and the temperature which an adhesive layer softens or melts. The heating temperature may be a temperature below the melting point of the hermetic layer and a temperature at which the adhesive layer softens. Although the heating temperature and pressure depend on the configuration of the multilayer film and the base fabric, the heating temperature is preferably 100 ° C. or more, more preferably 120 ° C. or more, and / or 250 ° C. or less C. or less, more preferably 200.degree. C. or less. Moreover, the pressurizing pressure is preferable to be 5N / cm 2 or more, it can be 10 N / cm 2 or more, and / or preferable to be 700 N / cm 2 or less, to 500 N / cm 2 or less Can. Furthermore, it can be 5 to 50 N / cm 2 according to the operating conditions at the time of manufacturing the laminate.
 (用途)
 本形態による多層フィルム及び積層体は、車両用エアバッグ、アウトドア用品、包装用途等において好適に用いられ、特に車両用エアバッグ、とりわけカーテンエアバッグの製造に好適に用いられる。カーテンエアバッグとは、サイドウインドウ上部のルーフライン等に取り付けられており、衝突時等に高荷重が作用した場合に、サイドウインドウに沿わせて鉛直下方にカーテン状に展開させるエアバッグを指す。
(Use)
The multilayer film and the laminate according to the present embodiment are suitably used in vehicle airbags, outdoor products, packaging applications and the like, and particularly suitably used in the manufacture of vehicle airbags, particularly curtain airbags. The curtain airbag is attached to a roof line or the like in the upper portion of the side window, and refers to an airbag that is deployed in a curtain shape vertically downward along the side window when a high load is applied in a collision or the like.
 カーテンエアバッグは、展開時には、作動後数秒間、例えば6~7秒間にわたり膨らんだ状態で維持される必要があるため、カーテンエアバッグの材料には耐圧性が求められ、具体的には、引張強度、引裂強度等の機械的強度が求められる。また、カーテンエアバッグは、展開前は、長期間にわたり、折り畳まれた又は丸められた状態でケーシング等に収納されることが多いため、柔軟性も求められる。また、収納時には、高温・高湿の環境に晒されることも多い。しかしながら、本形態による多層フィルム及び積層体は、そのような用途であっても好適に使用することができる。 Since the curtain airbag needs to be maintained in a state of being inflated for several seconds, for example, 6 to 7 seconds after its operation, the material of the curtain airbag is required to have pressure resistance, specifically, Mechanical strength such as strength and tear strength is required. In addition, since the curtain airbag is often stored in a casing or the like in a folded or rolled state for a long time before deployment, flexibility is also required. In addition, when stored, it is often exposed to high temperature and high humidity environments. However, the multilayer film and the laminate according to the present embodiment can be suitably used even in such applications.
 なお、フィルムと基布とを有する積層体が、車両のエアバッグとして用いられる場合には、安全性を考慮した様々な性能が要求される。安全性については各国で基準が設定されているが、その基準は厳しくなる傾向にある。例えば、米国においては近年、エアバッグの安全性基準が引き上げられ、高温及び高湿下での耐久性について言えば、例えば、従来の高温高湿接着性の試験における温度及び湿度の条件が、温度40℃、相対湿度92%であったものが、温度70℃、相対湿度95%というより過酷なものとなった。そのため、かかる過酷な高温高湿の環境下で耐えうるエアバッグの材料が求められていた。これに対し、本形態による多層フィルム及び積層体は、このような過酷な高温高湿下で保存された後であっても層間剥離を起こしにくく、優れた耐久性を示すことができる。 In addition, when the laminated body which has a film and base cloth is used as an airbag of a vehicle, the various performance which considered safety | security is requested | required. The standards for safety are set in each country, but the standards tend to be strict. For example, in the United States in recent years, safety standards for air bags have been raised, and in terms of durability under high temperature and high humidity conditions, for example, temperature and humidity conditions in the conventional high temperature and high humidity adhesion test are temperature What was 40.degree. C. and 92% relative humidity becomes more severe as 70.degree. C. temperature and 95% relative humidity. Therefore, there has been a demand for an air bag material that can withstand such severe high temperature and high humidity environment. On the other hand, the multilayer film and the laminate according to the present embodiment are unlikely to cause delamination even after being stored under such severe high temperature and high humidity, and can exhibit excellent durability.
 以下、実施例によって本発明をさらに詳細に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.
 本実施例においては、多層フィルムを形成し、さらにその多層フィルムを基布に接着して積層体を製造し、評価を行った。 In this example, a multilayer film was formed, and the multilayer film was further adhered to a base fabric to produce a laminate, which was evaluated.
 [評価]
 <高温高湿接着性(高温高湿下での耐久性)>
 多層フィルムと基布とを積層させて得られた積層体から、50×150mmの試験片を作製し、この試験片を密閉容器内に入れ、容器内の条件を温度70℃、相対湿度95%にして168時間にわたり保った。その後、容器から取り出した試験片(積層体)の基布の部分を固定しつつ、多層フィルムの部分を180°方向に引張速度100mm/分で引きはがした際に要した力を剥離力(N/mm)として測定した。評価基準は以下の通りである。
〇:剥離力が0.5N/mm超であった。
△:剥離力が0.3~0.5N/mmであった。
×:剥離力が0.3N/mm未満であった、又は多層フィルム内で層間剥離が生じた。
[Evaluation]
<High temperature and high humidity adhesion (durability under high temperature and high humidity)>
From the laminate obtained by laminating the multilayer film and the base fabric, a test piece of 50 × 150 mm is prepared, and this test piece is placed in a closed container, and the conditions in the container are 70 ° C., 95% relative humidity. And kept for 168 hours. Thereafter, while fixing the portion of the base fabric of the test piece (laminate) taken out of the container, the force required when peeling off the portion of the multilayer film in the direction of 180 ° at a tensile speed of 100 mm / min It measured as N / mm). Evaluation criteria are as follows.
Good: Peeling force was over 0.5 N / mm.
Δ: Peeling force was 0.3 to 0.5 N / mm.
X: Peeling force was less than 0.3 N / mm, or delamination occurred in the multilayer film.
 なお、剥離力測定では、剥離試験中に多層フィルムが破断したり延伸されたりすることを防ぐため、多層フィルムの気密層側に、接着剤を介して厚さ100μmのポリエチレンテレフタレートフィルムを貼り合せて補強して用いた。 In the peeling force measurement, in order to prevent the multilayer film from being broken or stretched during the peeling test, a 100 μm-thick polyethylene terephthalate film is attached to the airtight layer side of the multilayer film through an adhesive. It reinforced and used.
 [実施例1]
 (多層フィルムの作製)
 4つの押出機を有するインフレーション押出装置(Collin社製)に、エチレン、アクリルエステル、及びグリシジルメタクリレートのターポリマー(Arkema社製「LOTADER(登録商標)AX8900」、グリシジルメタクリレートの含有量:8質量%、融点:65℃)と、高密度ポリエチレン(Exxonmobile社製「HMA014」、融点:134℃)と、無水マレイン酸変性の低密度ポリエチレン(Lyondell Basell社製「Plexar PX800」、融点117~125℃)と、ポリアミド(Evonik社製「Vestamid(登録商標)」、融点170℃)とを其々投入して、各樹脂の融点以上で溶融し、インフレーション法にて4層フィルムを作製した。各層の押出量は、10g/mであった。
Example 1
(Preparation of multilayer film)
In an inflation extrusion apparatus (manufactured by Collin) having four extruders, terpolymers of ethylene, acrylic ester, and glycidyl methacrylate (“LOTADER® AX 8900” manufactured by Arkema, content of glycidyl methacrylate: 8% by mass, Melting point: 65 ° C), high density polyethylene ("HMA014" manufactured by Exxonmobile, melting point: 134 ° C), and low density polyethylene modified with maleic anhydride ("Plexar PX800" manufactured by Lyondell Basell, melting point 117 ° C to 125 ° C) A polyamide (“Vestamid (registered trademark)” manufactured by Evonik, melting point 170 ° C.) was frequently added, and melted at a temperature higher than the melting point of each resin to prepare a four-layer film by an inflation method. The extrusion rate of each layer was 10 g / m 2 .
 得られた4層フィルムは、接着層としてエチレンとアクリルエステルとグリシジルメタクリレートとのターポリマー、第1中間層として高密度ポリエチレン、第2中間層として無水マレイン酸変性の低密度ポリエチレン、気密層としてポリアミドが、記載順に積層されたものであった。 The obtained four-layer film is a terpolymer of ethylene, acrylic ester and glycidyl methacrylate as an adhesive layer, high density polyethylene as a first intermediate layer, low density polyethylene modified with maleic anhydride as a second intermediate layer, and polyamide as an airtight layer. Were stacked in the order described.
 (基布と多層フィルムとの積層)
 積層装置(Mayer製 Twin-belt flat lamination system)を用いて、ポリエチレンテレフタレート(PET)製基布と上記4層フィルムを接着層が基布表面に接した状態で、170℃に加熱したニップロールで18N/cmに加圧しながら、上記接着層を軟化させて、基布と4層フィルムを積層した。PET製基布としては、総繊度470dtexの経糸・緯糸で、織り密度が各22本/cmの平織基布を使用した。
(Lamination of base cloth and multilayer film)
Using a laminating device (Twin-belt flat lamination system manufactured by Mayer), with an adhesive layer made of polyethylene terephthalate (PET) base fabric and the above-mentioned four-layer film in contact with the base fabric surface, 18 N with a nip roll heated to 170 ° C. The above adhesive layer was softened while being pressurized to 2 cm 2 to laminate the base cloth and the four-layer film. As a base fabric made of PET, a plain weave base fabric with a weave density of 22 / cm was used, with warps and wefts having a total fineness of 470 dtex.
 上述のように高温高湿接着性を測定したところ、剥離力は0.52N/mmであった。よって、実施例1の積層体は、優れた高温高湿接着性を示すことが分かった。 When the high temperature and high humidity adhesion was measured as described above, the peeling force was 0.52 N / mm. Therefore, it turned out that the layered product of Example 1 shows the outstanding high temperature high humidity adhesiveness.
 以下、本発明の好ましい態様を付記する。
(付記1)
 ポリエステルを含む基布に接着して使用される多層フィルムであって、
 前記基布に接着される側となる接着層と、当該接着層に結合されている気密層とを有し、
 前記接着層は、エポキシ基を含有するオレフィン系ポリマーを含み、
 前記気密層の融点は前記接着層の融点よりも高い、多層フィルム。
(付記2)
 前記オレフィン系ポリマーのエポキシ基の含有率は、前記オレフィン系ポリマーの全量に対して0.05~5質量%である、付記1に記載の多層フィルム。
(付記3)
 前記オレフィン系ポリマーは、エチレンと、(メタ)アクリルエステルと、グリシジル(メタ)アクリレートとを含むターポリマーである、請求項1又は2に記載の多層フィルム。
(付記4)
 前記気密層は、160℃以上の融点を有するポリマーを含む、付記1から3のいずれか一項に記載の多層フィルム。
(付記5)
 前記気密層はポリアミドを含む、付記1から4のいずれか一項に記載の多層フィルム。
(付記6)
 前記多層フィルムは、前記接着層と前記気密層との間に中間層を有する、付記5に記載の多層フィルム。
(付記7)
 前記中間層の融点は、前記接着層の融点より高く、前記気密層の融点より低い、付記6に記載の多層フィルム。
(付記8)
 前記中間層は、第1中間層と第2中間層とを有し、前記第1中間層は前記接着層に接合されており、前記第2中間層は前記気密層に接合されおり、
 前記第1中間層は、無水マレイン酸変性されていないポリエチレンを含み、前記第2中間層は、無水マレイン酸変性されたポリエチレンを含む、付記6又は7に記載の多層フィルム。
(付記9)
 付記1から8のいずれか一項に記載の多層フィルムと、ポリエステルを含む基布とが接着されてなる、積層体。
(付記10)
 基布と多層フィルムとを備えた積層体の製造方法であって、
 前記基布はポリエステルを含み、
 前記多層フィルムは、エポキシ基を含有するオレフィン系ポリマーを含む接着層と、当該接着層に結合され、当該接着層の融点よりも高い融点を有し、ポリマーを含む気密層とを有する多層フィルムであり、
 前記気密層が融解しない温度で加熱しながら、前記多層フィルムと基布とを加圧することにより、前記多層フィルムと前記基布とを接着させる工程を含む、積層体の製造方法。
(付記11)
 前記加熱温度は130~200℃である、付記10に記載の製造方法。
(付記12)
 前記加圧圧力は10~30N/cmである、付記10又は11に記載の製造方法。
(付記13)
 前記積層体を、前記接着層の融点以下の温度に冷却する工程をさらに含む、付記10から12のいずれか一項に記載の製造方法。
(付記14)
 付記1から8のいずれか一項に記載の多層フィルムを用いてなる、エアバッグ。
Hereinafter, preferred embodiments of the present invention will be additionally stated.
(Supplementary Note 1)
A multilayer film used by bonding to a base fabric containing polyester,
An adhesive layer on the side to be adhered to the backing, and an airtight layer bonded to the adhesive layer,
The adhesive layer comprises an olefin-based polymer containing an epoxy group,
The multilayer film, wherein the melting point of the hermetic layer is higher than the melting point of the adhesive layer.
(Supplementary Note 2)
The multilayer film according to claim 1, wherein the content of epoxy group of the olefin-based polymer is 0.05 to 5% by mass with respect to the total amount of the olefin-based polymer.
(Supplementary Note 3)
The multilayer film according to claim 1, wherein the olefin-based polymer is a terpolymer including ethylene, (meth) acrylic ester, and glycidyl (meth) acrylate.
(Supplementary Note 4)
5. The multilayer film of any of Appendices 1 to 3, wherein the hermetic layer comprises a polymer having a melting point of 160 ° C. or higher.
(Supplementary Note 5)
Additional layer according to any of the preceding claims, wherein the hermetic layer comprises a polyamide.
(Supplementary Note 6)
5. The multilayer film according to appendix 5, wherein the multilayer film has an intermediate layer between the adhesive layer and the airtight layer.
(Appendix 7)
Supplementary note 6, wherein the melting point of the intermediate layer is higher than the melting point of the adhesive layer and lower than the melting point of the hermetic layer.
(Supplementary Note 8)
The intermediate layer has a first intermediate layer and a second intermediate layer, the first intermediate layer is bonded to the adhesive layer, and the second intermediate layer is bonded to the air tight layer.
The multilayer film according to Appendix 6 or 7, wherein the first intermediate layer comprises polyethylene which is not maleic anhydride modified, and the second intermediate layer comprises maleic anhydride modified polyethylene.
(Appendix 9)
A laminate, wherein the multilayer film according to any one of appendices 1 to 8 and a base fabric containing polyester are adhered.
(Supplementary Note 10)
A method for producing a laminate comprising a base fabric and a multilayer film,
The base fabric comprises polyester and
The multilayer film is a multilayer film having an adhesive layer containing an olefin-based polymer containing an epoxy group, and an airtight layer bonded to the adhesive layer, having a melting point higher than that of the adhesive layer, and containing a polymer. Yes,
A method for producing a laminate, comprising the step of adhering the multilayer film and the base fabric by pressing the multilayer film and the base fabric while heating at a temperature at which the hermetic layer does not melt.
(Supplementary Note 11)
The method according to claim 10, wherein the heating temperature is 130 to 200 ° C.
(Supplementary Note 12)
The manufacturing method according to appendix 10 or 11, wherein the applied pressure is 10 to 30 N / cm 2 .
(Supplementary Note 13)
15. The manufacturing method according to any one of appendices 10 to 12, further comprising the step of cooling the laminate to a temperature not higher than the melting point of the adhesive layer.
(Supplementary Note 14)
An airbag comprising the multilayer film according to any one of appendices 1 to 8.
 本出願は、2017年8月24日に日本国特許庁に出願された特願2017-161160号に基づく優先権を主張するものであり、その全内容は参照をもってここに援用される。 This application claims the priority based on Japanese Patent Application No. 2017-161160 filed on Aug. 24, 2017 to the Japanese Patent Office, the entire contents of which are incorporated herein by reference.
1、1A、1B 多層フィルム
2、2A、2B 接着層
3 中間層
3a 第1中間層
3b 第2中間層
4、4A、4B 気密層
8 基布
9 OPW
10 積層体
100 積層体製造装置
102 加熱部
104 冷却部
DESCRIPTION OF SYMBOLS 1, 1A, 1B Multilayer film 2, 2A, 2B Adhesive layer 3 Intermediate layer 3a 1st intermediate layer 3b 2nd intermediate layer 4, 4A, 4B Air tight layer 8 Base cloth 9 OPW
DESCRIPTION OF SYMBOLS 10 Laminated body 100 Laminated body manufacturing apparatus 102 Heating part 104 Cooling part

Claims (13)

  1.  基布に接着して使用される多層フィルムであって、
     前記基布に接着される側となる接着層と、当該接着層に結合されている気密層とを有し、
     前記接着層は、エポキシ基を含有するオレフィン系ポリマーを含み、
     前記気密層の融点は前記接着層の融点よりも高い、多層フィルム。
    A multilayer film used by bonding to a base cloth,
    An adhesive layer on the side to be adhered to the backing, and an airtight layer bonded to the adhesive layer,
    The adhesive layer comprises an olefin-based polymer containing an epoxy group,
    The multilayer film, wherein the melting point of the hermetic layer is higher than the melting point of the adhesive layer.
  2.  前記オレフィン系ポリマーのエポキシ基の含有率は、前記オレフィン系ポリマーの全量に対して0.05質量%以上、5質量%以下である、請求項1に記載の多層フィルム。 The multilayer film according to claim 1, wherein the content of the epoxy group of the olefin-based polymer is 0.05% by mass or more and 5% by mass or less with respect to the total amount of the olefin-based polymer.
  3.  前記オレフィン系ポリマーは、エチレンと、(メタ)アクリルエステルと、グリシジル(メタ)アクリレートとを含むターポリマーである、請求項1又は2に記載の多層フィルム。 The multilayer film according to claim 1, wherein the olefin-based polymer is a terpolymer including ethylene, (meth) acrylic ester, and glycidyl (meth) acrylate.
  4.  前記気密層は、160℃以上の融点を有するポリマーを含む、請求項1から3のいずれか一項に記載の多層フィルム。 The multilayer film according to any one of claims 1 to 3, wherein the hermetic layer comprises a polymer having a melting point of 160 ° C or higher.
  5.  前記気密層はポリアミドを含む、請求項1から4のいずれか一項に記載の多層フィルム。 The multilayer film according to any one of claims 1 to 4, wherein the hermetic layer comprises a polyamide.
  6.  前記多層フィルムは、前記接着層と前記気密層との間に中間層を有する、請求項5に記載の多層フィルム。 The multilayer film according to claim 5, wherein the multilayer film has an intermediate layer between the adhesive layer and the airtight layer.
  7.  前記中間層の融点は、前記接着層の融点より高く、前記気密層の融点より低い、請求項6に記載の多層フィルム。 The multilayer film according to claim 6, wherein the melting point of the intermediate layer is higher than the melting point of the adhesive layer and lower than the melting point of the hermetic layer.
  8.  前記中間層は、第1中間層と第2中間層とを有し、前記第1中間層は前記接着層に接合されており、前記第2中間層は前記気密層に接合されおり、
     前記第1中間層は、無水マレイン酸変性されていないポリエチレンを含み、前記第2中間層は、無水マレイン酸変性されたポリエチレンを含む、請求項6又は7に記載の多層フィルム。
    The intermediate layer has a first intermediate layer and a second intermediate layer, the first intermediate layer is bonded to the adhesive layer, and the second intermediate layer is bonded to the air tight layer.
    The multilayer film according to claim 6 or 7, wherein the first intermediate layer comprises polyethylene not modified with maleic anhydride, and the second intermediate layer comprises polyethylene modified with maleic anhydride.
  9.  請求項1から8のいずれか一項に記載の多層フィルムと、ポリエステルを含む基布とが接着されてなる、積層体。 A laminated body in which the multilayer film according to any one of claims 1 to 8 and a base fabric containing polyester are adhered.
  10.  基布と多層フィルムとを備えた積層体の製造方法であって、
     前記多層フィルムは、エポキシ基を含有するオレフィン系ポリマーを含む接着層と、当該接着層に結合され、当該接着層の融点よりも高い融点を有し、ポリマーを含む気密層とを有する多層フィルムであり、
     前記気密層が融解しない温度で加熱しながら、前記多層フィルムと基布とを加圧することにより、前記多層フィルムと前記基布とを接着させる工程を含む、積層体の製造方法。
    A method for producing a laminate comprising a base fabric and a multilayer film,
    The multilayer film is a multilayer film having an adhesive layer containing an olefin-based polymer containing an epoxy group, and an airtight layer bonded to the adhesive layer, having a melting point higher than that of the adhesive layer, and containing a polymer. Yes,
    A method for producing a laminate, comprising the step of adhering the multilayer film and the base fabric by pressing the multilayer film and the base fabric while heating at a temperature at which the hermetic layer does not melt.
  11.  前記加熱温度は130℃以上、200℃以下である、請求項10に記載の製造方法。 The method according to claim 10, wherein the heating temperature is 130 ° C. or more and 200 ° C. or less.
  12.  前記積層体を、前記接着層の融点以下の温度に冷却する工程をさらに含む、請求項10又は11のいずれか一項に記載の製造方法。 The manufacturing method according to any one of claims 10 or 11, further comprising the step of cooling the laminated body to a temperature equal to or lower than the melting point of the adhesive layer.
  13.  請求項1から8のいずれか一項に記載の多層フィルムを用いてなる、エアバッグ。 An airbag comprising the multilayer film according to any one of claims 1 to 8.
PCT/JP2018/031191 2017-08-24 2018-08-23 Multilayered film, laminate, production method for laminate, and air bag WO2019039555A1 (en)

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