CN109476909B - Resin composition and laminate - Google Patents
Resin composition and laminate Download PDFInfo
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- CN109476909B CN109476909B CN201780043430.3A CN201780043430A CN109476909B CN 109476909 B CN109476909 B CN 109476909B CN 201780043430 A CN201780043430 A CN 201780043430A CN 109476909 B CN109476909 B CN 109476909B
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- polyol
- resin composition
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- adhesive layer
- laminate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
- B65D65/38—Packaging materials of special type or form
- B65D65/40—Applications of laminates for particular packaging purposes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D75/00—Packages comprising articles or materials partially or wholly enclosed in strips, sheets, blanks, tubes, or webs of flexible sheet material, e.g. in folded wrappers
- B65D75/28—Articles or materials wholly enclosed in composite wrappers, i.e. wrappers formed by associating or interconnecting two or more sheets or blanks
- B65D75/30—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding
- B65D75/32—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding one or both sheets or blanks being recessed to accommodate contents
- B65D75/34—Articles or materials enclosed between two opposed sheets or blanks having their margins united, e.g. by pressure-sensitive adhesive, crimping, heat-sealing, or welding one or both sheets or blanks being recessed to accommodate contents and having several recesses to accommodate a series of articles or quantities of material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The purpose of the present invention is to provide an adhesive that has excellent moldability, does not cause a decrease in the interlayer adhesive strength even after a long-term durability test, and does not cause appearance defects such as a bulge between layers, and a laminate using the same. The resin composition comprises a polyol, a polyisocyanate compound and a ketone resin, and more specifically, a resin composition in which the ratio of the mass of the solid components of the ketone resin and the polyol (mass of the solid component of the ketone resin/mass of the solid component of the polyol) is in the range of 1/100-20/100.
Description
Technical Field
The present invention relates to a resin composition containing a polyol, a polyisocyanate compound and a ketone resin, and an adhesive and a laminate using the resin composition.
Background
In recent years, as the use of electric storage devices for vehicles and homes has expanded, the capacity of secondary batteries has been increased, and good moldability has been required for battery packaging materials.
Further, since aluminum-plastic packages can store a pharmaceutical product for a long period of time, they are widely used as packaging materials for pharmaceutical products, and particularly, laminates for PTP having a metal foil layer are used in large quantities because of their high light-shielding property and moisture-proof property. In particular, aluminum-plastic packages are also used as bags for food or pet food, and from the viewpoint of protecting the contents, the same high moisture resistance is required.
Further, packaging materials using metal foils and plastic films are required to have interlayer adhesion strength that maintains long-term durability test and have no appearance defects.
Patent document 1 describes a polyurethane adhesive for a battery packaging material, which is characterized by containing a main agent and a curing agent, wherein the main agent contains an acrylic polyol (a) having a number average molecular weight of 10000 to 100000 and a hydroxyl value of 1 to 53mgKOH/g, and the equivalent ratio [ NCO ]/[ OH ] of an isocyanate group derived from an aromatic polyisocyanate (B) contained in the curing agent to a hydroxyl group derived from the acrylic polyol (a) is 10 to 30.
Patent document 2 describes a laminate in which a base layer, a barrier layer and a sealant layer are laminated in this order with an adhesive layer interposed therebetween, the barrier layer including a metal foil, the adhesive layer between the barrier layer and the sealant layer being made of a polyurethane adhesive containing a polyester polyol and an epoxy compound as main components and a polyisocyanate as a curing agent, and the ratio of the main component to the curing agent being 10: 1.269 to 10: 2.885 in terms of a solid content mass ratio, and describes that the laminate is used as a packaging body for a packaging container suitable for packaging a liquid material containing an alcohol at a high concentration.
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 5578269
Patent document 2: japanese patent laid-open publication No. 2015-157363
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of the above-mentioned background, and an object of the present invention is to provide an adhesive having excellent moldability, free from a decrease in interlayer adhesive strength even after a long-term durability test, and free from appearance defects such as a bulge between layers, and a laminate using the same.
Means for solving the problems
The present invention solves this problem by providing a resin composition containing a polyol, a polyisocyanate compound and a ketone resin.
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention provides an adhesive having excellent moldability, free from a decrease in interlayer adhesive strength even after a long-term durability test, and free from appearance defects such as a bulge between layers, and a laminate using the same.
Detailed Description
1. A resin composition contains a polyol, a polyisocyanate compound and a ketone resin.
2. The resin composition according to 1, wherein the polyol is polyethylene glycol, polypropylene glycol, polyether polyol, polyester polyol, polyether polyester polyol, polyester polyurethane polyol or a mixture thereof.
3. The resin composition according to 1. or 2, wherein the ratio of the mass of the solid content of the ketone resin to the mass of the solid content of the polyol (mass of the solid content of the ketone resin/mass of the solid content of the polyol) is in the range of 1/100 to 20/100.
4. The resin composition according to any one of claims 1 to 3, wherein an equivalent ratio (NCO/OH) of an isocyanate group (NCO) derived from a polyisocyanate compound and a hydroxyl group (OH) derived from a polyol is in a range of 1 to 30.
5. The resin composition according to any one of claims 1 to 4, wherein the polyisocyanate compound is an aromatic group-containing polyisocyanate compound.
6. A resin composition for adhesives, which comprises the resin composition according to any one of claims 1 to 5.
7. A laminate comprising a base material laminated via an adhesive layer, wherein the adhesive layer comprises the resin composition for an adhesive according to claim 6.
8. A battery packaging material comprising the laminate according to claim 7.
9. A medical PTP comprising the laminate according to item 7.
10. A packaging material for food, which comprises the laminate according to item 7.
11. A pet food bag using the laminate of claim 7.
In the present invention, as the polyol, polyethylene glycol, polypropylene glycol, polyester polyol obtained by reacting a polybasic acid with a polyhydric alcohol, polyester polyurethane polyol obtained by crosslinking polyester polyol with polyisocyanate, polyether polyol obtained by reacting a polyhydric alcohol with polyisocyanate, polyether polyester polyurethane polyol obtained by blending or crosslinking 2 or more of the above-mentioned polyols, and the like can be used. Any known starting material may be used as the polybasic acid.
As the polybasic acid, a dimer acid may also be used. Dimer acid is a product produced by diels-alder type 2 polymerization of unsaturated fatty acids of C18 such as oleic acid and linoleic acid, and various products are commercially available such as those obtained by hydrogenating unsaturated bonds to saturate them. Typically, the composition contains 0 to 5 wt% of C18 monocarboxylic acid, 70 to 98 wt% of C36 dimer acid and 0 to 30 wt% of C54 trimer acid. The dimer alcohol is a substance obtained by reducing the dimer acid described above.
Further, for example, succinic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, maleic anhydride, fumaric acid, 1, 3-cyclopentanedicarboxylic acid, 1, 4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, 1, 4-naphthalenedicarboxylic acid, 2, 5-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, biphenyldicarboxylic acid, 1, 2-bis (phenoxy) ethane-p, p' -dicarboxylic acid, and anhydride-or ester-forming derivatives of the dicarboxylic acids thereof; and polybasic acids such as p-hydroxybenzoic acid, p- (2-hydroxyethoxy) benzoic acid, ester-forming derivatives of their dihydroxy carboxylic acids, and dimer acids.
The polyol may be used as it is known to exist.
Specific examples thereof include glycols such as ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, methylpentanediol, dimethylbutylene glycol, butylethylpropanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, bishydroxyethoxybenzene, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol, triethylene glycol, polycaprolactone diol, bisphenol A, hydrogenated bisphenol A, and the like; polyesters obtained by ring-opening polymerization of cyclic ester compounds such as propiolactone, butyrolactone, epsilon-caprolactone, delta-valerolactone and beta-methyl-delta-valerolactone; and a polyol component such as a polyether obtained by addition polymerization of 1 or 2 or more kinds of monomers such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexene using 1 or 2 or more kinds of compounds having 2 active hydrogen atoms such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1, 3-butanediol, 1, 4-butanediol, 1, 6-hexanediol, and neopentyl glycol as an initiator by a conventional method.
The polyester may be a urethane-modified polyester or a polyurethane. Examples of the organic diisocyanates to be used for the urethanization include: aromatic diisocyanates (prepolymers of diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, tolylene diisocyanate, low-molecular-weight diols, the aforementioned aromatic diisocyanates, and the like); aliphatic diisocyanates (prepolymers of low molecular glycols such as 1, 6-hexamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, lysine diisocyanate, ethylene glycol and propylene glycol with the aforementioned aliphatic diisocyanates); alicyclic diisocyanates (prepolymers of isophorone diisocyanate, hydrogenated 4,4 '-diphenylmethane diisocyanate, methylcyclohexene diisocyanate, isopropylidene dicyclohexyl-4, 4' -diisocyanate, low-molecular glycols and the aforementioned alicyclic diisocyanates, etc.); and mixtures of 2 or more thereof. In the case of urethanization, the polyol described above and the polyether polyol described below may be used in addition to the polyester described above. In addition, the polyester and polyurethane may be used by blending the polyol and the polyether polyol component described later.
Examples of polyether polyols include: for example, a polyether polyol obtained by polymerizing an epoxide such as ethylene oxide, propylene oxide, butylene oxide, or tetrahydrofuran with a low molecular weight polyol such as water, ethylene glycol, propylene glycol, trimethylolpropane, or glycerin as an initiator.
The polyisocyanate used in the present invention may be any of those conventionally known.
Examples thereof include: polyisocyanates such as toluene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, 4' -methylenebis (cyclohexyl isocyanate), lysine diisocyanate, trimethylhexamethylene diisocyanate, 1,3- (isocyanatomethyl) cyclohexane, 1, 5-naphthalene diisocyanate, and triphenylmethane triisocyanate; and polyisocyanate derivatives (modified products) such as adduct of these polyisocyanates, biuret (urea) form of these polyisocyanates, and isocyanurate form of these polyisocyanates.
The polyisocyanate is not limited, but aromatic polyisocyanates are more excellent in peel strength and moldability than aliphatic polyisocyanates.
The adhesive composition of the present invention is characterized by comprising a polyol and a polyisocyanate, wherein the polyol is a polyethylene glycol, a polypropylene glycol, a polyether polyol, a polyester polyol, a polyether polyester polyol, a polyester polyurethane polyol, or a mixture thereof.
The resin composition of the present invention is characterized by containing a ketone resin.
The ketone resin used in the present invention includes known and conventional ones, and a formaldehyde resin, a cyclohexanone-formaldehyde resin, a ketone-aldehyde condensation resin, or the like can be suitably used.
The invention has the following characteristics: the ratio of the solid content mass of the ketone resin to the solid content mass of the polyol (solid content mass of the ketone resin/solid content mass of the polyol) is in the range of 1/100-20/100. Within this range, the balance of peel strength (7N/15mm or more), moldability (30 mm. times.30 mm square, depth 6mm or more), moist heat resistance (no bulge at 65 ℃ C. -90%/72 hours in the vicinity of the boundary between the molded flange part and the side wall part having the depth 6.5 mm), and heat sealability (no bulge at 190 ℃ C./3 seconds in the vicinity of the boundary between the molded flange part and the side wall part having the depth 6.5 mm) was the best.
When the content is less than 1/100, moldability is deteriorated, and when the content is more than 20/100, adhesion to the substrate is deteriorated and peel strength is deteriorated.
In addition, the present invention has the following features: the equivalent ratio (NCO/OH) of the isocyanate group (NCO) derived from the polyisocyanate compound and the hydroxyl group (OH) derived from the polyol is in the range of 1 to 30. When the amount is within this range, the balance between the moist heat resistance (no bulge at 65 ℃ C. -90%/72 hours in the vicinity of the boundary between the flange portion and the side wall portion formed at a depth of 6.5 mm) and the heat sealability (no bulge at 190 ℃ C./3 seconds in the vicinity of the boundary between the flange portion and the side wall portion formed at a depth of 6.5 mm) is the best, and the peel strength and the moist heat resistance are inferior when the value is less than 1.
When the amount is more than 30, the peel strength and heat sealability are deteriorated.
Preferable ranges are 1 to 30, and more preferably 5 to 20.
The adhesive may be in the form of either a solvent type or a solvent-free type. In the case of the solvent type, the solvent is used as a reaction medium in the production of the main agent and the curing agent, and is further used as a diluent in the coating. Examples of the solvent that can be used include esters such as ethyl acetate, butyl acetate, and cellosolve acetate, ketones such as acetone, methyl ethyl ketone, isobutyl ketone, and cyclohexanone, ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as dichloromethane and dichloroethane, dimethyl sulfoxide, and dimethyl sulfonamide. Among these, it is generally preferable to use ethyl acetate or methyl ethyl ketone alone or in combination.
In the adhesive of the present invention, as another preferable embodiment, a known phosphoric acid compound or a derivative thereof can be used in combination. This further improves the initial adhesion of the adhesive, and eliminates problems such as tunneling.
Examples of the phosphoric acids or derivatives thereof used herein include phosphoric acids such as hypophosphorous acid, phosphorous acid, orthophosphoric acid, hypophosphoric acid (hypophosphoric acid), condensed phosphoric acids such as metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid, and ultraphosphoric acid, and monoesters such as monomethyl n-phosphate, monoethyl n-phosphate, monopropyl n-phosphate, monobutyl n-phosphate, mono-2-ethylhexyl n-phosphate, monophenyl n-phosphate, monomethyl phosphite, monoethyl phosphite, monopropyl phosphite, monobutyl phosphite, mono-2-ethylhexyl phosphite, monophenyl phosphite, di-2-ethylhexyl n-phosphate, diphenyldimethyl n-phosphate, diethyl phosphite, dipropyl phosphite, dibutyl phosphite, di-2-ethylhexyl phosphite, diphenyl phosphite, and monoesters such as dibutyl phosphite, Diesters, monoesters and diesters derived from condensed phosphoric acids and alcohols, for example, those obtained by adding an epoxy compound such as ethylene oxide or propylene oxide to the above-mentioned phosphoric acids, and epoxy phosphate esters obtained by adding the above-mentioned phosphoric acids to an aliphatic or aromatic diglycidyl ether.
The phosphoric acid or its derivative can be used in 1 or 2 or more. The method of incorporating the compound may be simply mixing.
In the adhesive of the present invention, an adhesion promoter may be used. Examples of the adhesion promoter include silane coupling agents, titanate coupling agents, aluminum-based coupling agents, and epoxy resins.
Examples of the silane coupling agent include: aminosilanes such as γ -aminopropyltriethoxysilane, γ -aminopropyltrimethoxysilane, N- β (aminoethyl) - γ -aminopropyltrimethyldimethoxysilane, and N-phenyl- γ -aminopropyltrimethoxysilane; epoxy silanes such as beta- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, and gamma-glycidoxypropyltriethoxysilane; vinyl silanes such as vinyltris (β -methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane and γ -methacryloxypropyltrimethoxysilane; hexamethyldisilazane, gamma-mercaptopropyltrimethoxysilane, and the like.
Examples of the titanate-based coupling agent include: titanium tetraisopropoxide, titanium tetra-n-butoxide, butyl titanate dimer, tetrastearyl titanate, titanium acetylacetonate, titanium lactate, tetraoctanediol titanate, titanium lactate, titanium tetrastearoxy, and the like.
Examples of the aluminum-based coupling agent include: aluminum (ll) acetoacetoxy diisopropanoate, and the like.
The adhesive of the present invention can be applied by any known coating method, and is generally applied by gravure roll coating. The coating amount of the adhesive is 1.5 to 5g/m in terms of solid content2Preferably 2 to 4g/m2The coating conditions of (3) were used. Generally, the solvent-type coating is applied in an amount of about 1.0 to 4.0g/m2The amount of the solvent is about 0.5 to 3.0g/m2Can be used from left to right.
In addition, the present invention has the following features: contains a polyol and a ketone resin, and the mass ratio of the solid components of the ketone resin and the polyol is 1/100-20/100 (ketone resin/polyol).
When the solid content mass ratio of the ketone resin to the polyol is outside this range, the laminate is broken during molding, and the vicinity of the boundary between the molded flange portion and the side wall portion bulges after the wet heat test, which is not preferable.
The laminate of the present invention has the following features: the base layer and the metal foil are laminated via an adhesive layer. The substrate to be used may be any of the known and conventional substrates.
Examples of materials including polyamide, polyester, and polyolefin include, for example, the following: polyethylene [ PE ] and polypropylene [ PP ], poly (vinyl chloride) [ PVC ], polyvinylidene chloride [ PVdC ], cyclic olefin copolymer [ COC ], polystyrene [ PS ], acrylic resin, etc., preferably comprising a material selected from the group consisting of polyamide, polyolefin, cyclic olefin copolymer [ COC ], polyester, poly (vinyl chloride) [ PVC ], polyvinylidene chloride [ PVdC ], polystyrene and acrylic resin, most preferably polyester, poly (vinyl chloride) [ PVC ]. Examples of the polyethylene include: low density polyethylene [ LDPE ], linear low density polyethylene [ LLDPE ], linear medium density polyethylene [ LMDPE ], linear and very low density polyethylene [ VLDPE ], linear ultra low density polyethylene [ ULDPE ], high density polyethylene [ HDPE ], preferably low density polyethylene. Examples of the polyester include: polyethylene terephthalate [ PET ] and glycol-modified polyethylene terephthalate [ PETG ]. The cyclic olefin copolymer [ COC ] is preferably a copolymer of ethylene and norbornene.
The polyamide is preferably a polyamide homopolymer or copolymer. Examples of polyamide homopolymers include: poly (4-aminobutyric acid) [ nylon 4 ], poly (6-aminocaproic acid) [ nylon 6, or poly (caprolactam) ], poly (7-aminoheptanoic acid) [ nylon 7 ], poly (8-aminocaprylic acid) [ nylon 8 ], poly (9-aminononanoic acid) [ nylon 9 ], poly (10-aminodecanoic acid) [ nylon 10 ], poly (11-aminoundecanoic acid) [ nylon 11 ], poly (12-aminododecanoic acid) [ nylon 12 ], and the like. Examples of polyamide copolymers include: nylon 4,6, poly (hexamethylene adipamide) [ nylon 6,6 ], poly (hexamethylene sebacamide) [ nylon 6,10 ], poly (heptamethylene pimelimide) [ nylon 7,7 ], poly (octamethylene suberamide) [ nylon 8,8 ], poly (hexamethylene azelamide) [ nylon 6,9 ], poly (nonamethylene azelamide) [ nylon 9,9 ], poly (decamethylene azelamide) [ nylon 10,9 ], poly (tetramethylene diamine-co-oxalic acid) [ nylon 4, 2], polyamides of n-dodecanedioic acid and hexamethylene diamine [ nylon 6,12 ], polyamides of dodecamethylene diamine and n-dodecanedioic acid [ nylon 12,12 ], and the like. Other useful polyamide copolymers include: caprolactam/hexamethylene adipamide copolymer [ nylon 6,6/6 ], hexamethylene adipamide/caprolactam copolymer [ nylon 6/6,6 ], trimethylene adipamide/hexamethylene azelaiamide copolymer [ nylon trimethyl 6,2/6, 2], hexamethylene adipamide-hexamethylene-azelaiamide caprolactam copolymer [ nylon 6,6/6,9/6 ], poly (tetramethylene diamine-co-isophthalic acid) [ nylon 4, I ], polyhexamethylene isophthalamide [ nylon 6, 1], hexamethylene adipamide/hexamethylene-isophthalamide [ nylon 6,6/6I ], hexamethylene adipamide/hexamethylene terephthalamide [ nylon 6,6/6I ], 6/6T, poly (2,2, 2-trimethylhexamethylene terephthalamide), poly (m-xylylene adipamide) [ MXD6 ], poly (p-xylylene adipamide), poly (hexamethylene terephthalamide), poly (dodecamethylene terephthalamide), polyamide 6T/6I, polyamide 6/MXDT/I, polyamide MXDI and the like.
Further, other nylons not specifically described in the present specification and combinations of the substances described in the present specification may be mentioned. Among these, the polyamide is more preferably nylon 6, nylon 6/6,6 or a mixture thereof, and still more preferably nylon 6. The thickness of the other material layer is usually about 20 to 250 μm. In particular, SiOx-deposited PET sheets are preferable when moisture resistance is required. The thickness is usually about 10 to 20 μm.
The lid material is preferably provided with a heat-sealable resin layer because the contents stored therein can be sealed by heat sealing. The heat-sealable resin layer is not particularly limited as long as it is a layer to be fused to the surface of a substrate containing contents at the time of heat sealing, and examples thereof include 1 or 2 or more layers including low density polyethylene [ LDPE ], medium density polyethylene [ MDPE ], high density polyethylene [ HDPE ], linear low density polyethylene [ LLDPE ], ethylene vinyl acetate copolymer [ EVA ], polypropylene [ PP ], ethylene acrylic acid copolymer [ EAA ], ethylene methacrylic acid copolymer [ EMA ], ethylene methyl acrylate copolymer [ EMAA ], ethylene ethyl acrylate copolymer [ EEA ], ethylene methyl methacrylate copolymer [ EMMA ], and ionomer [ IO ]. The cover material preferably contains a metal-plated film layer such as an aluminum layer and a metal layer such as a metal foil layer, and more preferably contains an aluminum foil layer, from the viewpoint of good low water vapor permeability.
Further, from the viewpoint of excellent light-shielding properties and moisture-proofing properties, a configuration having a metal foil layer (aluminum foil layer) on both surfaces thereof is particularly preferable, wherein a base material having a recess for accommodating contents formed therein and a lid material bonded to a flange portion of the base material contain the metal foil layer.
The laminate thus obtained can be suitably used as a packaging material for aluminum-plastic packaging.
The PTP package of the present invention can be produced by the following production method using the above-described base material and lid material.
The PTP package of the present invention is a PTP package including a base material in which a recess for accommodating contents is formed, and a lid material bonded to a flange portion of the base material.
The PTP package described above can be made as follows: the sheet is produced by molding a predetermined number of recesses in a base sheet, then storing the contents such as tablets in each of the molded recesses, and heat-sealing a lid material to a flange portion of the base sheet by using a molding filling and sealing machine for PTP packaging.
The concave portion of the base sheet is formed by the following method.
Heated compressed air forming: a method of forming the concave portion by holding the base sheet between a lower die having a hole through which high-temperature and high-pressure air is supplied and an upper die having a concave portion in a cavity (pocket) shape and supplying air while heating and softening the base sheet.
Preheater flat plate type compressed air forming method: the method comprises heating and softening a base material sheet, clamping the base material sheet between a lower die having a hole for supplying high-pressure air and an upper die having a cavity-shaped recess, and supplying air to form the recess.
Roll-to-roll vacuum forming: a method of forming a concave portion by heating a substrate sheet to a heating roller and partially heat-softening the substrate sheet, and then evacuating the concave portion of the roller having a cavity-shaped concave portion.
Needle molding method: heating and softening the substrate sheet, and then pressing and connecting the substrate sheet by a concave-convex mould in the shape of a groove cavity.
Preheater plug assisted compressed air forming method: the method is a method in which a base material sheet is heated and softened, and then sandwiched between a lower die having a hole for supplying high-pressure air and an upper die having a cavity-shaped recess, and air is supplied to form the recess.
Among them, from the viewpoint of uniformly obtaining the thickness of the molded substrate, a preheater plug assist compressed air molding method which is a heating vacuum molding method is preferable.
The PTP package of the present invention is a PTP package including a base material and a lid material, in which a recess portion is formed in a base material sheet by vacuum or compressed air molding or the like. The base material has a recess for receiving the content and a flange formed at the periphery of the recess, and a lid material is fixed to the flange by heat sealing or the like.
In order to package the contents in such a base material, the contents are sealed between the recess of the base material and the lid material, and the flange portion and the lid material are fixed by fixing means such as heat sealing.
The laminate of the present invention can be used as a bag for food or pet food, and the same substrate as used for PTP packaging can be used for the bag for storing the contents.
The aluminum may be coated with a coating agent to bond the lid material to the base material.
In addition, the laminate of the present invention has no reduction in the interlayer adhesive strength and no appearance defects such as the occurrence of interlayer swelling even after a long-term durability test. Therefore, a battery using such a laminate as a battery electrolyte sealing film or a battery electrode part protecting film, and a secondary battery using such a laminate as a secondary battery electrolyte sealing film or a secondary battery electrode part protecting film can be stably used for a long period of time.
Examples
The present invention will be described in detail below.
The details of each sample used are described in the lower part of table 2.
(example 1)
After 0.5 part of TEGO Variplus AP was added to 10 parts of DIC DRYLX 906 and sufficiently stirred until the TEGO Variplus AP was completely dissolved, 2 parts of KW-75 and methyl ethyl ketone were added to make the nonvolatile content to be 25%, and sufficiently stirred, a coating liquid (1) for an adhesive was prepared.
(example 2) to (example 7)
Adhesive coating liquids (2) to (7) were produced in the same manner as in example 1, except that the materials and the compounding ratios described in table 1 were used.
Production examples 1 to 5
Adhesive coating liquids (8) to (13) were produced in the same manner as in example 1, except that the materials and the compounding ratios described in table 2 were used.
Example 1 < production of laminate >
The coating liquid (1) for an adhesive, which is an adhesive for an outer layer, was applied to the matte surface of an aluminum foil having a thickness of 30 μm in an amount such that the amount of the coating liquid was 4g/m by a dry laminator, the solvent was evaporated, and then a stretched polyamide film having a thickness of 25 μm was laminated.
Then, the adhesive was applied to the glossy surface of the aluminum foil of the obtained laminated film in an amount of 4g/m by a dry laminator to evaporate the solvent, and then an unstretched polypropylene film having a thickness of 25 μm was laminated, followed by curing (aging) at 60 ℃ for 3 days to cure the adhesive, thereby obtaining a laminate.
Base material: polyimide film "EMBLM" 25 μm (manufactured by UNITIKA corporation), aluminum foil "1N 30" 30 μm (manufactured by Toyo aluminum Co., Ltd.)
(example 1) to (example 7)
In the same manner as in (example 1) < production of laminate > the adhesive coating liquids (2) to (7) were used (example 2) to (example 7).
(comparative examples 1) to 6 < production of laminate >
The adhesive coating liquids (8) to (13) were used to perform the operations (comparative examples 1) to (comparative example 6) in the same manner as in (example 1).
Each evaluation was performed as follows.
< adhesion Strength >
Tensilon test, manufactured by A & D, 15mm wide 180 DEG peel strength
< method for evaluating moldability >
The battery packaging material was cut into a size of 60X 60mm to prepare a blank sample (molded material, raw material). The blank sample was subjected to stretch forming with a flat die having a free forming height, with the aluminum foil matte surface facing outward, and formability was evaluated based on the unsent aluminum foil fracture, the bulge between the layers, and the maximum forming height.
The punch shape of the die used was a square with a side of 30mm, a corner R of 2mm, and a punch shoulder (punch) R of 1 mm. The die hole of the used die is in the shape of a square with 34mm, the corner R of the die hole is 2mm, the shoulder R of the die hole is 1mm, and the clearance between the punch and the die hole is 0.3mm on one side. The inclination corresponding to the molding height is generated by the gap. The following three-stage evaluation was performed in accordance with the molding height.
Good: 8mm or more (practically excellent)
And (delta): more than 6mm (practical area)
X: less than 6mm
< moist Heat resistance after Molding >
The aluminum foil was cut into a size of 60X 60mm so that the matte surface of the aluminum foil was on the outside, and was subjected to stretch molding at a molding height of 6.5mm using a flat die having a free molding height. The obtained tray of 30mm square was placed in a constant temperature and humidity chamber at 65 ℃ under an atmosphere of 90% RH and allowed to stand for 72 hours. The tray was taken out from the constant temperature and humidity chamber, and appearance near the boundary between the flange portion and the side wall portion was confirmed to evaluate whether or not a bulge occurred between the stretched polyamide film and the aluminum foil.
O: without ridges
X: bulge occurs
< Heat resistance after Molding >
The aluminum foil was cut into a size of 60X 60mm so that the matte surface of the aluminum foil was on the outside, and was subjected to stretch molding at a molding height of 6.5mm using a flat die having a free molding height. The resulting tray was brought into contact with the side wall portion at a temperature of 190 ℃ for 3 seconds so that the flange portion of the tray was in contact with the side wall portion, and the appearance of the tray in the vicinity of the boundary between the flange portion and the side wall portion was confirmed to evaluate whether or not the bulging occurred between the stretched polyamide film and the aluminum foil.
O: without ridges
X: bulge occurs
The results are shown in tables 1 and 2.
[ Table 1]
[ Table 2]
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | |
| DIC DRY LX906 | 10 | 10 | 10 | |||
| DIC DRY LX963 | 10 | 10 | ||||
| VYLON GK150 | ||||||
| TEGO Variplus AP | ||||||
| K-90 | ||||||
| KE-100 | 0.6 | |||||
| ACRYDIC 57-451 | 1 | 10 | ||||
| EPICLON 1050-70X | 3 | |||||
| KBM-403 | 0.15 | 0.15 | 0.15 | |||
| KW-75 | 2 | 2 | 2 | 1 | 9.5 | 2 |
| Solid content Mass of ketone resin/solid content Mass of polyol (%) | 0 | 0 | 0 | 0 | 0 | 0 |
| Peel strength | 5.3 | 7.1 | 6.3 | 1.0 | 1.5 | 2.5 |
| Formability | Δ | Δ | ○ | Δ | × | Δ |
| Moisture and heat resistance | × | × | × | × | ○ | × |
| Heat sealability | × | × | × | × | ○ | × |
DIC DRYLX 906(DIC Co., Ltd.) polyester polyol nonvolatile component: 60% hydroxyl value: 5.5
DIC DRYLX 963 (available from DIC) polyester polyol nonvolatile fraction: 50% hydroxyl value: 4
VYLON GKl50 (manufactured by toyobo co.) polyester polyol non-volatile components: 100% hydroxyl value: 7
TEGOVariplus AP (manufactured by EVONIC) ketone resin nonvolatile components: 100 percent
K-90 (available from Mitsukawa chemical Co., Ltd.) non-volatile component of ketone resin: 100 percent
KE-100 (available from Mitsukawa chemical Co., Ltd.) rosin ester resin nonvolatile Components: 100 percent
ACRYDIC 57-451(DIC Co., Ltd.) acrylic resin nonvolatile Components: 50% hydroxyl value: 11
EPICLON 1050-70X (available from DIC Co.) epoxy resin nonvolatile Components: 70% hydroxyl value: 110
KBM-403 (manufactured by shin-Etsu chemical Co., Ltd.) silane coupling agent nonvolatile component: 100 percent
KW-75 (available from DIC Co.) non-volatile polyisocyanate: 75% NCO%: 13.3
It is clear from the examples and comparative examples that the examples satisfying the requirements of the present invention can solve the problems of the present invention, and the examples containing no ketone resin and no resin other than ketone resins (comparative examples 1 to 3) and the examples containing a resin other than ketone resins (comparative examples 4 to 6) cannot solve the problems of the present invention.
Industrial applicability
The laminate of the present invention can be suitably used as a packaging material for a battery, PTP, a bag for food or pet food, and the like.
Claims (15)
1. A two-component adhesive comprising a polyol, a polyisocyanate compound and a ketone resin, wherein the polyol contains at least 1 selected from the group consisting of a polyether polyol, a polyester polyol, a polyether polyester polyol, a polyester polyurethane polyol, a polyurethane polyol and a polyether polyurethane polyol, and the solid content mass of the ketone resin/the solid content mass of the polyol is in the range of 1/100-20/100.
2. The two-component adhesive according to claim 1, wherein an equivalent ratio of NCO groups derived from the polyisocyanate compound to OH groups derived from the polyol, i.e., NCO/OH, is in a range of 1 to 30.
3. The two-component adhesive according to claim 1, wherein the polyisocyanate compound is an aromatic polyisocyanate compound.
4. The two-component adhesive according to claim 1, wherein the polyether polyol is a polyether polyol obtained by polymerizing an epoxy compound using at least 1 selected from the group consisting of water and low-molecular-weight polyols as an initiator.
5. The two-component adhesive according to claim 4, wherein the epoxide is ethylene oxide or propylene oxide.
6. A resin composition for adhesives, which is used for a two-component adhesive comprising a polyol and a polyisocyanate compound, comprising:
comprising at least 1 polyol selected from the group consisting of polyether polyols, polyester polyols, polyether polyester polyols, polyester polyurethane polyols, polyurethane polyols; and
a ketone resin,
the solid content mass of the ketone resin/the solid content mass of the polyol is 1/100-20/100.
7. The resin composition for adhesives according to claim 6, wherein the equivalent ratio of NCO groups derived from the polyisocyanate compound to OH groups derived from the polyol, i.e., NCO/OH, is in the range of 1 to 30.
8. The resin composition for adhesive according to claim 6, wherein the polyisocyanate compound is an aromatic polyisocyanate compound.
9. The resin composition for adhesives according to claim 6, wherein the polyether polyol is obtained by polymerizing an epoxy compound using at least 1 selected from the group consisting of water and low-molecular-weight polyols as an initiator.
10. The resin composition for adhesive according to claim 9, wherein the epoxide is ethylene oxide or propylene oxide.
11. A packaging material for aluminum-plastic packaging, which comprises a laminate comprising substrates laminated together via an adhesive layer, wherein the adhesive layer is the two-component adhesive according to any one of claims 1 to 5 or a cured product of the resin composition for adhesives according to any one of claims 6 to 10.
12. A battery packaging material using a laminate comprising substrates laminated via an adhesive layer, wherein the adhesive layer is the two-component adhesive according to any one of claims 1 to 5 or a cured product of the adhesive resin composition according to any one of claims 6 to 10.
13. A medical PTP comprising a laminate formed by laminating substrates with an adhesive layer therebetween, wherein the adhesive layer is the two-component adhesive according to any one of claims 1 to 5 or a cured product of the resin composition for adhesives according to any one of claims 6 to 10.
14. A packaging material for food, which comprises a laminate comprising substrates laminated together with an adhesive layer interposed therebetween, wherein the adhesive layer is the two-component adhesive according to any one of claims 1 to 5 or a cured product of the resin composition for adhesives according to any one of claims 6 to 10.
15. A pet food bag using a laminate formed by laminating base materials via an adhesive layer, wherein the adhesive layer is the two-component adhesive according to any one of claims 1 to 5 or a cured product of the adhesive resin composition according to any one of claims 6 to 10.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016-146346 | 2016-07-26 | ||
| JP2016146346 | 2016-07-26 | ||
| PCT/JP2017/026221 WO2018021132A1 (en) | 2016-07-26 | 2017-07-20 | Resin composition and laminate |
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| CN109476909A CN109476909A (en) | 2019-03-15 |
| CN109476909B true CN109476909B (en) | 2021-04-23 |
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| JP (1) | JP6384622B2 (en) |
| CN (1) | CN109476909B (en) |
| TW (1) | TWI724212B (en) |
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| WO2018047672A1 (en) * | 2016-09-06 | 2018-03-15 | Dic株式会社 | Adhesive, blister pack laminate and blister pack using same |
| JP7416313B1 (en) | 2023-05-26 | 2024-01-17 | 東洋インキＳｃホールディングス株式会社 | Adhesives for packaging materials for power storage devices, packaging materials for power storage devices, containers for power storage devices, and power storage devices |
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| CN1649926A (en) * | 2002-04-25 | 2005-08-03 | 西柏控股有限公司 | Polyurethane resin produced from poly hydroxylated resin |
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| US4311620A (en) * | 1980-05-08 | 1982-01-19 | Hooker Chemicals & Plastics Corp. | Foundry aggregate binders and foundry compositions prepared therefrom |
| JP3344732B2 (en) * | 1991-07-17 | 2002-11-18 | 三井化学株式会社 | Reactive hot melt adhesive composition |
| JPH08170064A (en) * | 1994-10-20 | 1996-07-02 | Sekisui Chem Co Ltd | Urethane-based aqueous adhesive composition |
| JPH1060258A (en) * | 1996-08-22 | 1998-03-03 | Sakata Corp | Cold-curable water-based polyurethane resin composition and its use |
| JPH1060259A (en) * | 1996-08-22 | 1998-03-03 | Sakata Corp | Cold-curable water-based polyurethane resin composition and its use |
| JP2008001780A (en) * | 2006-06-21 | 2008-01-10 | Kansai Paint Co Ltd | Aqueous resin composition, aqueous coating composition, and method for forming coated film using the same |
| EP2708566A1 (en) * | 2012-09-14 | 2014-03-19 | Sika Technology AG | Dual component polyurethane compounds, particularly suitable for use as tough elastic structural adhesives or sealing compounds |
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2017
- 2017-07-20 JP JP2017561024A patent/JP6384622B2/en active Active
- 2017-07-20 WO PCT/JP2017/026221 patent/WO2018021132A1/en active Application Filing
- 2017-07-20 CN CN201780043430.3A patent/CN109476909B/en active Active
- 2017-07-26 TW TW106125014A patent/TWI724212B/en active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1649926A (en) * | 2002-04-25 | 2005-08-03 | 西柏控股有限公司 | Polyurethane resin produced from poly hydroxylated resin |
| JP2008001779A (en) * | 2006-06-21 | 2008-01-10 | Kansai Paint Co Ltd | Aqueous resin composition, aqueous coating composition, and method for forming coated film by using the same |
| CN103635553A (en) * | 2011-09-22 | 2014-03-12 | 琳得科株式会社 | Flame retardant adhesive sheet |
| CN105602426A (en) * | 2015-12-28 | 2016-05-25 | 安徽安大华泰新材料有限公司 | Waterproof aqueous polyurethane coating |
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| JP6384622B2 (en) | 2018-09-05 |
| JPWO2018021132A1 (en) | 2018-07-26 |
| TWI724212B (en) | 2021-04-11 |
| CN109476909A (en) | 2019-03-15 |
| TW201829520A (en) | 2018-08-16 |
| WO2018021132A1 (en) | 2018-02-01 |
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