JP2017152349A - Battery packaging material, battery container and battery - Google Patents
Battery packaging material, battery container and battery Download PDFInfo
- Publication number
- JP2017152349A JP2017152349A JP2016036394A JP2016036394A JP2017152349A JP 2017152349 A JP2017152349 A JP 2017152349A JP 2016036394 A JP2016036394 A JP 2016036394A JP 2016036394 A JP2016036394 A JP 2016036394A JP 2017152349 A JP2017152349 A JP 2017152349A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- component
- polybasic acid
- battery
- packaging material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000005022 packaging material Substances 0.000 title claims abstract description 48
- 239000010410 layer Substances 0.000 claims abstract description 156
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 52
- 239000011888 foil Substances 0.000 claims abstract description 48
- 150000007519 polyprotic acids Polymers 0.000 claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- 239000002184 metal Substances 0.000 claims abstract description 43
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 239000011347 resin Substances 0.000 claims abstract description 40
- 239000012790 adhesive layer Substances 0.000 claims abstract description 35
- 125000003118 aryl group Chemical group 0.000 claims abstract description 21
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 19
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 19
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 15
- 229920005862 polyol Polymers 0.000 claims description 34
- 150000003077 polyols Chemical class 0.000 claims description 29
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 18
- 239000007795 chemical reaction product Substances 0.000 claims description 15
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical class O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 14
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 229920006267 polyester film Polymers 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 58
- 230000001070 adhesive effect Effects 0.000 abstract description 55
- 239000004814 polyurethane Substances 0.000 abstract description 18
- 229920002635 polyurethane Polymers 0.000 abstract description 18
- 230000032683 aging Effects 0.000 abstract description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 69
- 239000003795 chemical substances by application Substances 0.000 description 61
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 30
- -1 acryl Chemical group 0.000 description 24
- 239000002253 acid Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 16
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000000465 moulding Methods 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 13
- 238000005886 esterification reaction Methods 0.000 description 13
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 11
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 235000011007 phosphoric acid Nutrition 0.000 description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- 230000001476 alcoholic effect Effects 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000012948 isocyanate Substances 0.000 description 7
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 238000005809 transesterification reaction Methods 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 6
- 150000002513 isocyanates Chemical class 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 239000001361 adipic acid Substances 0.000 description 5
- 235000011037 adipic acid Nutrition 0.000 description 5
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 5
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 5
- 239000000314 lubricant Substances 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000000565 sealant Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000002421 anti-septic effect Effects 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- WMYWOWFOOVUPFY-UHFFFAOYSA-L dihydroxy(dioxo)chromium;phosphoric acid Chemical compound OP(O)(O)=O.O[Cr](O)(=O)=O WMYWOWFOOVUPFY-UHFFFAOYSA-L 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
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- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/116—Primary casings; Jackets or wrappings characterised by the material
- H01M50/124—Primary casings; Jackets or wrappings characterised by the material having a layered structure
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/306—Resistant to heat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2439/00—Containers; Receptacles
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、リチウムイオン電池などの二次電池用の電池用容器や電池パックを形成するための電池用包装材用のポリウレタン接着剤に関する。また、本発明は外層側樹脂フィルム層（１１）と金属箔層（１３）とをポリウレタン接着剤を用いて積層した電池用包装材に関する。さらに本発明は、外層側樹脂フィルム層（１１）が外層に位置するように前記電池用包装材を成型してなる電池用容器、および前記電池用容器を用いてなる電池に関する。 The present invention relates to a polyurethane adhesive for a battery packaging material for forming a battery container or battery pack for a secondary battery such as a lithium ion battery. Moreover, this invention relates to the packaging material for batteries which laminated | stacked the outer layer side resin film layer (11) and the metal foil layer (13) using the polyurethane adhesive. Furthermore, the present invention relates to a battery container formed by molding the battery packaging material such that the outer layer side resin film layer (11) is located in the outer layer, and a battery using the battery container.
携帯電話、携帯型パソコン等の電子機器の急速な成長により、軽量かつ小型のリチウムイオン電池などの二次電池の需要が増大してきた。二次電池の外装体としては、従来、金属製缶が用いられてきたが、軽量化や生産性の観点よりプラスチックフィルムや金属箔などを積層した包装材が主流となりつつある。
最もシンプルな包装材としては、図１のような外層側から順に外層側樹脂フィルム層（１１）、外層側接着剤層（１２）、金属箔層（１３）、内層側接着剤層（１４）およびヒートシール層（１５）からなる積層体が挙げられる。電池用容器は、図２に示すように、前記外層側樹脂フィルム層（１１）が凸面を構成し、前記ヒートシール層（１５）が凹面を構成するように前記包装材を成型（深絞り成型加工、張出し成型加工等）したものである。そして、電池用容器の凹面側に、電極や電解液等を封入してシールすることにより電池を製造している。
Due to the rapid growth of electronic devices such as mobile phones and portable personal computers, the demand for secondary batteries such as lightweight and small lithium-ion batteries has increased. Conventionally, metal cans have been used as outer bodies of secondary batteries, but packaging materials in which plastic films, metal foils, and the like are laminated are becoming mainstream from the viewpoints of weight reduction and productivity.
As the simplest packaging material, the outer layer side resin film layer (11), the outer layer side adhesive layer (12), the metal foil layer (13), and the inner layer side adhesive layer (14) in order from the outer layer side as shown in FIG. And a laminate comprising the heat seal layer (15). As shown in FIG. 2, the battery container is formed by molding the packaging material so that the outer resin film layer (11) has a convex surface and the heat seal layer (15) has a concave surface (deep drawing molding). Processing, overhang molding processing, etc.). And the battery is manufactured by enclosing and sealing an electrode, electrolyte solution, etc. on the concave surface side of the battery container.
電池用包装材としては、外層側樹脂フィルム層と金属箔層の間に、特定の分子量、ポリエステル組成、引っ張り応力の接着剤層を設けて接着させることにより成型性や耐久性に優れた電池用包材が提供できることが開示されている（特許文献１：特許５３８２２５６号）。 As battery packaging material, an adhesive layer with a specific molecular weight, polyester composition, and tensile stress is provided between the outer resin film layer and the metal foil layer, and the battery is excellent in moldability and durability. It is disclosed that a packaging material can be provided (Patent Document 1: Patent 5382256).
また、電池用包装材の製造方法として、外層樹脂フィルムとアルミニウム箔を貼り合わせ後に、５０〜８５℃の温度範囲で第１段エージングを行い、滑剤が練り込まれた内層樹脂フィルムとアルミニウム箔を貼り合わせ後に３０〜５０℃の温度範囲で第２段エージングを行う事により、エージングによる滑り性低下を抑制し、成型性に優れた成型用包装材料が製造出来る事が開示されている。（特許文献２：特開２００５−３２４５６）。 In addition, as a method for producing a battery packaging material, after the outer layer resin film and the aluminum foil are bonded together, the first stage aging is performed in a temperature range of 50 to 85 ° C., and the inner layer resin film and the aluminum foil into which the lubricant is kneaded are obtained. It has been disclosed that by performing second-stage aging in a temperature range of 30 to 50 ° C. after bonding, it is possible to produce a molding packaging material that suppresses a decrease in slipperiness due to aging and is excellent in moldability. (Patent Document 2: JP-A-2005-32456).
また、耐熱樹脂層と金属箔層の間に着色顔料を含んだ接着剤層を設けて、前記接着剤層には、特定の分子量と分散度のポリエステル樹脂と５０モル％以上の芳香族ポリイソシアネートを含む事により、成型性やヒートシール耐性に優れた成型用包装材が開示されている（特許文献３：特開２０１５−１６６２６１）。 Further, an adhesive layer containing a color pigment is provided between the heat-resistant resin layer and the metal foil layer, and the adhesive layer includes a polyester resin having a specific molecular weight and a degree of dispersion and an aromatic polyisocyanate having a molecular weight of 50 mol% or more. , A molding packaging material excellent in moldability and heat seal resistance is disclosed (Patent Document 3: JP-A-2015-166261).
さらに、基材層、接着剤層、バリア層、及びシーラント層を有する積層体からなり、前記接着層が熱硬化樹脂と硬化促進剤とエラストマー樹脂を含む事により、熱ジワ不良が無く短時間で硬化が完了し、優れた密着性や成型性の電池包装材料が開示されている（特開２０１４−１８６９８３）。 Furthermore, it consists of a laminate having a base material layer, an adhesive layer, a barrier layer, and a sealant layer, and the adhesive layer contains a thermosetting resin, a curing accelerator, and an elastomer resin, so that there is no thermal wrinkle defect in a short time. Curing has been completed and a battery packaging material having excellent adhesion and moldability has been disclosed (Japanese Patent Application Laid-Open No. 2014-186893).
さらに、基材層、第１接着層、金属箔層、腐食防止処理層、第２接着層及びシーラント層を有する積層体からなり、前記第１接着層が水酸基を側鎖に有するポリエステルポリオール及びアクリルポリオールの少なくとも１種と脂肪族イソシアネート硬化剤から形成される事で、優れた耐電解液性を有する蓄電デバイス外装材が開示されている（特開２０１３−１５７２８５）。 Furthermore, the polyester polyol and the acryl which consist of a laminate having a base material layer, a first adhesive layer, a metal foil layer, a corrosion prevention treatment layer, a second adhesive layer and a sealant layer, wherein the first adhesive layer has a hydroxyl group in the side chain. An electricity storage device exterior material having excellent electrolytic solution resistance by being formed from at least one kind of polyol and an aliphatic isocyanate curing agent is disclosed (Japanese Patent Laid-Open No. 2013-157285).
近年、車載や家庭蓄電など用途が拡大すると共に、二次電池の大容量化が求められており、優れた成型性が電池用包装材には求められるようになっている。
また、優れた成型性を得る為には、成型する包装材と金型が適度に滑らせ、延伸率の高い角型コーナー部における金属箔のピンホールを抑制する事が重要になる。そこで、包装材の外層側樹脂フィルム層やシーラント層には予め滑剤を練り込む場合がある。
また、外層側樹脂フィルム層と金属箔を貼り合わせる接着剤は成型性や耐熱性の面から硬化型ポリウレタン接着剤が使用し、優れた性能を得る為には６０℃以上で１週間程度の高温エージングを必要とする。しかし、６０℃以上ではフィルムやヒートシール層に予め練り込んだ滑剤が内部に潜り込み、本来の滑り性を失ってしまう。また、エージング後に滑剤をコーティングする事も可能だが、経済性を損なう。
更に、電池用容器作成時及び電解液充填時における成型物の変形により、角型凸部中央が窪み、凸部コーナーにエクボ状の皺が寄る事で、ヒートシールにおいて凸部コーナーの層間に浮きが発生しやすくなる。
本発明は、上記背景を鑑みてなされたものであり、滑剤の滑り性を保持した４０℃のエージングでも優れた成型性や耐熱接着性を有し、成型物が変形しても層間の浮きが無い電池、電池用包装材を提供する事を課題とする。
In recent years, applications such as in-vehicle and household power storage have been expanded, and the capacity of secondary batteries has been increased, and excellent moldability has been required for battery packaging materials.
In addition, in order to obtain excellent moldability, it is important that the packaging material to be molded and the mold are appropriately slid to suppress pinholes in the metal foil at the corners having a high stretch rate. Therefore, a lubricant may be kneaded in advance in the outer layer side resin film layer or sealant layer of the packaging material.
The adhesive that bonds the outer resin film layer to the metal foil is a curable polyurethane adhesive from the viewpoints of moldability and heat resistance. In order to obtain excellent performance, a high temperature of about 1 week at 60 ° C or higher is required. Requires aging. However, at 60 ° C. or higher, the lubricant previously kneaded into the film or the heat seal layer sinks into the inside and loses its original slipperiness. In addition, it is possible to coat the lubricant after aging, but this is not economical.
Furthermore, due to the deformation of the molded product during battery container preparation and electrolyte filling, the center of the square-shaped convex part is recessed, and an exaggerated wrinkle approaches the convex part corner. Is likely to occur.
The present invention has been made in view of the above background, and has excellent moldability and heat-resistant adhesive properties even at 40 ° C. aging that keeps the slipperiness of the lubricant. It is an object to provide a battery and a packaging material for the battery that are not present.
本発明者らは、以下の外層側接着剤を用いることによって、上記課題を解決できることを見出した。
本発明は、外層側樹脂フィルム層（１１）、外層側接着剤層（１２）、金属箔層（１３）、内層側接着剤層（１４）およびヒートシール層（１５）が順次積層されてなる電池用包装材において、
前記外層側接着剤層（１２）が、ポリオール成分（Ａ）を含有する主剤とポリイソシアネート成分（Ｂ）を含有する硬化剤とを含有するポリウレタン接着剤から形成された、電池用包装材に関する。
本発明の電池用包装材の形成に用いられる前記ポリウレタン接着剤は、ポリオール成分（Ａ）が多塩基酸成分と多価アルコール成分との反応生成物であって、数平均分子量１００００〜４００００のポリエステルポリオールであるか、
もしくは
多塩基酸成分（１）と多価アルコール成分（１）との反応生成物（１）、および多塩基酸成分（２）と多価アルコール成分（２）との反応生成物（２）の混合物であって、前記多塩基酸成分（１）と前記多塩基酸成分（２）との合計１００モル％中、芳香族多塩基酸成分を４５〜９５モル％含み、前記混合物の数平均分子量１００００〜４００００のポリエステルポリオールであり、
ポリイソシアネート成分（Ｂ）がジフェニルメタンジイソシアネート（以下、ＭＤＩと略すこともある）に３官能アルコールが付加したアダクト体と、ヘキサメチレンジイソシアネート（以下、ＨＤＩと略すこともある）の多官能誘導体とを含み、イソシアネート基１００モル％中、ジフェニルメタンジイソシアネート由来のイソシアネート基が４０〜９０モル％である、ことを特徴とする電池用包装材。
The present inventors have found that the above problem can be solved by using the following outer layer side adhesive.
In the present invention, an outer resin film layer (11), an outer adhesive layer (12), a metal foil layer (13), an inner adhesive layer (14) and a heat seal layer (15) are sequentially laminated. In battery packaging materials,
The said outer layer side adhesive bond layer (12) is related with the battery packaging material formed from the polyurethane adhesive containing the main ingredient containing a polyol component (A) and the hardening | curing agent containing a polyisocyanate component (B).
In the polyurethane adhesive used for forming the battery packaging material of the present invention, the polyol component (A) is a reaction product of a polybasic acid component and a polyhydric alcohol component, and has a number average molecular weight of 10,000 to 40,000. A polyol,
Or the reaction product (1) of the polybasic acid component (1) and the polyhydric alcohol component (1), and the reaction product (2) of the polybasic acid component (2) and the polyhydric alcohol component (2). A mixture comprising 45 to 95 mol% of an aromatic polybasic acid component in a total of 100 mol% of the polybasic acid component (1) and the polybasic acid component (2), and the number average molecular weight of the mixture A polyester polyol of 10,000 to 40,000,
The polyisocyanate component (B) includes an adduct obtained by adding a trifunctional alcohol to diphenylmethane diisocyanate (hereinafter sometimes abbreviated as MDI) and a polyfunctional derivative of hexamethylene diisocyanate (hereinafter sometimes abbreviated as HDI). The battery packaging material characterized in that the isocyanate group derived from diphenylmethane diisocyanate is 40 to 90 mol% in 100 mol% of the isocyanate groups.
また、本発明は、前記の電池用包装材から成型されてなる電池用容器であって、外層側樹脂フィルム層（１１）が凸面を構成し、ヒートシール層（１５）が凹面を構成している、電池用容器に関する。 Moreover, this invention is a battery container formed from the said battery packaging material, Comprising: The outer layer side resin film layer (11) comprises a convex surface, and the heat seal layer (15) comprises a concave surface. The present invention relates to a battery container.
さらに、本発明は、前記の電池用容器を使用してなる電池に関する。 Furthermore, this invention relates to the battery formed using the said battery container.
外層側樹脂フィルム層（１１）、外層側接着剤層（１２）、金属箔層（１３）、内層側接着剤層（１４）、ヒートシール層（１５）が順次積層されてなる電池用包装材において、特定の数平均分子量と、芳香族多塩基酸成分における特定のモル％を有するポリエステルポリオールを含み、特定のポリイソシアネート成分を含む接着剤を外層側接着剤層に用いる事により、６０℃未満のエージングでも優れた成型性や耐熱接着性を有し、成型物が変形しても層間の浮きが無い電池用包装材が提供できる。前記電池用包装材を用いてなる電池用容器により、信頼性に優れた電池が提供できる。 Battery packaging material in which outer layer side resin film layer (11), outer layer side adhesive layer (12), metal foil layer (13), inner layer side adhesive layer (14), and heat seal layer (15) are sequentially laminated. In particular, the polyester polyol having a specific number average molecular weight and a specific mol% in the aromatic polybasic acid component, and using an adhesive containing a specific polyisocyanate component in the outer layer side adhesive layer is less than 60 ° C. Thus, it is possible to provide a battery packaging material that has excellent moldability and heat-resistant adhesion even during aging, and does not float between layers even when the molded product is deformed. A battery container using the battery packaging material can provide a battery with excellent reliability.
以下、本発明の実施の形態を、詳細に説明する。なお、本明細書において「任意の数Ａ〜任意の数Ｂ」なる記載は、数Ａおよび数Ａより大きい範囲であって、数Ｂおよび数Ｂより小さい範囲を意味する。
本発明のポリウレタン接着剤は、電池用容器を得るための電池用包装材の形成に使用される。電池用容器は、図２に示すようなトレイ状のものの他、筒状（円筒、四角筒、楕円筒等）のものがある。これらの電池用容器は、平たい状態の電池用包装材を成型加工して得る。電池用容器の内側、即ち電解液と接する面は、ヒートシール層（１５）である。フランジ部のヒートシール層（１５）と、別の電池用包装材を構成するヒートシール層（１５）や別の電池用容器のフランジ部のヒートシール層（１５）とを対向・接触させ、加熱することにより、ヒートシール層（１５）同士を融着させ、電解液を封入する。
Hereinafter, embodiments of the present invention will be described in detail. In the present specification, the description “arbitrary number A to arbitrary number B” means a range larger than the number A and the number A and smaller than the number B and the number B.
The polyurethane adhesive of the present invention is used for forming a battery packaging material for obtaining a battery container. The battery container has a cylindrical shape (cylinder, square tube, elliptical tube, etc.) in addition to the tray shape as shown in FIG. These battery containers are obtained by molding a flat battery packaging material. The inside of the battery container, that is, the surface in contact with the electrolyte is a heat seal layer (15). Heating the heat seal layer (15) of the flange portion with the heat seal layer (15) constituting another battery packaging material or the heat seal layer (15) of the flange portion of another battery container, and heating By doing so, the heat seal layers (15) are fused together, and the electrolytic solution is sealed.
電池用容器は金属箔（１３）を具備する。電池用容器において、通常、金属箔（１３）を境に電解液に近い側を「内側」、「内層」、遠い側を「外側」、「外層」という。そこで、電池用容器を形成する予定の電池用包装材においても、金属箔（１３）を境に電解液に近くに位置する予定の側を「内側」、「内層」、遠くに位置する予定の側を「外側」、「外層」という。
尚、記載するポリウレタン系接着剤は、外層側樹脂フィルム層（１１）と金属箔層（１３）とを積層（貼りあわせ）するためのものである。
The battery container comprises a metal foil (13). In the battery container, the side closer to the electrolyte solution with the metal foil (13) as a boundary is generally referred to as “inner side”, “inner layer”, and the far side as “outer side” and “outer layer”. Therefore, even in the battery packaging material that is to form the battery container, the side that is to be located near the electrolytic solution with the metal foil (13) as a boundary is designated as “inside”, “inner layer”, and far away. The sides are called “outside” and “outer layer”.
In addition, the polyurethane-type adhesive to describe is for laminating | stacking (bonding) an outer layer side resin film layer (11) and a metal foil layer (13).
前記ポリウレタン系接着剤は、主剤と硬化剤とを用いるものである。主剤と硬化剤とを使用時に混合する、いわゆる２液混合タイプの接着剤であってもよいし、主剤と硬化剤とが予め混合された１液タイプの接着剤であってもよい。さらに、複数の主剤および／または複数の硬化剤を使用時に混合するタイプであってもよい。 The polyurethane adhesive uses a main agent and a curing agent. It may be a so-called two-component mixed adhesive in which the main agent and the curing agent are mixed at the time of use, or may be a one-component adhesive in which the main agent and the curing agent are mixed in advance. Furthermore, the type which mixes a several main ingredient and / or several hardening | curing agent at the time of use may be sufficient.
主剤に含まれるポリオール成分（Ａ）としては、例えば、ポリエステルポリオール、ポリエーテルポリオール、ポリカーボネートポリオール、ポリオレフィンポリオール、アクリルポリオールなどの比較的分子量の大きなポリオールや、エチレングリコールやトリメチロールプロパンなどの比較的分子量の小さなポリオールが挙げられる。さらに、前記ポリオールをイソシアネート成分と水酸基過剰の条件下に反応させたポリウレタンポリオールなどもポリオール成分（Ａ）の１つとして挙げられる。これらは、接着強度や成型性に悪影響が出ない範囲で、単独で使用したり、または２種類以上を併用したりすることができる。 Examples of the polyol component (A) contained in the main agent include relatively high molecular weight polyols such as polyester polyols, polyether polyols, polycarbonate polyols, polyolefin polyols and acrylic polyols, and relatively molecular weights such as ethylene glycol and trimethylolpropane. Small polyol. Furthermore, a polyurethane polyol obtained by reacting the polyol with an isocyanate component under a hydroxyl group-excess condition can be cited as one of the polyol components (A). These can be used alone or in combination of two or more, as long as the adhesive strength and moldability are not adversely affected.
ポリエステルポリオールとしては、多塩基酸成分と多価アルコール成分を反応させて得られたポリエステルポリオールを挙げることができる。
多塩基酸成分としては、例えば、イソフタル酸、テレフタル酸、ナフタレンジカルボン酸、無水フタル酸、アジピン酸、アゼライン酸、セバシン酸、コハク酸、グルタル酸、無水テトラヒドロフタル酸、無水ヘキサヒドロフタル酸、無水マレイン酸、無水イタコン酸およびそのエステル化合物などを挙げることができる。これらは単独で使用したり２種以上を併用したりできる。
多価アルコール成分としては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール、１，６−ヘキサンジオール、ネオペンチルグリコール、１，４−ブチレングリコール、１，４−シクロヘキサンジメタノール、トリメチロールプロパン、グリセリン、１，９−ナノンジオール、３−メチル−１，５−ペンタンジオール、ポリエーテルポリオール、ポリカーボネートポリオール、ポリオレフィンポリオール、アクリルポリオール、ポリウレタンポリオールなどを挙げることができる。これらは単独で使用したり２種以上を併用したりできる。
Examples of the polyester polyol include a polyester polyol obtained by reacting a polybasic acid component and a polyhydric alcohol component.
Examples of the polybasic acid component include isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, phthalic anhydride, adipic acid, azelaic acid, sebacic acid, succinic acid, glutaric acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, anhydrous Mention may be made of maleic acid, itaconic anhydride and ester compounds thereof. These can be used alone or in combination of two or more.
Examples of the polyhydric alcohol component include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,6-hexanediol, neopentyl glycol, 1,4-butylene glycol, 1,4-cyclohexanedimethanol. , Trimethylolpropane, glycerin, 1,9-nanonediol, 3-methyl-1,5-pentanediol, polyether polyol, polycarbonate polyol, polyolefin polyol, acrylic polyol, polyurethane polyol, and the like. These can be used alone or in combination of two or more.
また、前記ポリエステルポリオールを、例えばフタル酸、トリメリット酸、ピロメリット酸等の多塩基酸およびそれらの無水物とさらに反応させて得られる、分子中（分子内部や分子末端）にカルボキシル基を有するポリエステルポリオールもポリエステルポリオールの一種として挙げることができる。 In addition, the polyester polyol has a carboxyl group in the molecule (inside the molecule or at the end of the molecule) obtained by further reacting with, for example, a polybasic acid such as phthalic acid, trimellitic acid, pyromellitic acid or the anhydride thereof. Polyester polyol can also be mentioned as a kind of polyester polyol.
さらに、前記ポリエステルポリオールを、例えば、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、キシリレンジイソシアネート、ジフェニルメタンジイソシアネート、イソホロンジイソシアネート、１，５−ナフタレンジイソシアネート、ヘキサメチレンジイソシアネート、水添化ジフェニルメタンジイソシアネートなどのポリイソシアネートと反応させて得られるポリエステルウレタンポリオールもポリエステルポリオールの一種として挙げることができる。 Further, the polyester polyol is, for example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate, hydrogenated diphenylmethane. A polyester urethane polyol obtained by reacting with a polyisocyanate such as diisocyanate can also be mentioned as a kind of polyester polyol.
ポリエステルポリオールの数平均分子量は１００００〜４００００であり、１５０００〜３００００であることが好ましい。
また、構成成分である多塩基酸成分１００モル％中、芳香族多塩基酸成分の含有量は４５〜９５モル％であり、５５〜８５モル％とすることが好ましい。
ポリエステルポリオールの数平均分子量が１００００以上であったり、芳香族多塩基酸成分が４５モル％以上であったりすることにより、耐熱接着性が向上する傾向にある。
一方、数平均分子量が４００００以下であることにより、希釈溶剤への溶解性が向上し、接着剤塗工時の粘度制御がし易くなり、塗工し易くなる。また、外層側樹脂フィルム層（１１）と金属箔層（１３）との層間の接着強度向上の点から、多塩基酸成分が９５モル％以下であることが好ましい。
即ち、このようなポリエステルポリオールを用いることによって、外層側樹脂フィルム層（１１）と金属箔層（１３）との層間の耐熱接着強度をより高めると共に、成型物のヒートシール耐性がより良好な電池用包装材を得ることができる。
The number average molecular weight of the polyester polyol is 10,000 to 40,000, preferably 15,000 to 30,000.
The content of the aromatic polybasic acid component is 45 to 95 mol%, preferably 55 to 85 mol%, in 100 mol% of the polybasic acid component which is a constituent component.
When the number average molecular weight of the polyester polyol is 10,000 or more, or the aromatic polybasic acid component is 45 mol% or more, the heat resistant adhesiveness tends to be improved.
On the other hand, when the number average molecular weight is 40,000 or less, the solubility in a diluting solvent is improved, the viscosity can be easily controlled during the coating of the adhesive, and the coating becomes easy. Moreover, it is preferable that a polybasic acid component is 95 mol% or less from the point of the adhesive strength improvement of the interlayer of an outer layer side resin film layer (11) and a metal foil layer (13).
That is, by using such a polyester polyol, the heat resistance adhesion strength between the outer resin film layer (11) and the metal foil layer (13) is further enhanced, and the molded product has better heat seal resistance. Packaging material can be obtained.
本発明ではポリオール成分（Ａ）として、複数のポリエステルポリオールの混合物を用いることもできる。即ち、多塩基酸成分（１）と多価アルコール成分（１）との反応生成物（１）、多塩基酸成分（２）と多価アルコール成分（２）との反応生成物（２）をそれぞれ用意し、前記多塩基酸成分（１）と前記多塩基酸成分（２）との合計１００モル％中、芳香族多塩基酸成分を４５〜９５モル％含まれるように、かつ数平均分子量が１００００〜４００００となるように、反応生成物（１）と反応生成物（２）とを混合したものも使用できる。
例えば、芳香族多塩基酸成分のみを含む多塩基酸成分（１）と多価アルコール成分（１）との反応生成物（１）と、芳香族多塩基酸成分の含有量の少ない多塩基酸成分（２）と多価アルコール成分（２）との反応生成物（２）を混合し、混合物全体として前記多塩基酸成分（１）と前記多塩基酸成分（２）との合計１００モル％中、芳香族多塩基酸成分を４５〜９５モル％含まれればよい。
同様に、数平均分子量の異なる反応生成物（１）、（２）を混合し、混合物全体として数平均分子量が１００００〜４００００であればよい。
In the present invention, a mixture of a plurality of polyester polyols can also be used as the polyol component (A). That is, the reaction product (1) between the polybasic acid component (1) and the polyhydric alcohol component (1), and the reaction product (2) between the polybasic acid component (2) and the polyhydric alcohol component (2). Each prepared, the polybasic acid component (1) and the polybasic acid component (2) in a total of 100 mol%, the aromatic polybasic acid component is contained in 45 to 95 mol%, and the number average molecular weight A mixture of the reaction product (1) and the reaction product (2) can also be used so that becomes 10000-40000.
For example, a reaction product (1) of a polybasic acid component (1) containing only an aromatic polybasic acid component and a polyhydric alcohol component (1), and a polybasic acid having a low content of the aromatic polybasic acid component The reaction product (2) of the component (2) and the polyhydric alcohol component (2) is mixed, and the total mixture of the polybasic acid component (1) and the polybasic acid component (2) as a whole is 100 mol%. Among them, the aromatic polybasic acid component may be contained in an amount of 45 to 95 mol%.
Similarly, reaction products (1) and (2) having different number average molecular weights may be mixed, and the number average molecular weight of the mixture as a whole may be 10,000 to 40,000.
ポリエステルポリオールの数平均分子量は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）によるポリスチレン換算の値である。例えば、機種：ショウデックス（昭和電工（株）製）、カラム：ＫＦ−８０５Ｌ、ＫＦ−８０３Ｌ、及びＫＦ−８０２（昭和電工（株）製）、にてカラムの温度を４０℃として、溶離液としてＴＨＦを用い、流速を０．２ｍｌ/ｍｉｎとし、検出をＲＩ、試料濃度を０．０２％とし、標準試料としてポリスチレンを用いて行ったものである。本発明の数平均分子量は、上記の方法により測定した値を記載している。 The number average molecular weight of the polyester polyol is a value in terms of polystyrene by gel permeation chromatography (GPC). For example, the column temperature is set to 40 ° C. with a model: Showdex (manufactured by Showa Denko KK), columns: KF-805L, KF-803L, and KF-802 (manufactured by Showa Denko KK), and an eluent. Was used, and the flow rate was 0.2 ml / min, the detection was RI, the sample concentration was 0.02%, and polystyrene was used as the standard sample. The number average molecular weight of the present invention describes the value measured by the above method.
硬化剤に含まれるポリイソシアネート成分（Ｂ）は、ジフェニルメタンジイソシアネートに３官能アルコールが付加したアダクト体と、ヘキサメチレンジイソシアネートの多官能誘導体とを含む。
前記３官能アルコールとはグリセリン、トリメチロールプロパン（以下、ＴＭＰと略すこともある）、トリメチロールエタン、トリメチロールブタン、１，２，６−ヘキサントリオール等が挙げられる。
前記多官能誘導体としては、ダイマー、ヌレート体、ビウレット体、アロファネート体の他、炭酸ガスと上記ポリイソシアネート単量体とから得られる２，４，６−オキサジアジントリオン環を有するポリイソシアネートや、前記３官能アルコールをヘキサメチレンジイソシアネートに付加したアダクト体が挙げられる。
中でもジフェニルメタンジイソシアネートにトリメチロールプロパンが付加したアダクト体とヘキサメチレンジイソシアネートのヌレート体の混合物が、低温硬化性や変形後成型物のヒートシール耐性の観点からより好ましい。
The polyisocyanate component (B) contained in the curing agent contains an adduct obtained by adding a trifunctional alcohol to diphenylmethane diisocyanate and a polyfunctional derivative of hexamethylene diisocyanate.
Examples of the trifunctional alcohol include glycerin, trimethylolpropane (hereinafter sometimes abbreviated as TMP), trimethylolethane, trimethylolbutane, 1,2,6-hexanetriol, and the like.
As the polyfunctional derivative, in addition to dimer, nurate body, biuret body, allophanate body, polyisocyanate having 2,4,6-oxadiazinetrione ring obtained from carbon dioxide gas and the above polyisocyanate monomer, Examples thereof include adducts obtained by adding the trifunctional alcohol to hexamethylene diisocyanate.
Among them, a mixture of an adduct obtained by adding trimethylolpropane to diphenylmethane diisocyanate and a nurate of hexamethylene diisocyanate is more preferable from the viewpoints of low temperature curability and heat seal resistance of a molded product after deformation.
更に、ポリイソシアネート成分（Ｂ）は、イソシアネート基１００モル％中、ジフェニルメタンジイソシアネート由来のイソシアネート基を４０〜９０モル％含み、６０〜８０モル％であることが好ましい。４０モル％以上であることにより耐熱接着強度及びヒートシール耐性が向上し、９０モル％以下であることにより変形後成型物のヒートシール耐性が向上する。 Furthermore, polyisocyanate component (B) contains 40 to 90 mol% of isocyanate groups derived from diphenylmethane diisocyanate in 100 mol% of isocyanate groups, and preferably 60 to 80 mol%. When it is 40 mol% or more, the heat-resistant adhesive strength and heat seal resistance are improved, and when it is 90 mol% or less, the heat seal resistance of the molded product after deformation is improved.
本発明におけるポリウレタン接着剤は、主剤中に含まれるポリオール成分（Ａ）の有しているヒドロキシル基とカルボキシル基の合計に対する硬化剤（２）中に含まれるイソシアネート基の当量比［ＮＣＯ］／（［ＯＨ］＋［ＣＯＯＨ］）が１０〜３０であることが好ましく、１５〜３０であることがより好ましい。即ち、ヒドロキシル基とカルボキシル基の合計１モルに対し、イソシアネート基が１０モル以上であることにより変形後成型物のヒートシール耐性が向上する傾向にあり、３０モル以下であることにより硬化が速やかに進行し、外層側樹脂フィルム層（１１）と金属箔層（１３）の間の耐熱接着性が強くなる。 In the polyurethane adhesive of the present invention, the equivalent ratio of the isocyanate group contained in the curing agent (2) to the total of the hydroxyl group and the carboxyl group contained in the polyol component (A) contained in the main agent [NCO] / ( [OH] + [COOH]) is preferably from 10 to 30, and more preferably from 15 to 30. That is, the heat seal resistance of the molded product after deformation tends to be improved when the isocyanate group is 10 mol or more with respect to 1 mol in total of the hydroxyl group and the carboxyl group, and the curing is quick due to 30 mol or less. It progresses and the heat-resistant adhesiveness between the outer layer side resin film layer (11) and the metal foil layer (13) becomes strong.
本発明におけるポリウレタン接着剤には、その他、接着剤用として公知の添加剤を主剤、もしくは硬化剤に配合することができる。
たとえば、反応促進剤を使用することができる。
反応促進剤としては、たとえば、ジブチルチンジアセテート、ジブチルチンジラウレート、ジオクチルチンジラウレート、ジブチルチンジマレート等金属系触媒；１，８−ジアザ−ビシクロ（５，４，０）ウンデセン−７、１，５−ジアザビシクロ（４，３，０）ノネン−５、６−ジブチルアミノ−１，８−ジアザビシクロ（５，４，０）ウンデセン−７等の３級アミン；トリエタノールアミンのような反応性３級アミン等が挙げられ、これらの群から選ばれた１種または２種以上の反応促進剤を使用できる。
In addition to the polyurethane adhesive in the present invention, other additives known for adhesives can be added to the main agent or the curing agent.
For example, a reaction accelerator can be used.
Examples of the reaction accelerator include metal catalysts such as dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, and dibutyltin dimaleate; 1,8-diaza-bicyclo (5,4,0) undecene-7,1,5 A tertiary amine such as diazabicyclo (4,3,0) nonene-5,6-dibutylamino-1,8-diazabicyclo (5,4,0) undecene-7; a reactive tertiary amine such as triethanolamine 1 type, or 2 or more types of reaction accelerators selected from these groups can be used.
金属箔等の金属系素材に対する接着強度を向上させる観点から、シランカップリング剤を使用することができる。シランカップリング剤としては、たとえばビニルトリメトキシシラン、ビニルトリエトキシシランなどのビニル基を有するトリアルコキシシラン、３−アミノプロピルトリエトキシシラン、Ｎ−（２−アミノエチル）３−アミノプロピルトリメトキシシランなどのアミノ基を有するトリアルコキシシラン；３−グリシドキシプロピルトリメトキシシラン、２−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、３−グリシドキシプロピルトリエトキシシランなどのグリシジル基を有するトリアルコキシシランが挙げられる。これらは、それぞれ単独で、または２種以上を任意に組み合わせて使用できる。
シランカップリング剤の添加量は、ポリオール成分（Ａ）の固形分１００重量部に対し、０．１〜５重量部であることが好ましく、０．５〜３重量部であることがより好ましい。上記範囲のシランカップリング剤を添加することによって金属箔に対する接着強度を向上できる。
A silane coupling agent can be used from a viewpoint of improving the adhesive strength with respect to metal-type materials, such as metal foil. Examples of the silane coupling agent include trialkoxysilane having a vinyl group such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-aminopropyltriethoxysilane, and N- (2-aminoethyl) 3-aminopropyltrimethoxysilane. A trialkoxysilane having an amino group such as 3-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycidoxypropyltriethoxysilane. A trialkoxysilane is mentioned. These may be used alone or in any combination of two or more.
The addition amount of the silane coupling agent is preferably 0.1 to 5 parts by weight, and more preferably 0.5 to 3 parts by weight with respect to 100 parts by weight of the solid content of the polyol component (A). By adding the silane coupling agent in the above range, the adhesion strength to the metal foil can be improved.
同様に、金属箔等の金属系素材に対する接着強度を向上させる観点から、リン酸又はリン酸誘導体を使用することができる。リン酸またはその誘導体の内、リン酸としては、遊離の酸素酸を少なくとも１個有しているものであればよく、例えば、次亜リン酸、亜リン酸、オルトリン酸、次リン酸等のリン酸類、メタリン酸、ピロリン酸、トリポリリン酸、ポリリン酸、ウルトラリン酸等の縮合リン酸類が挙げられる。また、リン酸の誘導体としては、上記のリン酸を遊離の酸素酸を少なくとも１個残した状態でアルコール類と部分的にエステル化されたもの等が挙げられる。これらのアルコールとしては、メタノール、エタノール、エチレングリコール、グリセリン等の脂肪族アルコール、フェノール、キシレノール、ハイドロキノン、カテコール、フロログリシノール等の芳香族アルコール等が挙げられる。リン酸またはその誘導体は、２種以上を組み合わせて用いてもよい。リン酸またはその誘導体の添加量は、接着剤の固形分を基準として０．０１〜１０重量％であることが好ましく、０．０５〜５重量％であることがより好ましく、０．０５〜１重量％であることが特に好ましい。 Similarly, phosphoric acid or a phosphoric acid derivative can be used from the viewpoint of improving the adhesive strength to metal-based materials such as metal foil. Of phosphoric acid or its derivatives, phosphoric acid may be any one having at least one free oxygen acid, such as hypophosphorous acid, phosphorous acid, orthophosphoric acid, hypophosphoric acid, etc. Examples thereof include condensed phosphoric acids such as phosphoric acids, metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid, and ultraphosphoric acid. Examples of phosphoric acid derivatives include those in which the above phosphoric acid is partially esterified with alcohols with at least one free oxygen acid remaining. Examples of these alcohols include aliphatic alcohols such as methanol, ethanol, ethylene glycol, and glycerin, and aromatic alcohols such as phenol, xylenol, hydroquinone, catechol, and phlorogricinol. Phosphoric acid or a derivative thereof may be used in combination of two or more. The addition amount of phosphoric acid or a derivative thereof is preferably 0.01 to 10% by weight, more preferably 0.05 to 5% by weight, based on the solid content of the adhesive, and 0.05 to 1 It is particularly preferred that it is wt%.
ラミネート外観を向上させる目的で、公知のレベリング剤または消泡剤を、主剤に配合することもできる。レベリング剤としては、たとえば、ポリエーテル変性ポリジメチルシロキサン、ポリエステル変性ポリジメチルシロキサン、アラルキル変性ポリメチルアルキルシロキサン、ポリエステル変性水酸基含有ポリジメチルシロキサン、ポリエーテルエステル変性水酸基含有ポリジメチルシロキサン、アクリル系共重合物、メタクリル系共重合物、ポリエーテル変性ポリメチルアルキルシロキサン、アクリル酸アルキルエステル共重合物、メタクリル酸アルキルエステル共重合物、レシチンなどが挙げられる。
消泡剤としては、シリコーン樹脂、シリコーン溶液、アルキルビニルエーテルとアクリル酸アルキルエステルとメタクリル酸アルキルエステルとの共重合物などの公知のものが挙げられる。
For the purpose of improving the appearance of the laminate, a known leveling agent or antifoaming agent can be added to the main agent. Examples of leveling agents include polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, aralkyl-modified polymethylalkylsiloxane, polyester-modified hydroxyl group-containing polydimethylsiloxane, polyetherester-modified hydroxyl group-containing polydimethylsiloxane, and acrylic copolymers. Methacrylic copolymer, polyether-modified polymethylalkylsiloxane, acrylic acid alkyl ester copolymer, methacrylic acid alkyl ester copolymer, lecithin and the like.
Examples of the antifoaming agent include known resins such as silicone resins, silicone solutions, and copolymers of alkyl vinyl ether, alkyl acrylate ester and alkyl methacrylate ester.
本発明の電池用包装材は、例えば、通常用いられている方法により製造することができる。
たとえば、外層側樹脂フィルム層（１１）と金属箔層（１３）とを前述のポリオール成分（Ａ）とポリイソシアネート成分（Ｂ）とを含む接着剤（以下、外層側接着剤とも略す）を用いて積層し、中間積層体を得る。次いで、内層側接着剤を用いて中間積層体の金属箔層（１３）面にヒートシール層（１４）を積層することができる。
あるいは、内層側接着剤を用いて金属箔層（１３）とヒートシール層（１４）とを積層し、中間積層体を得る。次いで、前述の外層側接着剤を用いて、中間積層体の金属箔層（１３）と外層側樹脂フィルム層（１１）とを積層することができる。
前者の場合、外層側接着剤は、外層側樹脂フィルム層（１１）もしくは金属箔層（１３）いずれか一方の基材の片面に塗布し、溶剤を揮散させた後、接着剤層に他方の基材を加熱加圧下に重ね合わせ、次いで加温下でエージングし、接着剤層を硬化させれば良い。接着剤層量は、１〜１０ｇ／ｍ２程度であることが好ましい。
後者の場合も同様に、外層側接着剤は、外層側樹脂フィルム層（１１）もしくは中間積層体の金属箔層（１３）面のいずれかに塗布すればよい。
The battery packaging material of the present invention can be produced, for example, by a commonly used method.
For example, the outer layer side resin film layer (11) and the metal foil layer (13) are used using an adhesive (hereinafter also abbreviated as an outer layer side adhesive) containing the aforementioned polyol component (A) and polyisocyanate component (B). To obtain an intermediate laminate. Subsequently, a heat seal layer (14) can be laminated | stacked on the metal foil layer (13) surface of an intermediate | middle laminated body using an inner layer side adhesive agent.
Or a metal foil layer (13) and a heat seal layer (14) are laminated | stacked using an inner layer side adhesive agent, and an intermediate laminated body is obtained. Subsequently, the metal foil layer (13) of the intermediate laminate and the outer layer side resin film layer (11) can be laminated using the outer layer side adhesive described above.
In the former case, the outer layer side adhesive is applied to one side of either the outer layer side resin film layer (11) or the metal foil layer (13), and the solvent is stripped, and then the other adhesive layer is applied to the adhesive layer. The substrate may be overlaid under heat and pressure, then aged under heating to cure the adhesive layer. The adhesive layer amount is preferably about 1 to 10 g / m 2.
Similarly, in the latter case, the outer layer side adhesive may be applied to either the outer layer side resin film layer (11) or the metal foil layer (13) surface of the intermediate laminate.
外層側接着剤を基材に塗工する際、塗液を適度な粘度に調整するために、乾燥工程において基材への影響がない範囲内で溶剤が含まれてもよい。
溶剤としては、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系化合物、酢酸メチル、酢酸エチル、酢酸ブチル、乳酸エチル、酢酸メトキシエチル等のエステル系化合物、ジエチルエーテル、エチレングリコールジメチルエーテル等のエーテル系化合物、トルエン、キシレン等の芳香族化合物、ペンタン、ヘキサン等の脂肪族化合物、塩化メチレン、クロロベンゼン、クロロホルム等のハロゲン化炭化水素化合物、エタノール、イソプロピルアルコール、ノルマルブタノール等のアルコール類、水等が挙げられる。これら溶剤は単独でも、２種類以上を併用してもよい。
なお、アルコール類、水を溶剤として用いる場合は、ポリイソシアネート成分（Ｂ）中のイソシアネート基は適切なブロック化剤でブロックしておくことが好ましい。
When the outer layer side adhesive is applied to the substrate, a solvent may be contained within a range that does not affect the substrate in the drying step in order to adjust the coating liquid to an appropriate viscosity.
Solvents include ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ester compounds such as methyl acetate, ethyl acetate, butyl acetate, ethyl lactate and methoxyethyl acetate, ethers such as diethyl ether and ethylene glycol dimethyl ether. Compounds, aromatic compounds such as toluene and xylene, aliphatic compounds such as pentane and hexane, halogenated hydrocarbon compounds such as methylene chloride, chlorobenzene and chloroform, alcohols such as ethanol, isopropyl alcohol and normal butanol, and water It is done. These solvents may be used alone or in combination of two or more.
In addition, when using alcohol and water as a solvent, it is preferable to block the isocyanate group in a polyisocyanate component (B) with a suitable blocking agent.
本発明において外層側接着剤を塗工する装置としては、コンマコーター、ドライラミネーター、ロールナイフコーター、ダイコーター、ロールコーター、バーコーター、グラビアロールコーター、リバースロールコーター、ブレードコーター、グラビアコーター、マイクログラビアコーター等が挙げられる。 As an apparatus for coating the outer layer side adhesive in the present invention, a comma coater, a dry laminator, a roll knife coater, a die coater, a roll coater, a bar coater, a gravure roll coater, a reverse roll coater, a blade coater, a gravure coater, a micro gravure Examples include coaters.
本発明の電池用外装材を構成する外層側樹脂フィルム層（１１）は特に限定されるものではないが、ポリアミドフィルムまたはポリエステルフィルムであることが好ましく、これらフィルムは延伸フィルムであることが好ましい。また、カーボンブラックや酸化チタンなどの顔料により着色されていても良い。また、傷つき防止コート剤などのコート剤や、インキなどがコーティングされていても良い。また、２層以上のフィルムがあらかじめ積層されていても良い。フィルム層の厚さは特に限定されるものではないが１２〜１００μｍである事が好ましい。 Although the outer layer side resin film layer (11) constituting the battery exterior material of the present invention is not particularly limited, it is preferably a polyamide film or a polyester film, and these films are preferably stretched films. Further, it may be colored with a pigment such as carbon black or titanium oxide. In addition, a coating agent such as an anti-scratch coating agent, or ink may be coated. Two or more films may be laminated in advance. Although the thickness of a film layer is not specifically limited, It is preferable that it is 12-100 micrometers.
本発明の電池用外装材を構成する金属箔層（１３）は特に限定されるものではないが、アルミニウム箔層が好ましい。フィルム層の厚さは特に限定されるものではないが、２０〜８０μｍであることが好ましい。また、金属箔表面にはリン酸クロメート処理、クロム酸クロメート処理、３価クロム処理、リン酸亜鉛処理、リン酸ジルコニウム処理、酸価ジルコニウム処理、リン酸チタン処理、フッ酸処理、セリウム処理、ハイドロタルサイト処理などによる公知な防腐処理を行うことが好ましい。防腐処理を施すことによって、電池の電解液による金属箔表面の腐食劣化を抑制することができる。更に防腐処理表面上の有機プライマー又は防腐処理剤と有機ポリマーを配合した塗布型防腐処理剤として、フェノール樹脂、アミド樹脂、アクリル樹脂、ポリビニルアルコール、カップリング剤など公知な有機物を２００℃ほどの高温で金属に焼付けて、処理する事が好ましい。防腐処理剤と有機物を金属箔表面に塗布することで、金属箔と接着剤をより強固に接着させ、金属箔と接着剤間の浮きを更に抑制することができる。 Although the metal foil layer (13) which comprises the battery exterior material of this invention is not specifically limited, An aluminum foil layer is preferable. Although the thickness of a film layer is not specifically limited, It is preferable that it is 20-80 micrometers. In addition, the surface of the metal foil is phosphoric acid chromate treatment, chromate chromate treatment, trivalent chromium treatment, zinc phosphate treatment, zirconium phosphate treatment, acid value zirconium treatment, titanium phosphate treatment, hydrofluoric acid treatment, cerium treatment, hydro It is preferable to perform a known antiseptic treatment such as talcite treatment. By performing the antiseptic treatment, corrosion deterioration of the surface of the metal foil due to the battery electrolyte can be suppressed. Furthermore, known organic substances such as phenol resin, amide resin, acrylic resin, polyvinyl alcohol, and coupling agent are used at a high temperature of about 200 ° C. It is preferable to bake and treat the metal. By applying the preservative and the organic substance to the surface of the metal foil, the metal foil and the adhesive can be bonded more firmly, and the floating between the metal foil and the adhesive can be further suppressed.
本発明の電池用外装材を構成するヒートシール層（１５）は特に限定されるものではないが、ポリエチレン、ポリプロピレン、オレフィン系共重合体、これらの酸変成物およびアイオノマーからなる群より選ばれた少なくとも１種類の熱可塑性樹脂からなる未延伸フィルムであることが好ましい。ヒートシール層の厚さは特に限定されるものではないが、２０〜１５０μｍであることが好ましい。 The heat seal layer (15) constituting the battery exterior material of the present invention is not particularly limited, but is selected from the group consisting of polyethylene, polypropylene, olefin copolymers, these acid-modified products, and ionomers. It is preferably an unstretched film made of at least one kind of thermoplastic resin. Although the thickness of a heat seal layer is not specifically limited, It is preferable that it is 20-150 micrometers.
本発明の電池用外装材を構成する内層側接着剤層（１４）を形成する接着剤は特に限定されるものではないが、電池の電解液によって金属箔層（１３）とヒートシール層（１５）の接着強度が低下しないものが好ましく、公知の接着剤が使用できる。
例えば、ポリオレフィン樹脂と多官能イソシアネートの組み合わせた接着剤やポリオールと多官能イソシアネートとを組み合わせた接着剤をグラビアコーターなどにて金属箔層に塗布して、溶剤を乾燥させ、接着剤層にヒートシール層（１５）を加熱加圧下に重ね合わせ、次いで加温下でエージングし金属箔層（１３）とヒートシール層（１５）とを貼り合せることができる。
あるいは、酸変性ポリプロピレンなどの接着剤をＴダイ押出し機で金属箔層（１３）上に溶融押出しして接着剤層を形成し、前記接着剤層上にヒートシール層（１５）を重ね、金属箔層（１３）とヒートシール層（１５）とを貼り合せることができる。
外層側接着剤層（１２）および内層側接着剤層（１４）の両方がエージングを必要とする場合には、本発明に用いる外層側接着剤を使用すると、４０℃において、まとめてエージングすることができる。
Although the adhesive agent which forms the inner layer side adhesive bond layer (14) which comprises the battery cladding | exterior_material of this invention is not specifically limited, A metal foil layer (13) and a heat seal layer (15) with the electrolyte solution of a battery. ) That does not decrease the adhesive strength, and known adhesives can be used.
For example, an adhesive combining polyolefin resin and polyfunctional isocyanate or an adhesive combining polyol and polyfunctional isocyanate is applied to the metal foil layer with a gravure coater, etc., dried, and heat sealed to the adhesive layer. The layer (15) can be superposed under heat and pressure, and then aged under heating to bond the metal foil layer (13) and the heat seal layer (15).
Alternatively, an adhesive such as acid-modified polypropylene is melt-extruded on a metal foil layer (13) with a T-die extruder to form an adhesive layer, and a heat seal layer (15) is stacked on the adhesive layer to form a metal. The foil layer (13) and the heat seal layer (15) can be bonded together.
When both the outer layer side adhesive layer (12) and the inner layer side adhesive layer (14) require aging, when the outer layer side adhesive used in the present invention is used, it is aged together at 40 ° C. Can do.
本発明の電池用容器は、前述の電池用外装材を用い、外層側樹脂フィルム層（１１）が凸面を構成し、ヒートシール層（１５）が凹面を構成するように成型して得ることができる。 The battery container of the present invention can be obtained by using the above-described battery packaging material and molding so that the outer resin film layer (11) has a convex surface and the heat seal layer (15) has a concave surface. it can.
次に、実施例及び比較例を挙げて本発明を更に具体的に説明する。実施例及び比較例中の％は総て質量％を意味する。
（合成例１）
イソフタル酸２３２．４ｇ、エチレングリコール４２．７ｇ、ネオペンチルグリコール７１．８ｇ、１，６−ヘキサンジオール１０８．６ｇを仕込み、２００〜２３０℃で６時間エステル化反応を行い、所定量の水の留出後、アジピン酸８７．６ｇ加え、更に６時間エステル化反応を行った。所定量の水の留出後、テトライソブチルチタネート０．１３ｇを添加し徐々に減圧し、１．３〜２．６ｈＰａ、２３０〜２５０℃で３時間エステル交換反応を行い、芳香族多塩基酸成分７０モル％、数平均分子量１９，０００のポリエステルポリオールを得た。
このポリエステルポリオールを酢酸エチルにて不揮発分５０％に調整し、水酸基価２．８５ｍｇＫＯＨ／ｇ、酸価０．１ｍｇＫＯＨ／ｇのポリエステルポリオール溶液（１）を得た。
Next, the present invention will be described more specifically with reference to examples and comparative examples. In the examples and comparative examples,% means mass%.
(Synthesis Example 1)
Charge 232.4 g of isophthalic acid, 42.7 g of ethylene glycol, 71.8 g of neopentyl glycol, and 108.6 g of 1,6-hexanediol, conduct esterification reaction at 200 to 230 ° C. for 6 hours, and maintain a predetermined amount of water. After exiting, 87.6 g of adipic acid was added and the esterification reaction was carried out for 6 hours. After distilling a predetermined amount of water, 0.13 g of tetraisobutyl titanate is added, the pressure is gradually reduced, and transesterification is carried out at 1.3 to 2.6 hPa and 230 to 250 ° C. for 3 hours to obtain an aromatic polybasic acid component. A polyester polyol having 70 mol% and a number average molecular weight of 19,000 was obtained.
This polyester polyol was adjusted to 50% nonvolatile content with ethyl acetate to obtain a polyester polyol solution (1) having a hydroxyl value of 2.85 mgKOH / g and an acid value of 0.1 mgKOH / g.
なお、数平均分子量は、ショウデックス（昭和電工（株）製）、カラム：ＫＦ−８０５Ｌ、ＫＦ−８０３Ｌ、及びＫＦ−８０２（昭和電工（株）製）、にてカラムの温度を４０℃として、溶離液としてＴＨＦを用い、流速を０．２ｍｌ/ｍｉｎとし、検出をＲＩ、試料濃度を０．０２％とし、標準試料とし、測定したものであり、標準ポリスチレン換算の値である。 In addition, the number average molecular weight is 40 ° C at a column temperature of SHOWEX (manufactured by Showa Denko KK), columns: KF-805L, KF-803L, and KF-802 (manufactured by Showa Denko KK). , THF was used as the eluent, the flow rate was 0.2 ml / min, the detection was RI, the sample concentration was 0.02%, the standard sample was measured, and the value is in terms of standard polystyrene.
また、酸価、水酸基価は以下のようにして求めた。
＜酸価（ＡＶ）の測定＞
共栓三角フラスコ中に試料（ポリエステルポリオール溶液）約１ｇを精密に量り採り、トルエン／エタノール（容量比：トルエン／エタノール＝２／１）混合液１００ｍｌを加えて溶解する。これに、フェノールフタレイン試液を指示薬として加え、３０秒間保持する。その後、溶液が淡紅色を呈するまで０．１Ｎアルコール性水酸化カリウム溶液で滴定する。酸価は次式により求めた（単位：ｍｇＫＯＨ／ｇ）。
酸価（ｍｇＫＯＨ／ｇ）＝（５．６１１×ａ×Ｆ）／Ｓ
ただし、Ｓ：試料の採取量（ｇ）
ａ：０．１Ｎアルコール性水酸化カリウム溶液の消費量（ｍｌ）
Ｆ：０．１Ｎアルコール性水酸化カリウム溶液の力価
The acid value and hydroxyl value were determined as follows.
<Measurement of acid value (AV)>
About 1 g of a sample (polyester polyol solution) is accurately weighed in a stoppered Erlenmeyer flask and dissolved by adding 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution. To this is added phenolphthalein reagent as an indicator and held for 30 seconds. Thereafter, the solution is titrated with a 0.1N alcoholic potassium hydroxide solution until the solution becomes light red. The acid value was determined by the following formula (unit: mgKOH / g).
Acid value (mgKOH / g) = (5.611 × a × F) / S
Where S: Amount of sample collected (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution
＜水酸基価（ＯＨＶ）の測定＞
共栓三角フラスコ中に試料（ポリエステルポリオール溶液）約１ｇを精密に量り採り、トルエン／エタノール（容量比：トルエン／エタノール＝２／１）混合液１００ｍｌを加えて溶解する。更にアセチル化剤（無水酢酸２５ｇをピリジンで溶解し、容量１００ｍｌとした溶液）を正確に５ｍｌ加え、約１時間攪拌した。これに、フェノールフタレイン試液を指示薬として加え、３０秒間持続する。その後、溶液が淡紅色を呈するまで０．１Ｎアルコール性水酸化カリウム溶液で滴定する。
水酸基価は次式により求めた（単位：ｍｇＫＯＨ／ｇ）。
水酸基価（ｍｇＫＯＨ／ｇ）
＝［｛（ｂ−ａ）×Ｆ×２８．０５｝／Ｓ］＋Ｄ
ただし、Ｓ：試料の採取量（ｇ）
ａ：０．１Ｎアルコール性水酸化カリウム溶液の消費量（ｍｌ）
ｂ：空実験の０．１Ｎアルコール性水酸化カリウム溶液の消費量（ｍｌ）
Ｆ：０．１Ｎアルコール性水酸化カリウム溶液の力価
Ｄ：酸価（ｍｇＫＯＨ／ｇ）
<Measurement of hydroxyl value (OHV)>
About 1 g of a sample (polyester polyol solution) is accurately weighed in a stoppered Erlenmeyer flask and dissolved by adding 100 ml of a toluene / ethanol (volume ratio: toluene / ethanol = 2/1) mixed solution. Further, exactly 5 ml of an acetylating agent (a solution in which 25 g of acetic anhydride was dissolved in pyridine to make a volume of 100 ml) was added and stirred for about 1 hour. To this, phenolphthalein reagent is added as an indicator and lasts for 30 seconds. Thereafter, the solution is titrated with a 0.1N alcoholic potassium hydroxide solution until the solution becomes light red.
The hydroxyl value was determined by the following formula (unit: mgKOH / g).
Hydroxyl value (mgKOH / g)
= [{(B−a) × F × 28.05} / S] + D
Where S: Amount of sample collected (g)
a: Consumption of 0.1N alcoholic potassium hydroxide solution (ml)
b: Consumption of 0.1N alcoholic potassium hydroxide solution in the empty experiment (ml)
F: Potency of 0.1N alcoholic potassium hydroxide solution D: Acid value (mgKOH / g)
（合成例２）
イソフタル酸２３２．４ｇ、エチレングリコール４２．７ｇ、ネオペンチルグリコール７１．８ｇ、１，６−ヘキサンジオール１０８．６ｇを仕込み、２００〜２３０℃で６時間エステル化反応を行い、所定量の水の留出後、アジピン酸８７．６ｇ加え、更に６時間エステル化反応を行った。所定量の水の留出後、テトライソブチルチタネート０．１３ｇを添加し徐々に減圧し、１．３〜２．６ｈＰａ、２３０〜２５０℃で３時間エステル交換反応を行い、ポリエステルポリオールを得た。
得られたこのポリエステルポリオールの水酸基の約９０％を無水ピロメリット酸と反応させるために、このポリエステルポリオールの全量に対して無水ピロメリット酸７．７ｇを添加し、１８０℃で約２時間反応させた。液体クロマトグラフを用いて反応系中に未反応の無水ピロメリット酸が残存しないことを確認し、芳香族多塩基酸成分７０モル％、数平均分子量２０，０００の無水ピロメリット酸変性したポリエステルポリオールを得た。
無水ピロメリット酸変性したポリエステルポリオールを酢酸エチルにて不揮発分５０％に調整し、水酸基価０．４１ｍｇＫＯＨ／ｇ、酸価２．４０ｍｇＫＯＨ／ｇのポリエステルポリオール溶液（２）を得た。
(Synthesis Example 2)
Charge 232.4 g of isophthalic acid, 42.7 g of ethylene glycol, 71.8 g of neopentyl glycol, and 108.6 g of 1,6-hexanediol, conduct esterification reaction at 200 to 230 ° C. for 6 hours, and maintain a predetermined amount of water. After exiting, 87.6 g of adipic acid was added and the esterification reaction was carried out for 6 hours. After distilling a predetermined amount of water, 0.13 g of tetraisobutyl titanate was added and the pressure was gradually reduced, and a transesterification reaction was performed at 1.3 to 2.6 hPa and 230 to 250 ° C. for 3 hours to obtain a polyester polyol.
In order to react about 90% of the hydroxyl groups of the obtained polyester polyol with pyromellitic anhydride, 7.7 g of pyromellitic anhydride was added to the total amount of the polyester polyol and reacted at 180 ° C. for about 2 hours. It was. It is confirmed that unreacted pyromellitic anhydride does not remain in the reaction system using a liquid chromatograph, and the polyester polyol has been modified with pyromellitic anhydride having an aromatic polybasic acid component of 70 mol% and a number average molecular weight of 20,000. Got.
The polyester polyol modified with pyromellitic anhydride was adjusted to 50% nonvolatile content with ethyl acetate to obtain a polyester polyol solution (2) having a hydroxyl value of 0.41 mgKOH / g and an acid value of 2.40 mgKOH / g.
（合成例３）
イソフタル酸２３２．４ｇ、エチレングリコール４２．７ｇ、ネオペンチルグリコール７１．８ｇ、１，６−ヘキサンジオール１０８．６ｇを仕込み、２００〜２３０℃で６時間エステル化反応を行い、所定量の水の留出後、アジピン酸８７．６ｇ加え、更に６時間エステル化反応を行った。所定量の水の留出後、テトライソブチルチタネート０．１３ｇを添加し徐々に減圧し、１．３〜２．６ｈＰａ、２３０〜２５０℃で３時間エステル交換反応を行い、ポリエステルポリオールを得た。
このポリエステルポリオールを酢酸エチルにて不揮発分８０％に調整して得られたポリエステルポリオール溶液６００ｇに対して、トリレンジイソシアネート３．２ｇを添加し、８０℃で８時間反応し、芳香族多塩基酸成分７０モル％、数平均分子量２０，０００のポリエステルポリウレタンポリオールを得た。
更にこのポリエステルウレタンポリオールを酢酸エチルにて不揮発分５０％に調整し、、水酸基価２．７１ｍｇＫＯＨ／ｇ、酸価０．１ｍｇＫＯＨ／ｇのポリエステルポリオール溶液（３）を得た。
(Synthesis Example 3)
Charge 232.4 g of isophthalic acid, 42.7 g of ethylene glycol, 71.8 g of neopentyl glycol, and 108.6 g of 1,6-hexanediol, conduct esterification reaction at 200 to 230 ° C. for 6 hours, and maintain a predetermined amount of water. After exiting, 87.6 g of adipic acid was added, and the esterification reaction was further performed for 6 hours. After distilling a predetermined amount of water, 0.13 g of tetraisobutyl titanate was added and the pressure was gradually reduced, and a transesterification reaction was performed at 1.3 to 2.6 hPa and 230 to 250 ° C. for 3 hours to obtain a polyester polyol.
To 600 g of a polyester polyol solution obtained by adjusting the polyester polyol to 80% nonvolatile content with ethyl acetate, 3.2 g of tolylene diisocyanate is added and reacted at 80 ° C. for 8 hours to obtain an aromatic polybasic acid. A polyester polyurethane polyol having a component of 70 mol% and a number average molecular weight of 20,000 was obtained.
Furthermore, this polyester urethane polyol was adjusted to 50% nonvolatile content with ethyl acetate to obtain a polyester polyol solution (3) having a hydroxyl value of 2.71 mgKOH / g and an acid value of 0.1 mgKOH / g.
（合成例４）
イソフタル酸１４９．４ｇ、テレフタル酸１４９．４ｇ、エチレングリコール７１．３ｇ、ネオペンチルグリコール１１９．６ｇを仕込み、２００〜２２０℃で６時間エステル化反応を行い、所定量の水の留出後、セバチン酸４０．４ｇを加え、更に６時間エステル化反応を行った。所定量の水の留出後、テトライソブチルチタネート０．１３ｇを添加し徐々に減圧し、１．３〜２．６ｈＰａ、２３０〜２５０℃で６時間エステル交換反応を行い、芳香族多塩基酸成分９０モル％、数平均分子量１９，８００のポリエステルポリオールを得た。
更にこのポスリエステルポリオールを酢酸エチルにて不揮発分５０％に調整し、水酸基価２．７３ｍｇＫＯＨ／ｇ、酸価０．１ｍｇＫＯＨ／ｇのポリエステルポリオール溶液（４）を得た。
(Synthesis Example 4)
Charge 149.4 g of isophthalic acid, 149.4 g of terephthalic acid, 71.3 g of ethylene glycol, and 119.6 g of neopentyl glycol, conduct an esterification reaction at 200 to 220 ° C. for 6 hours, distill a predetermined amount of water, and then sebatin 40.4 g of acid was added, and the esterification reaction was further performed for 6 hours. After distilling a predetermined amount of water, 0.13 g of tetraisobutyl titanate is added and the pressure is gradually reduced, and transesterification is carried out at 1.3 to 2.6 hPa and 230 to 250 ° C. for 6 hours to obtain an aromatic polybasic acid component. A polyester polyol having 90 mol% and a number average molecular weight of 19,800 was obtained.
Furthermore, this polyester ester polyol was adjusted to 50% nonvolatile content with ethyl acetate to obtain a polyester polyol solution (4) having a hydroxyl value of 2.73 mgKOH / g and an acid value of 0.1 mgKOH / g.
（合成例５）
イソフタル酸８３．２ｇ、テレフタル酸８３．２ｇ、エチレングリコール１４２．６ｇを仕込み、２００〜２２０℃で８時間エステル化反応を行い、所定量の水を留出後、アゼライン酸１８８ｇを加え、更に４時間エステル化反応を行った。所定量の水の留出後、テトライソブチルチタネート０．１３ｇを添加し、徐々に減圧し、１．３〜２．７ｈＰａ、２３０〜２５０℃で３時間エステル交換反応を行い、芳香族多塩基酸成分５０モル％、数平均分子量２２，０００のポリエステルポリオールを得た。
このポリエステルポリオールを酢酸エチルにて不揮発分５０％に調整し、水酸基価２．４５ｍｇＫＯＨ／ｇ、酸価０．１ｍｇＫＯＨ／ｇのポリエステルポリオール溶液（５）を得た。
(Synthesis Example 5)
Charge 83.2 g of isophthalic acid, 83.2 g of terephthalic acid and 142.6 g of ethylene glycol, conduct esterification reaction at 200 to 220 ° C. for 8 hours, distill a predetermined amount of water, add 188 g of azelaic acid, and add 4 A time esterification reaction was performed. After distilling a predetermined amount of water, 0.13 g of tetraisobutyl titanate was added, the pressure was gradually reduced, and transesterification was carried out at 1.3 to 2.7 hPa and 230 to 250 ° C. for 3 hours. A polyester polyol having a component of 50 mol% and a number average molecular weight of 22,000 was obtained.
This polyester polyol was adjusted to 50% nonvolatile content with ethyl acetate to obtain a polyester polyol solution (5) having a hydroxyl value of 2.45 mgKOH / g and an acid value of 0.1 mgKOH / g.
（合成例６）
イソフタル酸１６６．０ｇ、テレフタル酸１６６．０ｇ、エチレングリコール８５．６ｇ、ネオペンチルグリコール９５．６ｇを仕込み、２００〜２２０℃で６時間エステル化反応を行い、所定量の水の留出後、テトライソブチルチタネート０．１２ｇを添加し徐々に減圧し、１．３〜２．６ｈＰａ、２３０〜２５０℃で３時間エステル交換反応を行い、芳香族多塩基酸成分１００モル％、数平均分子量１５，０００のポリエステルポリオールを得た。
このポリエステルポリオールを酢酸エチルにて不揮発分５０％に調整し、水酸基価３．６４ｍｇＫＯＨ／ｇ、酸価０．１ｍｇＫＯＨ／ｇのポリエステルポリオール溶液（６）を得た。
(Synthesis Example 6)
166.0 g of isophthalic acid, 166.0 g of terephthalic acid, 85.6 g of ethylene glycol, and 95.6 g of neopentyl glycol are charged, and esterification is performed at 200 to 220 ° C. for 6 hours. After distilling a predetermined amount of water, tetra 0.12 g of isobutyl titanate was added and the pressure was gradually reduced, and transesterification was performed at 1.3 to 2.6 hPa and 230 to 250 ° C. for 3 hours. The aromatic polybasic acid component was 100 mol%, and the number average molecular weight was 15,000. The polyester polyol was obtained.
This polyester polyol was adjusted to 50% nonvolatile content with ethyl acetate to obtain a polyester polyol solution (6) having a hydroxyl value of 3.64 mgKOH / g and an acid value of 0.1 mgKOH / g.
（合成例７）
イソフタル酸１３２．８ｇ、エチレングリコール４２．７ｇ、ネオペンチルグリコール７１．８ｇ、１，６−ヘキサンジオール１０８．６ｇを仕込み、２００〜２３０℃で６時間エステル化反応を行い、所定量の水の留出後、アジピン酸１７５．２ｇ加え、更に６時間エステル化反応を行った。所定量の水の留出後、テトライソブチルチタネート０．１３ｇを添加し徐々に減圧し、１．３〜２．６ｈＰａ、２３０〜２５０℃で６時間エステル交換反応を行い、芳香族多塩基酸成分４０モル％、数平均分子量３０，０００のポリエステルポリオールを得た。
このポリエステルポリオールを酢酸エチルにて不揮発分５０％に調整し、水酸基価１．７７ｍｇＫＯＨ／ｇ、酸価０．１ｍｇＫＯＨ／ｇのポリエステルポリオール溶液（７）を得た。
(Synthesis Example 7)
132.8 g of isophthalic acid, 42.7 g of ethylene glycol, 71.8 g of neopentyl glycol, and 108.6 g of 1,6-hexanediol were charged and subjected to esterification reaction at 200 to 230 ° C. for 6 hours. After exiting, 175.2 g of adipic acid was added, and the esterification reaction was further performed for 6 hours. After distilling a predetermined amount of water, 0.13 g of tetraisobutyl titanate is added and the pressure is gradually reduced, and transesterification is carried out at 1.3 to 2.6 hPa and 230 to 250 ° C. for 6 hours to obtain an aromatic polybasic acid component. A polyester polyol having 40 mol% and a number average molecular weight of 30,000 was obtained.
This polyester polyol was adjusted to 50% nonvolatile content with ethyl acetate to obtain a polyester polyol solution (7) having a hydroxyl value of 1.77 mgKOH / g and an acid value of 0.1 mgKOH / g.
［主剤（１）の製造］
ポリエステルポリオール溶液（１）２００ｇ（固形分１００ｇ）と、ＫＢＭ−４０３（シランカップリング剤）１ｇとを配合した後、酢酸エチル２ｇを加え、不揮発分が５０％の主剤（１）を得た。
[Production of main agent (1)]
After blending 200 g of polyester polyol solution (1) (solid content 100 g) and 1 g of KBM-403 (silane coupling agent), 2 g of ethyl acetate was added to obtain a main agent (1) having a nonvolatile content of 50%.
［主剤（２）〜（９）の製造］
主剤（１）の場合と同様にして、ポリエステルポリオール溶液（１）〜（７）並びに下記に示すその他の成分を表１に示す割合（ｇ）で配合した後、不揮発分が５０％となるように酢酸エチルを加えて、主剤（２）〜（９）を得た。
なお、主剤（７）は、ポリエステルポリオール溶液（６）１００ｇ（固形分５０ｇ）とポリエステルポリオール溶液（７）１００ｇ（固形分５０ｇ）とを併用したものである。
[Production of main agents (2) to (9)]
In the same manner as in the case of the main agent (1), the polyester polyol solutions (1) to (7) and the other components shown below are blended in proportions (g) shown in Table 1, and the non-volatile content becomes 50%. Ethyl acetate was added to to obtain main agents (2) to (9).
The main agent (7) is a combination of 100 g of polyester polyol solution (6) (solid content 50 g) and 100 g of polyester polyol solution (7) (solid content 50 g).
＜その他の成分＞
ＫＢＭ−４０３：３−グリシドキシプロピルトリメトキシシラン（信越シリコーン（株）製）
ＫＢＭ−９０３：３−アミノプロピルトリメトキシシラン（信越シリコーン（株）製）
リン酸
<Other ingredients>
KBM-403: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd.)
KBM-903: 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd.)
phosphoric acid
＜硬化剤（１）＞
４，４′−ジフェニルメタンジイソシアネートにトリメチロールプロパンが付加したアダクト体９０重量部と、ヘキサメチレンジイソシアネートのヌレート体１０重量部を混合して、酢酸エチルで希釈して固形分７０％の樹脂溶液としたものを硬化剤（１）とした。硬化剤（１）のＮＣＯ％は１１．１％であった。
＜硬化剤（２）＞
４，４′−ジフェニルメタンジイソシアネートにトリメチロールプロパンが付加したアダクト体７０重量部と、ヘキサメチレンジイソシアネートのヌレート体３０重量部を混合して、酢酸エチルで希釈して固形分７０％の樹脂溶液としたものを硬化剤（１）とした。硬化剤（１）のＮＣＯ％は１２．０％であった。
＜硬化剤（３）＞
４，４′−ジフェニルメタンジイソシアネートにトリメチロールプロパンが付加したアダクト体５０重量部と、ヘキサメチレンジイソシアネートのヌレート体５０重量部を混合して、酢酸エチルで希釈して固形分７０％の樹脂溶液としたものを硬化剤（１）とした。硬化剤（１）のＮＣＯ％は１２．９％であった。
＜硬化剤（４）＞
４，４′−ジフェニルメタンジイソシアネートにトリメチロールプロパンが付加したアダクト体７０重量部と、ヘキサメチレンジイソシアネートのトリメチロールプロパンとのアダクト体３０重量部を混合して、酢酸エチルで希釈して固形分７０％の樹脂溶液としたものを硬化剤（１）とした。硬化剤（１）のＮＣＯ％は１０．９％であった。
＜硬化剤（５）＞
４，４′−ジフェニルメタンジイソシアネートにトリメチロールプロパンが付加したアダクト体７０重量部と、ヘキサメチレンジイソシアネートのビュレット体３０重量部を混合して、酢酸エチルで希釈して固形分７０％の樹脂溶液としたものを硬化剤（１）とした。硬化剤（１）のＮＣＯ％は１２．４％であった。
＜硬化剤（６）＞
４，４′−ジフェニルメタンジイソシアネートにトリメチロールプロパンが付加したアダクト体１００重量部を酢酸エチルで希釈して、固形分７０％の樹脂溶液としたものを硬化剤（１）とした。硬化剤（１）のＮＣＯ％は１０．６％であった。
＜硬化剤（７）＞
４，４′−ジフェニルメタンジイソシアネートにトリメチロールプロパンが付加したアダクト体３０重量部と、ヘキサメチレンジイソシアネートのビュレット体７０重量部を混合して、酢酸エチルで希釈して固形分７０％の樹脂溶液としたものを硬化剤（１）とした。硬化剤（１）のＮＣＯ％は１３．９％であった。
＜硬化剤（８）＞
ヘキサメチレンジイソシアネートのヌレート体１００重量部を酢酸エチルで希釈して、固形分７０％の樹脂溶液としたものを硬化剤（１）とした。硬化剤（１）のＮＣＯ％は１５．３％であった。
＜硬化剤（９）＞
トリレンジイソシアネートにトリメチロールプロパンが付加したアダクト体１００重量部を酢酸エチルで希釈して、固形分７０％の樹脂溶液としたものを硬化剤（１）とした。硬化剤（１）のＮＣＯ％は１２．０％であった。
<Curing agent (1)>
90 parts by weight of an adduct obtained by adding trimethylolpropane to 4,4'-diphenylmethane diisocyanate and 10 parts by weight of a hexamethylene diisocyanate nurate were mixed and diluted with ethyl acetate to obtain a resin solution having a solid content of 70%. This was used as a curing agent (1). The NCO% of the curing agent (1) was 11.1%.
<Curing agent (2)>
70 parts by weight of an adduct obtained by adding trimethylolpropane to 4,4'-diphenylmethane diisocyanate and 30 parts by weight of a hexamethylene diisocyanate nurate were mixed and diluted with ethyl acetate to obtain a resin solution having a solid content of 70%. The thing was made into the hardening | curing agent (1). The NCO% of the curing agent (1) was 12.0%.
<Curing agent (3)>
50 parts by weight of an adduct obtained by adding trimethylolpropane to 4,4'-diphenylmethane diisocyanate and 50 parts by weight of a hexamethylene diisocyanate nurate were mixed and diluted with ethyl acetate to obtain a resin solution having a solid content of 70%. The thing was made into the hardening | curing agent (1). The NCO% of the curing agent (1) was 12.9%.
<Curing agent (4)>
70 parts by weight of an adduct obtained by adding trimethylolpropane to 4,4'-diphenylmethane diisocyanate and 30 parts by weight of an adduct obtained by adding trimethylolpropane of hexamethylene diisocyanate were diluted with ethyl acetate to obtain a solid content of 70%. A resin solution was used as a curing agent (1). The NCO% of the curing agent (1) was 10.9%.
<Curing agent (5)>
70 parts by weight of an adduct obtained by adding trimethylolpropane to 4,4'-diphenylmethane diisocyanate and 30 parts by weight of a burette of hexamethylene diisocyanate were mixed and diluted with ethyl acetate to obtain a resin solution having a solid content of 70%. The thing was made into the hardening | curing agent (1). The NCO% of the curing agent (1) was 12.4%.
<Curing agent (6)>
Curing agent (1) was obtained by diluting 100 parts by weight of an adduct obtained by adding trimethylolpropane to 4,4'-diphenylmethane diisocyanate with ethyl acetate to obtain a resin solution having a solid content of 70%. The NCO% of the curing agent (1) was 10.6%.
<Curing agent (7)>
30 parts by weight of an adduct obtained by adding trimethylolpropane to 4,4'-diphenylmethane diisocyanate and 70 parts by weight of a burette of hexamethylene diisocyanate were mixed and diluted with ethyl acetate to obtain a resin solution having a solid content of 70%. This was used as a curing agent (1). The NCO% of the curing agent (1) was 13.9%.
<Curing agent (8)>
A curing solution (1) was prepared by diluting 100 parts by weight of a hexamethylene diisocyanate nurate with ethyl acetate to obtain a resin solution having a solid content of 70%. The NCO% of the curing agent (1) was 15.3%.
<Curing agent (9)>
A curing agent (1) was prepared by diluting 100 parts by weight of an adduct obtained by adding trimethylolpropane to tolylene diisocyanate with ethyl acetate to obtain a resin solution having a solid content of 70%. The NCO% of the curing agent (1) was 12.0%.
（実施例１〜１４、比較例１〜６、参考例）
各主剤と各硬化剤とを、主剤中に含まれるポリオール（Ａ）由来のヒドロキシル基とカルボキシル基の合計に対する硬化剤中に含まれるイソシアネート基の当量比［ＮＣＯ］／（［ＯＨ］＋［ＣＯＯＨ］）が表３、４に示す値となるように配合した後、不揮発分が３０％となるように酢酸エチルを加えて、外層側用のポリウレタン接着剤を得た。
厚さ４０μｍのアルミニウム箔の一方の面に、塗布型リン酸クロメート処理剤（日本ペイント株式会社製 サーフコートＮＲ−Ｘ）を塗布量：０．１ｇ／平方メートルとなる量で塗布し、２３０℃で焼き付けを行い、処理剤表面上に外層用接着剤として上記ポリウレタン接着剤を塗布量：５ｇ／平方メートルとなる量でドライラミネーターによって塗布し、溶剤を揮散させた後、厚さ３０μｍの延伸ポリアミドフィルムを積層した。
次に、得られた積層フィルムのアルミニウム箔の他方の面に下記内層用接着剤を乾燥後の塗布量：５ｇ／平方メートルとなる量でドライラミネーターによって塗布し、溶剤を揮散させた後、厚さ３０μｍの未延伸ポリプロピレンフィルムを積層し、その後、表３、４記載のエージング温度にて７日間硬化（エージング）を行い、外層用および内層用接着剤を硬化させて電池用包装材を得た。
＊内層用接着剤
ＡＤ−５０２（東洋モートン株式会社製・ポリエステルポリオール）を主剤とし、ＣＡＴ−１０Ｌ（東洋モートン株式会社製・イソシアネート系硬化剤）を重量比で主剤／硬化剤＝１００／１０で配合し、不揮発分が３０％となるように酢酸エチルを加えて内層用接着剤とした。
(Examples 1-14, Comparative Examples 1-6, Reference Example)
Equivalent ratio [NCO] / ([OH] + [COOH) of isocyanate groups contained in the curing agent with respect to the total of hydroxyl groups and carboxyl groups derived from the polyol (A) contained in the main agent ]) Were blended so as to have the values shown in Tables 3 and 4, and then ethyl acetate was added so that the non-volatile content was 30% to obtain a polyurethane adhesive for the outer layer side.
A coating type phosphoric acid chromate treatment agent (Surfcoat NR-X, manufactured by Nippon Paint Co., Ltd.) is applied to one surface of an aluminum foil having a thickness of 40 μm at an amount of 0.1 g / square meter. After baking, the polyurethane adhesive as an outer layer adhesive is applied on the surface of the treatment agent by a dry laminator in an amount of 5 g / m 2, the solvent is stripped, and a stretched polyamide film having a thickness of 30 μm is applied. Laminated.
Next, on the other surface of the aluminum foil of the obtained laminated film, the following inner layer adhesive was applied by a dry laminator in an amount to be applied: 5 g / m 2 after drying, and the solvent was stripped, and then the thickness was increased. A 30 μm unstretched polypropylene film was laminated, then cured (aging) for 7 days at the aging temperatures shown in Tables 3 and 4, and the outer layer and inner layer adhesives were cured to obtain battery packaging materials.
* Adhesive for inner layer AD-502 (manufactured by Toyo Morton Co., Ltd./polyester polyol), and CAT-10L (manufactured by Toyo Morton Co., Ltd./isocyanate curing agent) in weight ratio of main agent / curing agent = 100/10 It mix | blended and ethyl acetate was added so that the non volatile matter might be 30%, and it was set as the adhesive agent for inner layers.
（比較例７）
主剤にＡＤ−５０２（東洋モートン株式会社製・ポリエステルポリオール）を用いて、硬化剤にＣＡＴ−１０（東洋モートン株式会社製・イソシアネート硬化剤）を重量比で主剤／硬化剤＝１００／１０で配合し、不揮発分が３０％となるように酢酸エチルを加えて、ポリウレタン接着剤を得た。
得られたポリウレタン接着剤を外層用接着剤として用いた以外は、上記実施例、上記比較例と同様にして電池用包装材を得た。
(Comparative Example 7)
AD-502 (manufactured by Toyo Morton Co., Ltd., polyester polyol) is used as the main agent, and CAT-10 (manufactured by Toyo Morton Co., Ltd., isocyanate curing agent) is blended in the weight ratio of main agent / curing agent = 100/10. Then, ethyl acetate was added so that the nonvolatile content would be 30% to obtain a polyurethane adhesive.
A battery packaging material was obtained in the same manner as in the above Examples and Comparative Examples except that the obtained polyurethane adhesive was used as an adhesive for the outer layer.
＜１２０℃における貯蔵弾性率＞
離型紙上に乾燥膜厚が約６０μｍとなるように外層側用のポリウレタン接着剤を塗布し、２５℃、１日静置後、表３、４記載のエージング温度にて２週間エージングした後に、離型紙から接着剤層を剥離して試料を得る。試料を幅５ｍｍ、長さ３ｃｍとなるように切り出したサンプル片を動的粘弾性測定装置（ＤＶＡ−２００、アイティー計測制御株式会社製）にチャック間距離が２ｃｍとなるように保持し、昇温速度１０℃／分で−２０℃から２００℃の環境にて、周波数１０Ｈｚの発生応力を計測した。
なお、貯蔵弾性率測定では乾燥膜厚が厚いので、エージング時間を２週間とした。
<Storage elastic modulus at 120 ° C.>
After applying a polyurethane adhesive for the outer layer side on the release paper so that the dry film thickness becomes about 60 μm, after standing at 25 ° C. for 1 day, aging at the aging temperature described in Tables 3 and 4 for 2 weeks, A sample is obtained by peeling the adhesive layer from the release paper. A sample piece cut out to have a width of 5 mm and a length of 3 cm is held in a dynamic viscoelasticity measuring device (DVA-200, manufactured by IT Measurement Control Co., Ltd.) so that the distance between chucks is 2 cm, The generated stress at a frequency of 10 Hz was measured in an environment of −20 ° C. to 200 ° C. at a temperature rate of 10 ° C./min.
In addition, since the dry film thickness was thick in the storage elastic modulus measurement, the aging time was set to 2 weeks.
上記のようにして得られた電池用包装材に対して下記評価法に基づいて性能評価を行った。
＜耐熱接着強度＞
電池用包装材を２００ｍｍ×１５ｍｍの大きさに切断し、温度１２０℃の環境下にて、引張り試験機を用いて荷重速度１００ｍｍ／分で１８０度の剥離試験をおこなった。延伸ポリアミドフィルムとアルミニウム箔間の剥離強度（Ｎ／１５ｍｍ巾）を、それぞれ５個の試験片の平均値で示した。結果を表３、４に示す。
◎：３．５Ｎ以上（実用上優れる）
○：３．０Ｎ以上、３．５Ｎ未満（実用域）
△：２．５Ｎ以上、３．０Ｎ未満（実用下限）
×：２．５Ｎ未満
The battery packaging material obtained as described above was evaluated for performance based on the following evaluation method.
<Heat resistant adhesive strength>
The battery packaging material was cut into a size of 200 mm × 15 mm, and a 180 ° peel test was performed at a load rate of 100 mm / min using a tensile tester in an environment at a temperature of 120 ° C. The peel strength (N / 15 mm width) between the stretched polyamide film and the aluminum foil was shown as an average value of 5 test pieces each. The results are shown in Tables 3 and 4.
A: 3.5 N or more (excellent in practical use)
○: 3.0N or more and less than 3.5N (practical range)
Δ: 2.5N or more and less than 3.0N (practical lower limit)
X: Less than 2.5N
＜変形前・後のヒートシール耐性＞
（変形前のヒートシール耐性）
電池用包装材を６０×６０ｍｍの大きさに切断し、ブランク（被成型材、素材）とした。前記ブランクに対し、延伸ポリアミドフィルムが外側になるようにして、成型高さフリーのストレート金型にて張り出し１段成型を行い、フランジ４面を１９０℃・２ｋｇｆ・３秒ヒートシールした後、アルミニウム箔の破断や、各層間の浮きが発生しない、最大の成型高さにより成型性を評価した。
（変形後のヒートシール耐性）
前記と同様に張り出し１段成型した後に、張り出しコーナー４か所を直接窪ませて、谷折り皺をつけて変形させた後、フランジ４面を１９０℃・２ｋｇｆ・３秒ヒートシールし、アルミニウム箔の破断や、各層間の浮きが発生しない、最大の成型高さにより成型性を評価した。
<Heat seal resistance before and after deformation>
(Heat seal resistance before deformation)
The battery packaging material was cut into a size of 60 × 60 mm to obtain a blank (molded material, material). The blank is stretched with a straight mold with a molding height free so that the stretched polyamide film is on the outside, one-step molding is performed, and the flange 4 surface is heat sealed at 190 ° C., 2 kgf, 3 seconds, and then aluminum. The moldability was evaluated based on the maximum molding height that did not cause the foil to break or float between layers.
(Heat seal resistance after deformation)
After one-step overhanging as described above, the four corners of the overhang are directly recessed, deformed with valley creases, and the flange 4 surface is heat-sealed at 190 ° C., 2 kgf, 3 seconds, aluminum foil The moldability was evaluated based on the maximum molding height at which no breakage of the material or floating between layers occurred.
使用した金型のポンチ形状は、一辺２９．４ｍｍの正方形、コーナーＲ１ｍｍ、ポンチ肩Ｒ１ｍｍ。使用した金型のダイス孔形状は一片３０．０ｍｍの正方形、ダイス孔コーナーＲ２ｍｍ、ダイス孔肩Ｒ：１ｍｍであり、ポンチとダイス孔とのクリアランスは０．３ｍｍ。前記クリアランスにより成型高さに応じた傾斜が発生する。成型の高さに応じて、次の４段階の評価を行なった。 The punch shape of the mold used was a square with a side of 29.4 mm, a corner R1 mm, and a punch shoulder R1 mm. The die hole shape of the mold used was a square of 30.0 mm per piece, a die hole corner R2 mm, a die hole shoulder R: 1 mm, and the clearance between the punch and the die hole was 0.3 mm. An inclination corresponding to the molding height is generated by the clearance. The following four stages of evaluation were performed according to the molding height.
◎：６ｍｍ 以上（実用上優れる）
○：５ｍｍ 以上、６ｍｍ 未満（実用域）
△：３ｍｍ 以上、４ｍｍ 未満（実用下限）
×：３ｍｍ 未満
以上の結果を表３、４に併せて示す。
A: 6 mm or more (excellent in practical use)
○: 5 mm or more and less than 6 mm (practical range)
Δ: 3 mm or more and less than 4 mm (practical lower limit)
X: Less than 3 mm The above results are also shown in Tables 3 and 4.
表３の結果から、特定の数平均分子量と、芳香族多塩基酸成分における特定のモル％を有するポリエステルポリオールを含み、特定のポリイソシアネート成分を含む接着剤を外層側接着剤層に用いる事により、６０℃未満のエージングでも耐熱接着強度、変形前後における成型物のヒートシール耐性に優れる電池用包装材を提供できることが分かる。 From the results in Table 3, by using a polyester polyol having a specific number average molecular weight and a specific mol% in the aromatic polybasic acid component, and using an adhesive containing a specific polyisocyanate component for the outer layer side adhesive layer It can be seen that a battery packaging material excellent in heat-resistant adhesive strength and heat-seal resistance of a molded product before and after deformation can be provided even with aging of less than 60 ° C.
比較例１は、芳香族多塩基酸成分の含有率の多すぎる多塩基酸成分と、多価アルコールとの反応生成物であるポリオール成分（Ａ）を用いるので、塗膜が脆くなり過ぎて変形ヒートシール耐性が低下する。一方、比較例２は、芳香族多塩基酸成分の含有率の少なすぎる多塩基酸成分と、多価アルコールとの反応生成物であるポリオール成分（Ａ）を用いるので、耐熱接着性が低下する。
比較例３は、ポリイソシアネート成分（Ｂ）中にヘキサメチレンジイソシアネートの多官能誘導体が含まれない為、柔軟性が低下し、変形ヒートシール耐性が低下する。一方、比較例４は、ポリイソシアネート成分（Ｂ）中のジフェニルメタンジイソシアネートのアダクト体が少な過ぎ、比較例５はジフェニルメタンジイソシアネートのアダクト体が含まれていないので、１２０℃の貯蔵弾性率が低下し、ヒートシール耐性も低下する。
また、ポリイソシアネート成分（Ｂ）としてトリレンジイソシアネートを用いる場合、参考例に示すように６０℃、７日エージングでは硬化が完全に完了するため、１２０℃貯蔵弾性率が大きくなり、耐熱性が向上する。しかし、４０℃、７日エージングでは、硬化前ないし硬化途中の接着剤層が軟化しにくく、イソシアネートの活性度も低下する為、硬化不十分となり耐熱性が低下する。
Since the comparative example 1 uses the polyol component (A) which is a reaction product of the polybasic acid component having too much content of the aromatic polybasic acid component and the polyhydric alcohol, the coating film becomes too brittle and deformed. Heat seal resistance decreases. On the other hand, since the comparative example 2 uses the polyol component (A) which is a reaction product of a polybasic acid component having a too low content of the aromatic polybasic acid component and a polyhydric alcohol, the heat resistant adhesiveness is lowered. .
In Comparative Example 3, since the polyisocyanate component (B) does not contain a polyfunctional derivative of hexamethylene diisocyanate, flexibility is lowered and deformation heat seal resistance is lowered. On the other hand, Comparative Example 4 has too little adduct of diphenylmethane diisocyanate in polyisocyanate component (B), and Comparative Example 5 does not contain an adduct of diphenylmethane diisocyanate, so the storage elastic modulus at 120 ° C. is reduced, Heat seal resistance is also reduced.
Also, when tolylene diisocyanate is used as the polyisocyanate component (B), as shown in the reference example, curing is completely completed by aging at 60 ° C. for 7 days, so that the storage elastic modulus increases at 120 ° C. and heat resistance is improved. To do. However, with aging at 40 ° C. for 7 days, the adhesive layer before curing or during curing is difficult to soften, and the activity of the isocyanate also decreases, resulting in insufficient curing and reduced heat resistance.
本発明に係る電池用包装材は、成型性に優れ、環境耐性が高い。従って、ＰＴＰ包装や鋼板などの成型性を要する積層物や、防壁材、屋根材、太陽電池パネル材、窓材、屋外フローリング材、照明保護材、自動車部材などの建造物など屋外産業用途向けの積層体としても使用できる。 The battery packaging material according to the present invention has excellent moldability and high environmental resistance. Therefore, it is suitable for outdoor industrial applications such as laminates that require moldability, such as PTP packaging and steel plates, and building materials such as barrier materials, roofing materials, solar panel materials, window materials, outdoor flooring materials, lighting protection materials, and automobile members. It can also be used as a laminate.
（１１）：外層側樹脂フィルム層
（１２）：外層側接着剤層
（１３）：金属箔層
（１４）：内層側接着剤層
（１５）ヒートシール層
(11): Outer layer side resin film layer (12): Outer layer side adhesive layer (13): Metal foil layer (14): Inner layer side adhesive layer (15) Heat seal layer
Claims (5)
前記外層側接着剤層（１２）が、ポリオール成分（Ａ）とポリイソシアネート成分（Ｂ）との硬化物であり、
前記ポリオール成分（Ａ）が、多塩基酸成分１００モル％中、芳香族多塩基酸成分を４５〜９５モル％含む多塩基酸成分と、多価アルコール成分との反応生成物であって、数平均分子量１００００〜４００００のポリエステルポリオールであるか、
もしくは
多塩基酸成分（１）と多価アルコール成分（１）との反応生成物（１）、および多塩基酸成分（２）と多価アルコール成分（２）との反応生成物（２）の混合物であって、前記多塩基酸成分（１）と前記多塩基酸成分（２）との合計１００モル％中、芳香族多塩基酸成分を４５〜９５モル％含み、前記混合物の数平均分子量１００００〜４００００のポリエステルポリオールであり、
前記ポリイソシアネート成分（Ｂ）が、ジフェニルメタンジイソシアネートに３官能アルコールが付加したアダクト体と、ヘキサメチレンジイソシアネートの多官能誘導体とを含み、イソシアネート基１００モル％中、ジフェニルメタンジイソシアネート由来のイソシアネート基が４０〜９０モル％である、ことを特徴とする電池用包装材。 Battery packaging material in which outer layer side resin film layer (11), outer layer side adhesive layer (12), metal foil layer (13), inner layer side adhesive layer (14) and heat seal layer (15) are sequentially laminated. In
The outer layer side adhesive layer (12) is a cured product of the polyol component (A) and the polyisocyanate component (B),
The polyol component (A) is a reaction product of a polybasic acid component containing 45 to 95 mol% of an aromatic polybasic acid component in 100 mol% of the polybasic acid component and a polyhydric alcohol component, A polyester polyol having an average molecular weight of 10,000 to 40,000,
Or the reaction product (1) of the polybasic acid component (1) and the polyhydric alcohol component (1), and the reaction product (2) of the polybasic acid component (2) and the polyhydric alcohol component (2). A mixture comprising 45 to 95 mol% of an aromatic polybasic acid component in a total of 100 mol% of the polybasic acid component (1) and the polybasic acid component (2), and the number average molecular weight of the mixture A polyester polyol of 10,000 to 40,000,
The polyisocyanate component (B) includes an adduct obtained by adding a trifunctional alcohol to diphenylmethane diisocyanate and a polyfunctional derivative of hexamethylene diisocyanate, and the isocyanate group derived from diphenylmethane diisocyanate is 40 to 90 in 100 mol% of the isocyanate groups. A packaging material for batteries, characterized in that it is mol%.
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| JP2023006642A (en) * | 2021-06-30 | 2023-01-18 | 東洋インキＳｃホールディングス株式会社 | Packaging material for power storage device, container for power storage device and power storage device |
| JP7112573B1 (en) | 2021-07-21 | 2022-08-03 | 大日精化工業株式会社 | Moisture curable polyurethane hot melt adhesive |
| WO2023002992A1 (en) * | 2021-07-21 | 2023-01-26 | 大日精化工業株式会社 | Moisture-curable polyurethane hot-melt adhesive |
| JP2023016602A (en) * | 2021-07-21 | 2023-02-02 | 大日精化工業株式会社 | Moisture-curable polyurethane hot melt adhesive |
| CN117651749A (en) * | 2021-07-21 | 2024-03-05 | 大日精化工业株式会社 | Moisture-curable polyurethane hot-melt adhesive |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6323476B2 (en) | 2018-05-16 |
| TWI728056B (en) | 2021-05-21 |
| CN107129785B (en) | 2021-04-20 |
| TW201731143A (en) | 2017-09-01 |
| KR20170101122A (en) | 2017-09-05 |
| KR102668250B1 (en) | 2024-05-23 |
| CN107129785A (en) | 2017-09-05 |
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