WO2023047872A1 - 接着剤用組成物及び積層体 - Google Patents
接着剤用組成物及び積層体 Download PDFInfo
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- WO2023047872A1 WO2023047872A1 PCT/JP2022/031773 JP2022031773W WO2023047872A1 WO 2023047872 A1 WO2023047872 A1 WO 2023047872A1 JP 2022031773 W JP2022031773 W JP 2022031773W WO 2023047872 A1 WO2023047872 A1 WO 2023047872A1
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- modified
- acid
- adhesive composition
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- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000003097 polyterpenes Chemical class 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002397 thermoplastic olefin Polymers 0.000 description 1
- 239000012974 tin catalyst Substances 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 125000006839 xylylene group Chemical group 0.000 description 1
Images
Classifications
-
- 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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
- C09J123/30—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment by oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/28—Metal sheet
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
-
- 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
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
Definitions
- the present invention relates to an adhesive composition and a laminate obtained using the adhesive composition.
- a laminate having a laminated structure in which a metal foil and a resin film are laminated with an adhesive can be used as a packaging material for containing water, oil, food, medicines, chemicals, etc. Since such packaging materials may be exposed to high temperatures, the adhesive is required to have excellent adhesiveness at high temperatures.
- Patent Document 1 discloses an adhesive for laminating a metal foil and a resin film, and describes that it exhibits good adhesiveness even at high temperatures. Further improvement in adhesiveness is required.
- the present invention provides an adhesive composition that can provide an adhesive that can firmly bond a metal foil and a resin film even at high temperatures, and a metal foil and a resin film that are difficult to separate even at high temperatures.
- An object is to provide a laminate.
- the total number of moles of isocyanato groups possessed by the polyisocyanate compound of Component 2 is Ia
- the total number of moles of isocyanato groups possessed by the modified isocyanate compound of Component 3 is Ib
- the modified groups possessed by the modified isocyanate compound of Component 3 are wherein H is the total number of moles of Ia, Ib and H, the ratio H/(Ia+Ib+H) of H to the total number of moles of Ia, Ib and H is more than 0 and 0.5 or less.
- polyisocyanate compound is at least one compound selected from isocyanurate compounds of saturated aliphatic polyisocyanates and allophanate compounds of saturated aliphatic polyisocyanates.
- the adhesive composition according to item 1. [6] The acid-modified polyolefin according to any one of [1] to [5], wherein the acid-modified polyolefin contains an acid-modified polyolefin using one or more of propylene, ethylene, and butene as a monomer. adhesive composition.
- the present invention it is possible to strongly bond the metal foil and the resin film even at high temperatures, and it is possible to provide a laminate in which the metal foil and the resin film are difficult to separate even at high temperatures.
- a laminate 1 according to this embodiment will be described with reference to FIG. 1
- the laminate 1 shown in FIG. 1 includes a metal foil 2, a resin film 3, an adhesive layer 4 interposed between the metal foil 2 and the resin film 3 and bonding the metal foil 2 and the resin film 3, It has This adhesive layer 4 is formed of an adhesive containing a reaction product of an adhesive composition according to this embodiment, which will be described in detail later.
- This laminate 1 can be used as a packaging material for containing various articles, but the metal foil 2 and the resin film 3 are firmly adhered by the adhesive layer 4 even at high temperatures and are difficult to peel off.
- high temperatures for example, temperatures of 80°C or higher and temperatures of 100°C or higher.
- it can be used as a packaging material for containing water, oil, food, medicines, chemicals, and the like.
- foods include vinegar and highly acidic foods with high free fatty acid content.
- chemicals include acids, alkalis and organic solvents.
- Metal foil The type of metal forming the metal foil 2 is not particularly limited, but examples thereof include aluminum, aluminum alloys, stainless steel, and aluminum-iron alloys. When the laminate is used as a packaging material for containing foods, medicines, chemicals, etc., the metal foil 2 can provide a gas barrier property that suppresses the intrusion of oxygen and moisture into the interior of the packaging material. . Although the thickness of the metal foil 2 is not particularly limited, it may be 5 ⁇ m or more and 50 ⁇ m or less.
- the type of resin forming the resin film 3 is not particularly limited, but examples thereof include polyolefin, polyester, polyvinyl chloride, and polyamide.
- polyolefins include polyethylene, polypropylene, copolymers thereof, acid-modified products thereof and ionomers thereof.
- polyester include polyethylene terephthalate (PET) and polybutylene terephthalate (PBT).
- polyvinyl chloride include hard polyvinyl chloride and soft polyvinyl chloride containing no plasticizer.
- polyamides include polyhexamethylene adipamide (nylon 66) and polycaprolactam (nylon 6).
- the laminate 1 can be given heat-sealing properties.
- the type of heat-fusible resin that forms the heat-fusible resin film is not particularly limited as long as it is a resin having heat-fusibility and thermoplasticity. Examples include polypropylene and polypropylene copolymers. mentioned.
- the heat-fusibility refers to a resin made of the same material or a different material that softens when the heat-fusible resin is heated to a certain temperature or higher and is in close contact with the heat-fusible resin. It means that it can be fused.
- the thickness of the resin film 3 is not particularly limited, it may be set to, for example, 20 ⁇ m or more and 150 ⁇ m or less, or may be set to 30 ⁇ m or more and 100 ⁇ m or less. By setting the thickness to 20 ⁇ m or more, the occurrence of pinholes can be sufficiently prevented. Also, by setting the thickness to 150 ⁇ m or less, the amount of resin used can be reduced, and cost reduction can be achieved.
- the adhesive layer 4 that bonds the metal foil 2 and the resin film 3 is made of an adhesive containing a reaction product of the adhesive composition according to this embodiment.
- the adhesive composition according to this embodiment, which is used to obtain the adhesive that forms the adhesive layer 4, will be described below.
- the adhesive composition according to this embodiment contains the following (Component 1), (Component 2), (Component 3), (Component 4), and (Component 5).
- (Component 1) Acid-modified polyolefin having a carboxy group
- Component 2) A polyisocyanate compound, which is a compound in which p (p is an integer of 2 or more) isocyanato groups are bonded to a mother nucleus (Component 3) Component 2 poly
- Modified isocyanate compound that is a bonded compound Component 4)
- a reaction catalyst that accelerates the reaction between the carboxy group of Component 1 and the isocyanato group of Component 2 and Component 3 (Component 5) Solvent
- Acid-modified polyolefin (component 1) Acid-modified polyolefin is obtained by acid-modifying polyolefin to introduce carboxy groups. Acid-modified polyolefins include, for example, modified polyolefin resins grafted with at least one selected from ethylenically unsaturated carboxylic acids and their acid anhydrides, and monomers such as ethylene, propylene, and butene and ethylenically unsaturated A copolymer resin obtained by copolymerizing at least one selected from carboxylic acid and its acid anhydride can be used.
- polyolefin component of the acid-modified polyolefin examples include homopolymers of monomers such as ethylene, propylene and butene, and copolymers obtained by copolymerizing one or more of these monomers.
- Acid components of acid-modified polyolefins include, for example, acrylic acid, methacrylic acid, crotonic acid, maleic acid, maleic anhydride, fumaric acid, fumaric anhydride, itaconic acid, and itaconic anhydride. etc. can be used. These ethylenically unsaturated carboxylic acids may be used alone or in combination of two or more.
- copolymers of propylene and olefins other than propylene are preferred, and copolymers of propylene and olefins containing butene are more preferred.
- the copolymerization ratio of propylene:butene is preferably 90:10 to 70:30 (molar ratio), preferably 87:13 to 72:28. More preferably, it is 82:18 to 75:25.
- the acid-modified polyolefin it is preferable to use a modified polyolefin resin in which at least one selected from ethylenically unsaturated carboxylic acids and their acid anhydrides is grafted onto polyolefin. It is more preferable to use a modified polyolefin resin in which at least one of the selected resins is grafted onto polyolefin.
- the ratio of maleic anhydride to the total amount of the acid-modified polyolefin is 0.6% by mass or more. It is preferably in the range of 3.0% by mass or less, more preferably in the range of 0.7% by mass or more and 2.5% by mass or less, and in the range of 0.8% by mass or more and 2.0% by mass or less It is even more preferable to have
- the acid value of the acid-modified polyolefin is preferably 1 mgKOH/g or more and 40 mgKOH/g or less, more preferably 3 mgKOH/g or more and 30 mgKOH/g or less, and further preferably 5 mgKOH/g or more and 20 mgKOH/g or less. preferable.
- the acid value in the present invention is the mass of potassium hydroxide (KOH) required to neutralize 1 g of polyolefin resin, and can be determined according to the method described in JIS K0070.
- the melting point of the acid-modified polyolefin is preferably 70° C. or higher and 110° C. or lower, more preferably 70° C. or higher and 100° C. or lower, even more preferably 75° C. or higher and 95° C. or lower, and 75° C. or higher. 90° C. or lower is particularly preferred.
- the melting point here is measured by differential scanning calorimetry at a heating rate of 10° C./min under the conditions described later in Examples.
- the heat of fusion of the acid-modified polyolefin is preferably in the range of 5 J/g or more and 60 J/g or less, more preferably 10 J/g or more and 50 J/g or less, and 15 J/g or more and 40 J/g or less. A range is more preferred.
- the heat of fusion of the acid-modified polyolefin is in the range of 5 J / g or more and 60 J / g or less, the cohesive force derived from the crystal can be maintained, so the adhesiveness and heat resistance can be maintained, and the acid-modified polyolefin to the solvent described later. can maintain the dissolution stability and fluidity of As a result, the operability when handling the adhesive composition is improved.
- the heat of fusion here is measured under the same conditions as the melting point measurement, and the heat of fusion is calculated from the area surrounded by the extended line of the baseline and the melting peak.
- the weight average molecular weight (Mw) of the acid-modified polyolefin is preferably in the range of 60,000 to 150,000, more preferably in the range of 70,000 to 140,000, and even more preferably in the range of 80,000 to 130,000.
- the number average molecular weight (Mn) of the acid-modified polyolefin is preferably in the range of 30,000 to 90,000, more preferably in the range of 35,000 to 80,000, and even more preferably in the range of 40,000 to 70,000.
- the weight-average molecular weight (Mw) and number-average molecular weight (Mn) herein are polystyrene-equivalent weight-average molecular weight and number-average molecular weight measured by gel permeation chromatography.
- the melt mass flow rate of the acid-modified polyolefin is preferably in the range of 2 g/10 minutes or more and 60 g/10 minutes or less, more preferably in the range of 10 g/10 minutes or more and 50 g/10 minutes or less, and 25 g/10 minutes. More preferably, it is in the range of 45 g/10 minutes or less.
- the melt mass flow rate here is measured under conditions of a temperature of 130° C. and a load of 2.16 kg in accordance with JIS K7210-1:2014.
- the content of the acid-modified polyolefin in the adhesive composition according to the present embodiment is not particularly limited, but the non-volatile content in the adhesive composition according to the present embodiment, that is, the adhesive composition
- the content of the acid-modified polyolefin is preferably 55% by mass or more and 96% by mass or less, and 60% by mass or more and 90% by mass. It is more preferably 65% by mass or more and 85% by mass or less.
- the polyisocyanate compound of component 2 has a plurality of isocyanato groups (--NCO), and more specifically, it is a compound in which p (p is an integer of 2 or more) isocyanato groups are bonded to the mother nucleus.
- the mother nucleus refers to a portion obtained by removing the isocyanato group from the polyisocyanate compound of Component 2.
- Examples of the chemical structure constituting the mother nucleus that is, the chemical structure before the isocyanato group is bonded, include aromatic compounds such as benzene, toluene, xylene, naphthalene, and anthracene, methane, butane, n-hexane, cyclohexane, and the like. linear or cyclic saturated or unsaturated aliphatic compounds and heterocyclic compounds.
- Examples of the mother nucleus when p is 2 include a phenylene group, an alkylene group, and a cycloalkylene group.
- a saturated aliphatic polyisocyanate can be used as the polyisocyanate compound of component 2.
- the polyisocyanate compound of component 2 at least one compound selected from isocyanurate compounds of saturated aliphatic polyisocyanates and allophanate compounds of saturated aliphatic polyisocyanates can be used.
- polyisocyanate compound of Component 2 examples include butylene diisocyanate, pentadiisocyanate (PDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), cyclopentylene diisocyanate, cyclohexylene diisocyanate, norbornene diisocyanate, and hydrogenated xylylene.
- PDI pentadiisocyanate
- HDI hexamethylene diisocyanate
- IPDI isophorone diisocyanate
- cyclopentylene diisocyanate cyclohexylene diisocyanate
- norbornene diisocyanate norbornene diisocyanate
- hydrogenated xylylene examples include butylene diisocyanate, pentadiisocyanate (PDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI),
- polyisocyanate compound of component 2 examples include modified products of the above diisocyanates.
- isocyanurate which is a trimer of diisocyanate
- allophanate which is an adduct of urethane group and diisocyanate formed by reaction of diisocyanate and alcohol
- carbodiimide-modified diisocyanate and glycol-modified diisocyanate.
- the polyisocyanate compound of component 2 may be a diisocyanate having two isocyanato groups, a triisocyanate having three isocyanato groups, or an isocyanate compound having four or more isocyanato groups. These polyisocyanate compounds of component 2 may be used alone or in combination of two or more.
- Modified isocyanate compound (component 3)
- the modified group possessed by the modified isocyanate compound of component 3 is a group generated by the reaction between the isocyanato group bonded to the mother nucleus and the functional group having active hydrogen of the active hydrogen compound having the functional group having active hydrogen.
- the functional group having active hydrogen include hydroxy group, carboxy group, mercapto group and amino group, preferably at least one of hydroxy group and carboxy group. If the functional group having an active hydrogen is a hydroxy group, the modifying group will be a group having a urethane bond, and if the functional group having an active hydrogen is a carboxy group, the modifying group will be a group having an amide bond.
- this modified isocyanate compound can be produced by reacting a polyisocyanate compound having the same chemical structure as the polyisocyanate compound of component 2 with an active hydrogen compound.
- a modified isocyanate compound can be obtained by reacting an active hydrogen compound having one hydroxy group with a diisocyanate and appropriately controlling the amount of the active hydrogen compound having one hydroxy group used in this reaction.
- the modified isocyanate compound obtained in this example is a compound in which only one of the two isocyanato groups of the diisocyanate reacts with the hydroxy group of the active hydrogen compound to form a urethane bond. It is a compound having one modifying group.
- the polyisocyanate compound of component 2 and the modified isocyanate compound of component 3 may be separately prepared and used as raw materials for the adhesive composition, but may be prepared as follows. That is, by adding an active hydrogen compound to the polyisocyanate compound of component 2 and reacting the active hydrogen compound with a part of the polyisocyanate compound of component 2 to generate the modified isocyanate compound of component 3, the polyisocyanate of component 2 A mixture of the compound and the modified isocyanate compound of Component 3 may be prepared and this mixture used as a starting material for the adhesive composition.
- active hydrogen compounds include monovalent alcohols, monovalent carboxylic acids, monovalent thiols, and monovalent amines, and at least one selected from monovalent alcohols and monovalent carboxylic acids. is preferably a compound of The carbon number of the monohydric alcohol and the monohydric carboxylic acid is preferably 1 or more and 20 or less, more preferably 2 or more and 15 or less, and even more preferably 3 or more and 12 or less.
- monohydric alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, tert-butanol, 2-ethylhexanol, n-decanol, n-dodecanol and n-octanol. be done.
- monovalent carboxylic acids include acetic acid, propionic acid and butyric acid.
- An active hydrogen compound may be used individually by 1 type, and may use 2 or more types together.
- the total number of moles of isocyanato groups possessed by the polyisocyanate compound of Component 2 is Ia
- the total number of moles of isocyanato groups possessed by the modified isocyanate compound of Component 3 is Ib
- the ratio of H to the total number of moles of Ia, Ib and H is H / (Ia + Ib + H) exceeding 0 and 0.5 or less.
- An adhesive composition in which the ratio H/(Ia+Ib+H) is within the above range can provide an adhesive that can firmly bond a metal foil and a resin film even at high temperatures.
- the ratio H/(Ia+Ib+H) is preferably greater than 0 and 0.5 or less, more preferably 0.01 or more and 0.4 or less, and further preferably 0.015 or more and 0.34 or less. .
- C is the total number of moles of carboxyl groups possessed by the acid-modified polyolefin
- Ia is the total number of moles of isocyanato groups possessed by the polyisocyanate compound of Component 2
- Ia is the number of moles of Component 3.
- Ib is the total number of moles of isocyanato groups possessed by the modified isocyanate compound
- the ratio of the total number of moles of Ia and Ib to C (Ia+Ib)/C is preferably 0.3 or more and 30 or less.
- An adhesive composition in which the ratio (Ia+Ib)/C is within the above range can provide an adhesive that can more firmly bond a metal foil and a resin film even at high temperatures.
- the ratio (Ia+Ib)/C is more preferably 1.0 or more and 20 or less, further preferably 2.0 or more and 15 or less, and particularly preferably 3.0 or more and 12 or less.
- the total amount of the polyisocyanate compound of component 2 and the modified isocyanate compound of component 3 is preferably as follows. That is, when the amount obtained by subtracting the amount of component 5 from the total amount of the adhesive composition is 100% by mass, the total amount of components 2 and 3 is preferably more than 0% by mass and less than 40% by mass. , 2% by mass or more and 35% by mass or less.
- the reaction catalyst of Component 4 is a catalyst that accelerates the reaction between the carboxy groups of the acid-modified polyolefin of Component 1 and the isocyanato groups of the polyisocyanate compound of Component 2 and the modified isocyanate compound of Component 3.
- the type of the reaction catalyst of Component 4 is not particularly limited as long as it promotes the reaction between the carboxyl group and the isocyanato group.
- organotin compounds, tertiary amines, and the like can be used.
- organotin compounds include dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, and dioctyltin dilaurate.
- tertiary amines include tetraalkylethylenediamine such as tetramethylethylenediamine, N,N'-dialkylbenzylamine such as dimethylbenzylamine, triethylenediamine, pentamethylenediethylenetriamine, N-ethylmorpholine, N- methylmorpholine, 1-methyl-4-dimethylamineethylpiperazine, diazabicycloundecene and the like.
- This reaction catalyst may be used alone or in combination of two or more.
- the ratio of the amount of the reaction catalyst is preferably 0.01 parts by mass or more and 3 parts by mass or less, more preferably 0.05 parts by mass or more and 2.5 parts by mass or less, and 0.2 parts by mass or more and 2 parts by mass. Part or less is more preferable.
- the ratio of the amount of the reaction catalyst is within this range, the pot life after mixing and after bonding the metal foil and the resin film via the reaction product of the adhesive composition according to the present embodiment It is easy to balance with the time until the adhesive strength of is expressed.
- Solvent (Component 5) The type of solvent used in the adhesive composition according to the present embodiment is not particularly limited as long as it can dissolve or disperse the acid-modified polyolefin. Organic solvents that can be used are preferred. Moreover, as the organic solvent, an organic solvent that can be easily removed from the adhesive composition according to the present embodiment by volatilizing the organic solvent by heating or the like is preferable.
- organic solvents it is possible to use other types of organic solvents in combination with the organic solvent that can dissolve the acid-modified polyolefin and that can be easily volatilized and removed by heating or the like.
- organic solvents acetic acid ester organic solvents such as ethyl acetate, n-propyl acetate and n-butyl acetate are preferably used.
- the ratio of the amount of the solvent of component 5 is preferably 60% by mass or more and 97% by mass or less, and 70% by mass or more and 96% by mass, when the total amount of the adhesive composition according to this embodiment is 100% by mass. It is more preferably not more than 80% by mass and even more preferably 80% by mass or more and 95% by mass or less. When the ratio of the amount of the solvent is within this range, the viscosity of the adhesive composition can be properly maintained, and the thickness of the adhesive layer obtained by coating the adhesive composition and removing the solvent is easy to make appropriate.
- the viscosity of the adhesive composition when applied is preferably 200 mPa ⁇ s or less at 25°C.
- the adhesive composition according to the present embodiment may contain a tackifier, a plasticizer, or a polyolefin having no acidic functional group, as long as the effects of the present invention are not impaired.
- a thermoplastic resin other than polyolefin may be contained.
- the type of tackifier is not particularly limited, but examples of natural tackifiers include polyterpene-based resins and rosin-based resins, and petroleum-based tackifiers include decomposition of naphtha. Aliphatic (C5)-based resins, aromatic (C9)-based resins, copolymer (C5/C9)-based resins, alicyclic-based resins, etc. obtained from oil fractions can be mentioned. Hydrogenated resins obtained by hydrogenating the double bond portions of these resins can also be used. These tackifiers may be used alone or in combination of two or more.
- Polyolefins having no acidic functional groups and types of thermoplastic resins other than polyolefins are not particularly limited, but examples thereof include ethylene-vinyl acetate copolymer resins, ethylene-ethyl acrylate copolymer resins, and waxes. be done.
- examples of olefinic thermoplastic elastomers having no carboxy group include SEBS (styrene-ethylene-butylene-styrene) and SEPS (styrene-ethylene-propylene-styrene).
- the method for manufacturing the laminate 1 according to the present embodiment includes a film forming step of forming a film of the adhesive composition, a lamination step of bonding the metal foil 2 and the resin film 3 together, and a film of the adhesive composition. and a reaction step of heating the adhesive composition to react the adhesive composition to form the adhesive layer 4 .
- a film forming process, a stacking process, and a reaction process will be described below.
- the adhesive composition according to the present embodiment is applied to one or both of the surface of the metal foil 2 and the surface of the resin film 3 to form a film of the adhesive composition according to the present embodiment. It is a process of forming.
- the method of applying the adhesive composition is not particularly limited, and examples thereof include printing methods such as gravure printing, offset printing, screen printing and bar coat printing. However, considering the thickness of the film of the adhesive composition, the coating method by gravure printing is most preferable.
- Part or all of the component 5 solvent may be removed from the film of the adhesive composition.
- the method for removing the solvent of component 5 from the film of the adhesive composition is not particularly limited, and for example, methods such as heating and pressure reduction can be employed, but the method of removing the solvent of component 5 by heating. is preferred.
- the film of the adhesive composition may be exposed to a predetermined temperature above room temperature.
- the predetermined temperature is preferably a temperature below the boiling point of the solvent of component 5.
- the predetermined temperature is preferably lower than the lowest boiling point of the plurality of solvents used as component 5.
- the adhesive composition is formed between the metal foil 2 and the resin film 3.
- the metal foil 2 and the resin film 3 are overlapped and bonded together so that the film of the composition is arranged (lamination step).
- lamination step By such a lamination process, the metal foil 2, the resin film 3, and the film of the adhesive composition are laminated.
- the layer obtained by the lamination step is heated to react the adhesive composition to form the adhesive layer 4 (reaction step). More specifically, components 1, 2, and 3 in the adhesive composition are reacted by heating to crosslink and increase the molecular weight. As a result, the film of the adhesive composition becomes the adhesive layer 4 formed of the adhesive containing the reaction product of the adhesive composition, and the adhesive layer 4 forms the metal foil 2 and the resin film. 3 are adhered to form a laminate 1 . Heating in the reaction step accelerates the reaction between the carboxy group of the acid-modified polyolefin of component 1, the isocyanato group of the polyisocyanate compound of component 2, and the isocyanato group of the modified isocyanate compound of component 3, and the reaction progresses. .
- the heating temperature in the reaction step is not particularly limited as long as it is a temperature at which the reaction proceeds sufficiently, but is preferably 30° C. or higher, and preferably 40° C. or higher, in order to sufficiently progress the reaction. is more preferred.
- the heating temperature in the reaction step is preferably 70° C. or lower, more preferably 60° C. or lower.
- the heating time in the reaction step is not particularly limited as long as the reaction proceeds sufficiently, but it is preferably 1 hour or more, more preferably 3 hours or more, and 6 hours or more. is more preferable.
- the acid value of the above graft-modified product which is the acid-modified polyolefin of component 1, is 12.6 mg-KOH/g, and the melting point is 80°C.
- the weight average molecular weight (Mw) of the graft-modified product is 110,000, and the number average molecular weight (Mn) is 58,000.
- the melt mass flow rate of the above graft modified product is 29 g/10 min, and the heat of fusion is 35 J/g.
- More detailed measurement conditions are as follows. That is, a powdery sample of acid-modified polyolefin was heated from room temperature to 180°C at a heating rate of 10°C/min, held at 180°C for 5 minutes to melt, and then cooled to -30°C. was held for 5 minutes. After that, the temperature was raised again at a rate of temperature rise of 10° C./min, and the melting peak temperature detected during this temperature rise was taken as the melting point.
- the butene copolymerization ratio (mol%) was calculated by dividing the integral ratio of the peak at 34.0 ppm by the integral ratio of the peaks from 27.0 ppm to 28.0 ppm and multiplying the result by 100. Further, by subtracting the copolymerization ratio of butene calculated as described above from 100, the copolymerization ratio of propylene (mol%) was calculated.
- the weight average molecular weight and number average molecular weight of the acid-modified polyolefin are the polystyrene equivalent weight average molecular weight and number average molecular weight measured by gel permeation chromatography. Measurement conditions for gel permeation chromatography are as follows.
- Apparatus name HPLC unit HSS-2000 manufactured by JASCO Corporation Column: Showa Denko Co., Ltd. Shodex column LF-805L ⁇ 3 (series) Mobile phase: Tetrahydrofuran Flow rate: 1.0 mL/min Detector: RI-2031Plus manufactured by JASCO Corporation Temperature: 40.0°C Sample volume: sample loop 100 ⁇ L Sample concentration: about 0.1% by mass Polystyrene standard material: STANDARD SM-105 manufactured by Showa Denko K.K. (Measuring method of melt mass flow rate) Measured in accordance with JIS K7210-1:2014 under conditions of a temperature of 130° C. and a load of 2.16 kg.
- stirring of the contents of the three-necked flask was started with a stirrer, and the internal temperature of the three-necked flask was raised to 70°C using an oil bath.
- the ethyl acetate solution was dropped from the dropping funnel into the three-necked flask over 60 minutes to allow the isocyanurate of hexamethylene diisocyanate to react with n-butanol.
- the addition was performed while controlling the internal temperature of the three-necked flask to be 70°C or higher and 75°C or lower.
- an addition reaction product (urethane A mixture with a modified isocyanate compound having a bond) was obtained.
- the solid content concentration of the reaction liquid in the three-necked flask was 83.5% by mass.
- the total number of moles of isocyanato groups in the isocyanurate form of hexamethylene diisocyanate (polyisocyanate compound) is Ia
- the total number of moles of isocyanato groups in the addition reaction product (modified isocyanate compound) is Ib
- the ratio of H to the total number of moles of Ia, Ib and H is H/(Ia+Ib+H) is 0.017. is.
- Examples 1 to 11 and Comparative Examples 1 to 10 The resin composition of Production Example 1 or the acrylic copolymer solution of Production Example 2, the isocyanurate form of hexamethylene diisocyanate or the reaction solutions of Production Examples 3 to 16, the reaction catalyst dibutyltin dilaurate, and the solvent methyl Cyclohexane and ethyl acetate were mixed to obtain adhesive compositions of Examples 1 to 11 and Comparative Examples 1 to 10. The mass of each of these mixed components is shown in Table 2.
- the ratio H/(Ia+Ib+H) of H to the total number of moles of Ia, Ib and H is as shown in Table 2. Further, in these adhesive compositions, the total number of moles of carboxyl groups in the acid-modified polyolefin of Production Example 1 or the acrylic copolymer of Production Example 2 is C, and the total number of moles of isocyanato groups in the polyisocyanate compound is C. When the number is Ia and the total number of moles of isocyanato groups possessed by the modified isocyanate compound is Ib, the ratio of the total number of moles of Ia and Ib to C (Ia + Ib)/C is shown in Table 2.
- laminate test pieces were produced.
- a method for producing a laminate test piece will be described below. Prepare an aluminum foil (width: 10 cm, thickness: 40 ⁇ m) having a corrosion prevention treatment (chemical conversion treatment) layer on the surface, apply an adhesive composition to the surface of this aluminum foil, and A film of the adhesive composition was formed. A bar coater was used to apply the adhesive composition. Also, the coating amount of the adhesive composition was 2 g/m 2 .
- the aluminum foil having the film of the adhesive composition formed thereon was placed in a hot air drying oven at 80° C. for 20 seconds to evaporate the solvent in the adhesive composition and dry it.
- a non-stretched polypropylene film with a thickness of 80 ⁇ m is prepared as a heat-fusible resin film, and in a hot air drying oven, a film of the adhesive composition is arranged between the unstretched polypropylene film and the aluminum foil.
- An unstretched polypropylene film and an aluminum foil were superimposed and bonded together using a rubber roller. As a result, a sheet-like laminated film was obtained in which the unstretched polypropylene film, the film of the adhesive composition, and the aluminum foil were laminated.
- the obtained sheet-like laminated film was placed in a hot air circulating oven at a temperature of 40°C and held for one week.
- the reaction of the adhesive composition proceeds, and the film of the adhesive composition becomes an adhesive layer formed of the adhesive containing the reaction product of the adhesive composition,
- a laminate was obtained in which the non-stretched polypropylene film and the aluminum foil were adhered by the adhesive layer.
- the obtained laminate was taken out from the hot air circulating oven and cut to prepare a strip-shaped test piece having a width of 15 mm.
- the peel strength between the unstretched polypropylene film and the aluminum foil was measured at a temperature of 85°C to evaluate the adhesiveness of the adhesive at high temperature.
- the peel strength was measured by a T-shaped peel test according to the method specified in JIS K6854-3:1999. The tensile speed was set to 100 mm/min.
- the test pieces of Examples 1 to 11 have a ratio H/(Ia+Ib+H) within the range of more than 0 and 0.5 or less, so they have excellent peel strength even at a high temperature of 85 ° C. It can be seen that the adhesiveness of the adhesive is excellent at high temperatures.
- the test pieces of Comparative Examples 1 to 4 have a ratio H / (Ia + Ib + H) outside the range of more than 0 to 0.5 or less, so the peel strength at high temperatures is lower than that of Examples 1 to 11. , it can be seen that the adhesiveness of the adhesive under high temperature is insufficient.
- Comparative Examples 5 to 7 the amount of polyisocyanate compound (isocyanurate of hexamethylene diisocyanate) used was reduced, thereby reducing the number of isocyanato groups contained in the adhesive composition compared to Comparative Example 1. For example. Also for Examples 1 to 11, by replacing a part of the polyisocyanate compound (isocyanurate of hexamethylene diisocyanate) with a modified isocyanate compound, isocyanate contained in the adhesive composition was reduced in the same manner as in Comparative Examples 5 to 7. The number of groups is smaller than in Comparative Example 1.
- test pieces of Examples 1 to 11 have higher peel strength at high temperatures than the test pieces of Comparative Examples 5 to 7, and are superior in adhesiveness at high temperatures. From these results, in order to improve the adhesiveness of the adhesive at high temperatures, it is necessary not only to control the number of isocyanato groups contained in the adhesive composition, but also to include a modified isocyanate compound in the adhesive composition. It turns out that there is
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Abstract
Description
本発明は、高温下においても金属箔と樹脂製フィルムを強固に接着することが可能な接着剤が得られる接着剤用組成物、及び、高温下においても金属箔と樹脂製フィルムが剥離しにくい積層体を提供することを課題とする。
[1] 金属箔と樹脂製フィルムを接着する接着剤を得るための接着剤用組成物であって、
(成分1)カルボキシ基を有する酸変性ポリオレフィンと、
(成分2)母核にp個(pは2以上の整数である)のイソシアナト基が結合した化合物であるポリイソシアネート化合物と、
(成分3)前記成分2のポリイソシアネート化合物と同一構造の母核に、q個(qは1以上の整数である)のイソシアナト基と、r個(rは1以上の整数であり、q+r=pを満たす)の変性基とが結合した化合物である変性イソシアネート化合物と、
(成分4)前記成分1が有するカルボキシ基と前記成分2及び前記成分3が有するイソシアナト基との反応を促進する反応触媒と、
(成分5)溶剤と、
を含有し、
前記成分3の変性イソシアネート化合物が有する前記変性基は、前記母核に結合したイソシアナト基と、活性水素を有する官能基を備える活性水素化合物の前記活性水素を有する官能基との反応により生成する基であり、
前記成分2のポリイソシアネート化合物が有するイソシアナト基の総モル数をIaとし、前記成分3の変性イソシアネート化合物が有するイソシアナト基の総モル数をIbとし、前記成分3の変性イソシアネート化合物が有する前記変性基の総モル数をHとした場合に、IaとIbとHの合計モル数に対するHの比H/(Ia+Ib+H)が0超過0.5以下である接着剤用組成物。
[3] 前記活性水素化合物が、1価のアルコール及び1価のカルボン酸から選択される少なくとも1種の化合物である[1]に記載の接着剤用組成物。
[4] 前記ポリイソシアネート化合物が飽和脂肪族ポリイソシアネートである[1]~[3]のいずれか一項に記載の接着剤用組成物。
[6] 前記酸変性ポリオレフィンが、プロピレン、エチレン、及びブテンのうちの1種以上を単量体として使用したポリオレフィンの酸変性物を含有する[1]~[5]のいずれか一項に記載の接着剤用組成物。
[9] 前記金属箔がアルミニウム箔であり、前記樹脂製フィルムが熱融着性樹脂製フィルムである[8]に記載の積層体。
金属箔2を形成する金属の種類は特に限定されるものではないが、例えば、アルミニウム、アルミニウム合金、ステンレス鋼、アルミニウム-鉄合金が挙げられる。食品、医薬品、化学薬品等を収容する包装材として積層体を使用する場合には、包装材の内部に酸素や水分が侵入することを抑制するガスバリア性を、金属箔2によって付与することができる。金属箔2の厚さは特に限定されるものではないが、5μm以上50μm以下としてもよい。
樹脂製フィルム3を形成する樹脂の種類は特に限定されるものではないが、例えば、ポリオレフィン、ポリエステル、ポリ塩化ビニル、ポリアミドが挙げられる。ポリオレフィンの具体例としては、ポリエチレン、ポリプロピレンや、これらの共重合体や、これらの酸変性物及びアイオノマーが挙げられる。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)、ポリブチレンテレフタレート(PBT)が挙げられる。ポリ塩化ビニルの具体例としては、可塑剤を含有しない硬質ポリ塩化ビニル、軟質ポリ塩化ビニルが挙げられる。ポリアミドの具体例としては、ポリヘキサメチレンアジパミド(66ナイロン)、ポリカプロラクタム(6ナイロン)が挙げられる。食品、医薬品、化学薬品等を収容する包装材として積層体を使用する場合には、優れた耐酸性、耐薬品性を樹脂製フィルム3によって付与することができる。
金属箔2と樹脂製フィルム3を接着する接着剤層4は、本実施形態に係る接着剤用組成物の反応生成物を含有する接着剤で形成されている。以下に、接着剤層4を形成する接着剤を得るために使用される本実施形態に係る接着剤用組成物について説明する。
(成分1)カルボキシ基を有する酸変性ポリオレフィン
(成分2)母核にp個(pは2以上の整数である)のイソシアナト基が結合した化合物であるポリイソシアネート化合物
(成分3)成分2のポリイソシアネート化合物と同一構造の母核に、q個(qは1以上の整数である)のイソシアナト基と、r個(rは1以上の整数であり、q+r=pを満たす)の変性基とが結合した化合物である変性イソシアネート化合物
(成分4)成分1が有するカルボキシ基と成分2及び成分3が有するイソシアナト基との反応を促進する反応触媒
(成分5)溶剤
(1)酸変性ポリオレフィン(成分1)
酸変性ポリオレフィンは、ポリオレフィンに酸変性を施してカルボキシ基を導入したものである。
酸変性ポリオレフィンとしては、例えば、エチレン性不飽和カルボン酸及びその酸無水物から選択される少なくとも1種をグラフトさせた変性ポリオレフィン樹脂や、エチレン、プロピレン、ブテン等の単量体とエチレン性不飽和カルボン酸及びその酸無水物から選択される少なくとも1種とを共重合させた共重合樹脂を用いることができる。
成分2のポリイソシアネート化合物は、複数のイソシアナト基(-NCO)を有しており、詳述すると、母核にp個(pは2以上の整数である)のイソシアナト基が結合した化合物である。本発明において、母核とは、成分2のポリイソシアネート化合物からイソシアナト基を除いた部分をいう。母核を構成する化学構造、つまりイソシアナト基が結合する前の化学構造体の例としては、ベンゼン、トルエン、キシレン、ナフタレン、アントラセン等の芳香族化合物や、メタン、ブタン、n-ヘキサン、シクロヘキサン等の鎖状又は環状の飽和又は不飽和の脂肪族化合物や、複素環化合物が挙げられる。pが2である場合の母核の例としては、フェニレン基、アルキレン基、シクロアルキレン基が挙げられる。
成分3の変性イソシアネート化合物は、1個以上のイソシアナト基と1個以上の変性基を有するイソシアネート化合物であり、詳述すると、母核にq個のイソシアナト基とr個の変性基とが結合した化合物である。q及びrはいずれも1以上の整数であり、q+r=pを満たす。このpは、前述したように、成分2のポリイソシアネート化合物の母核に結合しているイソシアナト基の個数である。また、成分2のポリイソシアネート化合物の母核と、成分3の変性イソシアネート化合物の母核は、同一構造である。
例えば、1個のヒドロキシ基を備える活性水素化合物とジイソシアネートとを反応させ、この反応において1個のヒドロキシ基を備える活性水素化合物の使用量を適切に制御すれば、変性イソシアネート化合物を得ることができる。この例で得られる変性イソシアネート化合物は、ジイソシアネートが有する2個のイソシアナト基のうち一方のみが活性水素化合物のヒドロキシ基と反応して、ウレタン結合となった化合物であり、1個のイソシアナト基と1個の変性基を有する化合物である。
なお、本発明においては、カルボキシ基2個の脱水縮合生成物であるカルボン酸無水物基(-C(=O)-O-C(=O)-)は、カルボン酸無水物基1個で2個のカルボキシ基を有するものとする。
成分4の反応触媒は、成分1の酸変性ポリオレフィンが有するカルボキシ基と、成分2のポリイソシアネート化合物及び成分3の変性イソシアネート化合物が有するイソシアナト基との反応を促進する触媒である。成分4の反応触媒の種類は、カルボキシ基とイソシアナト基の反応を促進するものであれば特に限定されるものではないが、例えば、有機スズ化合物、第3級アミン等を用いることができる。
また、第3級アミンの具体例としては、テトラメチルエチレンジアミン等のテトラアルキルエチレンジアミン、ジメチルベンジルアミン等のN,N’-ジアルキルベンジルアミン、トリエチレンジアミン、ペンタメチレンジエチレントリアミン、N-エチルモルフォリン、N-メチルモルフォリン、1-メチル-4-ジメチルアミンエチルピペラジン及びジアザビシクロウンデセン等が挙げられる。
この反応触媒は、1種のみを単独で用いてもよいし、2種以上を併用してもよい。
本実施形態に係る接着剤用組成物に使用される溶剤の種類は、酸変性ポリオレフィンを溶解させる又は分散させることができるものであれば特に限定されるものではないが、酸変性ポリオレフィンを溶解させることができる有機溶剤が好ましい。また、有機溶剤としては、本実施形態に係る接着剤用組成物から該有機溶剤を加熱等により揮発させて除去することが容易な有機溶剤が好ましい。
粘着付与剤の種類は特に限定されるものではないが、例えば、天然系の粘着付与剤としては、ポリテルペン系樹脂、ロジン系樹脂等が挙げられ、石油系の粘着付与剤としては、ナフサの分解油留分より得られる脂肪族(C5)系樹脂、芳香族(C9)系樹脂、共重合(C5/C9)系樹脂、脂環族系樹脂等が挙げられる。また、これら樹脂の二重結合部分を水素化した水添樹脂も挙げることができる。これらの粘着付与剤は、1種のみを単独で用いてもよいし、2種以上を併用してもよい。
接着剤用組成物の塗布方法は特に限定されるものではないが、例えば、グラビア印刷、オフセット印刷、スクリーン印刷、バーコート印刷等の印刷方法を挙げることができる。ただし、接着剤用組成物の膜の厚さを考慮すると、グラビア印刷による塗布方法が最も好ましい。
反応工程における加熱によって、成分1の酸変性ポリオレフィンが有するカルボキシ基と、成分2のポリイソシアネート化合物が有するイソシアナト基及び成分3の変性イソシアネート化合物が有するイソシアナト基との反応が促進され、反応が進行する。
また、反応工程における加熱時間は、反応が十分に進行する時間であれば特に限定されるものではないが、1時間以上であることが好ましく、3時間以上であることがより好ましく、6時間以上であることがさらに好ましい。
〔製造例1〕
冷却管及び攪拌機を備えた容量1000mLのフラスコに、プロピレン-ブテン共重合体の無水マレイン酸グラフト変性物75.0質量部と、溶剤であるメチルシクロヘキサン290質量部及び酢酸エチル120質量部とを仕込み、60℃で10分間攪拌して液状の樹脂組成物を得た。その後、当該樹脂組成物を室温に冷却した。当該樹脂組成物の固形分濃度は15.0質量%であった。ここで、固形分濃度とは、樹脂組成物の総質量に対する、溶剤を除く他の成分の質量百分率である。固形分濃度は、105℃において1時間の真空乾燥を行った後の質量減少率から計算される。
(酸価の測定方法)
JIS K0070:1992に規定の方法に準拠して測定した。
(融点の測定方法)
融点は、JIS K7121(1987年制定)「プラスチックの転移温度測定方法」に規定された方法に準拠して測定した。測定には株式会社島津製作所製のDSC(示差走査熱量計)(型式DSC-60A)を用い、昇温速度10℃/分で示差走査熱量測定を行った結果得られた融解ピーク温度を「融点」とした。
溶媒として重クロロホルム(CDCl3)を用いて、酸変性ポリオレフィンの炭素13核磁気共鳴測定(13C NMR測定)を行い、以下の方法により解析した。13C NMRスペクトルの34.0ppmのピークはポリブテンのメチンの炭素由来であり、27.0ppm~28.0ppmのピークは、ポリブテンの側鎖のメチレンの炭素とポリプロピレンのメチンの炭素由来である。
酸変性ポリオレフィンの重量平均分子量及び数平均分子量は、ゲルパーミエーションクロマトグラフィーで測定したポリスチレン換算の重量平均分子量及び数平均分子量である。ゲルパーミエーションクロマトグラフィーの測定条件は以下の通りである。
カラム:昭和電工株式会社製ShodexカラムLF-805L×3本(直列)
移動相:テトラヒドロフラン
流速:1.0mL/min
検出器:日本分光株式会社製RI-2031Plus
温度:40.0℃
試料量:サンプルループ 100μL
試料濃度:約0.1質量%
ポリスチレン標準物質:昭和電工株式会社製STANDARD SM-105
(メルトマスフローレイトの測定方法)
JIS K7210-1:2014に準拠して、温度130℃、荷重2.16kgの条件で測定した。
冷却管、窒素導入管、温度計、及び攪拌機を備えた反応容器に、酢酸エチル470質量部、ブチルアクリレート172質量部、2-エチルヘキシルアクリレート172質量部、アクリル酸5.6質量部、2,2’-アゾビス(イソブチロニトリル)0.6質量部を仕込んだ。そして、窒素気流中で反応容器の内温を90℃に昇温し8時間保持して、ブチルアクリレート、2-エチルヘキシルアクリレート、及びアクリル酸を重合した後、30℃まで冷却してアクリル共重合体を得た。重合終了後に反応容器内のアクリル共重合体溶液中の固形分濃度を測定したところ、43.1質量%であった。
塩化カルシウム管を上部に取り付けた冷却管、温度計、滴下ロート、及び攪拌羽付きの攪拌機を備えた三口フラスコに、旭化成株式会社製のデュラネート(登録商標)TKA-100(ヘキサメチレンジイソシアネートのイソシアヌレート体、イソシアナト基濃度:21.7質量%)83.0質量部と、スズ触媒であるジオクチル錫ジラウレート0.003質量部と、を仕込んだ。
また、酢酸エチル16.5質量部にn-ブタノール0.53質量部を溶解させた酢酸エチル溶液を滴下ロートに仕込み、滴下の準備をした。
酢酸エチル溶液の滴下が終了したら、反応を1時間継続し、ガスクロマトグラフィーで三口フラスコ内の反応液の分析を行った。そして、n-ブタノールのピークが観測されなくなったことを確認したら、反応を終了した。
ヘキサメチレンジイソシアネートのイソシアヌレート体(ポリイソシアネート化合物)の使用量と、1価のアルコールの種類及び使用量とを、表1に記載のように変更した点以外は、製造例3と同様の操作を行った。これにより、ヘキサメチレンジイソシアネートのイソシアヌレート体(ポリイソシアネート化合物)と、ヘキサメチレンジイソシアネートのイソシアヌレート体が有するイソシアナト基に1価のアルコールのヒドロキシ基が付加反応して生成した付加反応物(変性イソシアネート化合物)との混合物を含有する反応液を得た。なお、三口フラスコ内の反応液の固形分濃度は、いずれの製造例においても83.5質量%であった。
製造例1の樹脂組成物又は製造例2のアクリル共重合体溶液と、ヘキサメチレンジイソシアネートのイソシアヌレート体又は製造例3~16の反応液と、反応触媒であるジブチル錫ジラウレートと、溶剤であるメチルシクロヘキサン及び酢酸エチルとを混合して、実施例1~11及び比較例1~10の接着剤用組成物を得た。混合したこれら各成分の質量は、表2に記載のとおりである。
表面に腐食防止処理(化成処理)層を有するアルミニウム箔(幅:10cm、厚さ:40μm)を用意し、このアルミニウム箔の表面に接着剤用組成物を塗布して、アルミニウム箔の表面上に接着剤用組成物の膜を形成した。接着剤用組成物の塗布は、バーコーターを使用して行った。また、接着剤用組成物の塗布量は、2g/m2である。
熱融着性樹脂製フィルムとして厚さ80μmの無延伸ポリプロピレンフィルムを用意し、熱風乾燥炉の中で、無延伸ポリプロピレンフィルムとアルミニウム箔の間に接着剤用組成物の膜が配されるように無延伸ポリプロピレンフィルムとアルミニウム箔を重ね合わせ、ゴムローラーを用いて貼り合わせた。これにより、無延伸ポリプロピレンフィルムと接着剤用組成物の膜とアルミニウム箔が積層されたシート状の積層フィルムが得られた。
これに対して、比較例1~4の試験片は、比H/(Ia+Ib+H)が0超過0.5以下の範囲外であるため、実施例1~11と比べて高温下における剥離強度が低く、高温下における接着剤の接着性が不十分であることが分かる。
2・・・金属箔
3・・・樹脂製フィルム
4・・・接着剤層
Claims (9)
- 金属箔と樹脂製フィルムを接着する接着剤を得るための接着剤用組成物であって、
(成分1)カルボキシ基を有する酸変性ポリオレフィンと、
(成分2)母核にp個(pは2以上の整数である)のイソシアナト基が結合した化合物であるポリイソシアネート化合物と、
(成分3)前記成分2のポリイソシアネート化合物と同一構造の母核に、q個(qは1以上の整数である)のイソシアナト基と、r個(rは1以上の整数であり、q+r=pを満たす)の変性基とが結合した化合物である変性イソシアネート化合物と、
(成分4)前記成分1が有するカルボキシ基と前記成分2及び前記成分3が有するイソシアナト基との反応を促進する反応触媒と、
(成分5)溶剤と、
を含有し、
前記成分3の変性イソシアネート化合物が有する前記変性基は、前記母核に結合したイソシアナト基と、活性水素を有する官能基を備える活性水素化合物の前記活性水素を有する官能基との反応により生成する基であり、
前記成分2のポリイソシアネート化合物が有するイソシアナト基の総モル数をIaとし、前記成分3の変性イソシアネート化合物が有するイソシアナト基の総モル数をIbとし、前記成分3の変性イソシアネート化合物が有する前記変性基の総モル数をHとした場合に、IaとIbとHの合計モル数に対するHの比H/(Ia+Ib+H)が0超過0.5以下である接着剤用組成物。 - 前記活性水素を有する官能基がヒドロキシ基及びカルボキシ基の少なくとも一方である請求項1に記載の接着剤用組成物。
- 前記活性水素化合物が、1価のアルコール及び1価のカルボン酸から選択される少なくとも1種の化合物である請求項1に記載の接着剤用組成物。
- 前記ポリイソシアネート化合物が飽和脂肪族ポリイソシアネートである請求項1~3のいずれか一項に記載の接着剤用組成物。
- 前記ポリイソシアネート化合物が、飽和脂肪族ポリイソシアネートのイソシアヌレート体、及び、飽和脂肪族ポリイソシアネートのアロファネート体から選択される少なくとも1種の化合物である請求項1~3のいずれか一項に記載の接着剤用組成物。
- 前記酸変性ポリオレフィンが、プロピレン、エチレン、及びブテンのうちの1種以上を単量体として使用したポリオレフィンの酸変性物を含有する請求項1~5のいずれか一項に記載の接着剤用組成物。
- 前記酸変性ポリオレフィンが、エチレン性不飽和カルボン酸及びその酸無水物から選択される少なくとも1種でポリオレフィンを変性した酸変性物を含有する請求項1~6のいずれか一項に記載の接着剤用組成物。
- 金属箔と、樹脂製フィルムと、前記金属箔と前記樹脂製フィルムの間に介在し前記金属箔と前記樹脂製フィルムを接着する接着剤層と、を備え、前記接着剤層が、請求項1~7のいずれか一項に記載の接着剤用組成物の反応生成物を含有する接着剤で形成されている積層体。
- 前記金属箔がアルミニウム箔であり、前記樹脂製フィルムが熱融着性樹脂製フィルムである請求項8に記載の積層体。
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010209229A (ja) * | 2009-03-11 | 2010-09-24 | Toyo Ink Mfg Co Ltd | 粘着剤組成物及びそれを用いてなる粘着積層体 |
WO2014123183A1 (ja) * | 2013-02-07 | 2014-08-14 | 三井化学株式会社 | 接着剤、積層体、電池ケース用包材、電池、高アルカリ溶液用包材、アルコール含有溶液用包材および包装体 |
WO2015133496A1 (ja) * | 2014-03-04 | 2015-09-11 | 三井化学株式会社 | ラミネート接着剤、ラミネートフィルムの製造方法、ラミネートフィルムおよびレトルトパウチ材料 |
JP2016132716A (ja) * | 2015-01-19 | 2016-07-25 | 三井化学株式会社 | 組成物、コーティング剤、接着剤および積層体 |
WO2019225254A1 (ja) * | 2018-05-24 | 2019-11-28 | 三井化学株式会社 | コーティング剤、フィルム、積層体および電池ケース用包材 |
JP2021181513A (ja) * | 2020-05-18 | 2021-11-25 | 東洋インキScホールディングス株式会社 | ガスバリア性ラミネート接着剤、積層体及び包装体 |
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Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010209229A (ja) * | 2009-03-11 | 2010-09-24 | Toyo Ink Mfg Co Ltd | 粘着剤組成物及びそれを用いてなる粘着積層体 |
WO2014123183A1 (ja) * | 2013-02-07 | 2014-08-14 | 三井化学株式会社 | 接着剤、積層体、電池ケース用包材、電池、高アルカリ溶液用包材、アルコール含有溶液用包材および包装体 |
WO2015133496A1 (ja) * | 2014-03-04 | 2015-09-11 | 三井化学株式会社 | ラミネート接着剤、ラミネートフィルムの製造方法、ラミネートフィルムおよびレトルトパウチ材料 |
JP2016132716A (ja) * | 2015-01-19 | 2016-07-25 | 三井化学株式会社 | 組成物、コーティング剤、接着剤および積層体 |
WO2019225254A1 (ja) * | 2018-05-24 | 2019-11-28 | 三井化学株式会社 | コーティング剤、フィルム、積層体および電池ケース用包材 |
JP2021181513A (ja) * | 2020-05-18 | 2021-11-25 | 東洋インキScホールディングス株式会社 | ガスバリア性ラミネート接着剤、積層体及び包装体 |
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