JP2013155282A - Resin composition, adhesive for two-component laminate, laminated film, and backsheet of solar cell - Google Patents
Resin composition, adhesive for two-component laminate, laminated film, and backsheet of solar cell Download PDFInfo
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- JP2013155282A JP2013155282A JP2012016502A JP2012016502A JP2013155282A JP 2013155282 A JP2013155282 A JP 2013155282A JP 2012016502 A JP2012016502 A JP 2012016502A JP 2012016502 A JP2012016502 A JP 2012016502A JP 2013155282 A JP2013155282 A JP 2013155282A
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- mass
- resin composition
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- 239000011342 resin composition Substances 0.000 title claims abstract description 56
- 239000000853 adhesive Substances 0.000 title claims abstract description 31
- 230000001070 adhesive effect Effects 0.000 title abstract description 29
- 239000002253 acid Substances 0.000 claims abstract description 97
- 150000003077 polyols Chemical class 0.000 claims abstract description 80
- 229920005862 polyol Polymers 0.000 claims abstract description 56
- 229920000728 polyester Polymers 0.000 claims abstract description 55
- 239000004814 polyurethane Substances 0.000 claims abstract description 54
- 229920002635 polyurethane Polymers 0.000 claims abstract description 54
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 49
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 34
- 150000007519 polyprotic acids Polymers 0.000 claims abstract description 30
- 239000003822 epoxy resin Substances 0.000 claims abstract description 26
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 26
- -1 diol compound Chemical class 0.000 claims abstract description 24
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 18
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 18
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 16
- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 239000004135 Bone phosphate Substances 0.000 claims description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 23
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 17
- 239000012939 laminating adhesive Substances 0.000 claims description 14
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 14
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000009826 distribution Methods 0.000 claims description 9
- 229930185605 Bisphenol Natural products 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 230000000447 dimerizing effect Effects 0.000 claims description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- 229920006267 polyester film Polymers 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 239000011888 foil Substances 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000007787 solid Substances 0.000 description 24
- 239000000203 mixture Substances 0.000 description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 20
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 14
- 238000011156 evaluation Methods 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 239000000758 substrate Substances 0.000 description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 9
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 9
- 239000005058 Isophorone diisocyanate Substances 0.000 description 8
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 8
- 239000001361 adipic acid Substances 0.000 description 7
- 235000011037 adipic acid Nutrition 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000012948 isocyanate Substances 0.000 description 7
- 150000002513 isocyanates Chemical class 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 235000013305 food Nutrition 0.000 description 6
- 150000003609 titanium compounds Chemical class 0.000 description 6
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 5
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 5
- 229920000515 polycarbonate Polymers 0.000 description 5
- 239000004417 polycarbonate Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 150000005846 sugar alcohols Polymers 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 125000005442 diisocyanate group Chemical group 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- 229920005906 polyester polyol Polymers 0.000 description 4
- 229920002620 polyvinyl fluoride Polymers 0.000 description 4
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 4
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WWZKQHOCKIZLMA-UHFFFAOYSA-N Caprylic acid Natural products CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder 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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 3
- 239000013638 trimer Substances 0.000 description 3
- YWWVWXASSLXJHU-AATRIKPKSA-N (9E)-tetradecenoic acid Chemical compound CCCC\C=C\CCCCCCCC(O)=O YWWVWXASSLXJHU-AATRIKPKSA-N 0.000 description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 2
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- YWWVWXASSLXJHU-UHFFFAOYSA-N 9E-tetradecenoic acid Natural products CCCCC=CCCCCCCCC(O)=O YWWVWXASSLXJHU-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
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- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- BTZVDPWKGXMQFW-UHFFFAOYSA-N Pentadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCC(O)=O BTZVDPWKGXMQFW-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
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Landscapes
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
本発明は、湿熱条件下での基材接着性に優れる樹脂組成物、２液型ラミネート用接着剤、積層フィルム及び太陽電池のバックシートに関する。 The present invention relates to a resin composition excellent in substrate adhesion under wet heat conditions, a two-component laminating adhesive, a laminated film, and a solar cell backsheet.
近年、クリーンエネルギーの代表として太陽光発電が注目されている。太陽電池モジュールの最背面に設置されるバックシートは、セルや配線などの発電機構を外部環境から保護して絶縁性を保つための部材であり、各種の機能性フィルムを接着剤で貼り合せた積層体で成る。このようなバックシートに用いられる接着剤には、ポリエステルフィルムやポリフッ化ビニルフィルム等の異なる特徴を有する種々のフィルムに対する高い接着性や、露天環境下でも長期的に接着性を維持するための耐湿熱性が高いレベルで要求される。 In recent years, photovoltaic power generation has attracted attention as a representative of clean energy. The back sheet installed on the back of the solar cell module is a member for protecting the power generation mechanism such as cells and wiring from the external environment and maintaining insulation, and various functional films are bonded together with adhesives. It consists of a laminate. Adhesives used for such backsheets include high adhesion to various films with different characteristics, such as polyester film and polyvinyl fluoride film, and moisture resistance to maintain long-term adhesion even in open-air environments. A high level of heat is required.
このようなバックシート用接着剤としては、ネオペンチルグリコール、１，６−へキサンジオール、エチレングリコール、イソフタル酸、及びセバシン酸を反応させてなるポリエステルポリオールと、イソホロンジイソシアネートとを反応させて得られるポリエステルポリウレタンポリオールを主剤とし、イソホロンジイソシアネートの三量体を硬化剤として用いた二液型のポリウレタン系接着剤が知られている（特許文献１参照）。しかしながら、特許文献１に記載のポリエステルポリウレタンポリオールは、そのポリエステル構成成分がいずれも、比較的低分子量の多塩基酸及び多官能ポリオールであるため、分子構造中に親水性の高いエステル結合部位が多く導入されてしまう結果、これを含有する接着剤は、湿熱条件下ではその硬化物が膨潤してしまい、基材接着性に劣るものであった。 Such an adhesive for backsheet is obtained by reacting a polyester polyol obtained by reacting neopentyl glycol, 1,6-hexanediol, ethylene glycol, isophthalic acid and sebacic acid with isophorone diisocyanate. A two-component polyurethane adhesive using a polyester polyurethane polyol as a main agent and a trimer of isophorone diisocyanate as a curing agent is known (see Patent Document 1). However, since the polyester polyurethane polyol described in Patent Document 1 is a polybasic acid and a polyfunctional polyol having a relatively low molecular weight, the polyester component has many ester bond sites with high hydrophilicity in the molecular structure. As a result of being introduced, the cured product of the adhesive containing this was swelled under wet heat conditions, and the substrate adhesiveness was poor.
従って、本発明が解決しようとする課題は、湿熱条件下での基材接着性に優れる樹脂組成物、該樹脂組成物を含有してなる２液型ラミネート用接着剤、該接着剤からなる層を有する積層フィルム及び太陽電池のバックシートを提供することにある。 Therefore, the problem to be solved by the present invention is a resin composition excellent in substrate adhesion under wet heat conditions, a two-component laminating adhesive containing the resin composition, and a layer comprising the adhesive It is providing the laminated sheet and solar cell backsheet which have these.
本発明者らは上記課題を解決すべく鋭意検討を重ねた結果、ポリエステルポリウレタンポリオールとポリイソシアネート化合物とを含有する樹脂組成物において、該ポリエステルポリウレタンポリオールが、炭素原子数が１４〜４６の範囲である炭化水素基を主骨格とする二塩基酸（Ｅ１）を含む多塩基酸（Ｅ）と、ジオール化合物（Ｆ）と、ジイソシアネート化合物（Ｇ）とを必須の成分として反応させて得られものであることにより、これを用いてなる２液型ラミネート用接着剤は湿熱条件下での基材接着性に優れることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that in a resin composition containing a polyester polyurethane polyol and a polyisocyanate compound, the polyester polyurethane polyol has a carbon atom number in the range of 14 to 46. It is obtained by reacting a polybasic acid (E) containing a dibasic acid (E1) having a hydrocarbon group as a main skeleton, a diol compound (F), and a diisocyanate compound (G) as essential components. As a result, it was found that a two-component laminating adhesive using the same has excellent substrate adhesion under wet heat conditions, and the present invention has been completed.
即ち、本発明は、炭素原子数が１４〜４６の範囲である炭化水素基を主骨格とする二塩基酸（Ｅ１）を含む多塩基酸（Ｅ）と、ジオール化合物（Ｆ）と、ジイソシアネート化合物（Ｇ）とを必須の成分として反応させて得られるポリエステルポリウレタンポリオール（Ａ）と、
ビスフェノール型エポキシ樹脂（Ｂ）と、
ポリカーボネート樹脂（Ｃ）と、
ポリイソシアネート化合物（Ｄ）とを必須の成分として含有する樹脂組成物に関する。
That is, the present invention relates to a polybasic acid (E) containing a dibasic acid (E1) whose main skeleton is a hydrocarbon group having 14 to 46 carbon atoms, a diol compound (F), and a diisocyanate compound. Polyester polyurethane polyol (A) obtained by reacting (G) as an essential component;
A bisphenol type epoxy resin (B);
Polycarbonate resin (C);
The present invention relates to a resin composition containing a polyisocyanate compound (D) as an essential component.
本発明は、更に、前記樹脂組成物を含む２液型ラミネート用接着剤に関する。 The present invention further relates to a two-component laminating adhesive containing the resin composition.
本発明は、更に、前記２液型ラミネート用接着剤からなる層を有する積層フィルムに関する。 The present invention further relates to a laminated film having a layer made of the two-component laminating adhesive.
本発明は、更に、前記２液型ラミネート用接着剤からなる層を有する太陽電池用バックシートに関する。 The present invention further relates to a solar cell backsheet having a layer comprising the two-component laminating adhesive.
本発明によれば、従来の２液型ラミネート用接着剤と比較して、湿熱条件下での基材接着性に優れる２液型ラミネート用接着剤を得ることが出来る。 According to the present invention, it is possible to obtain a two-component laminating adhesive that is superior in substrate adhesiveness under wet heat conditions as compared with a conventional two-component laminating adhesive.
本発明の樹脂組成物は、炭素原子数が１４〜４６の範囲である炭化水素基を主骨格とする二塩基酸（Ｅ１）を含む多塩基酸（Ｅ）と、ジオール化合物（Ｆ）と、ジイソシアネート化合物（Ｇ）とを必須の成分として反応させて得られるポリエステルポリウレタンポリオール（Ａ）を必須の成分として含有する。 The resin composition of the present invention comprises a polybasic acid (E) containing a dibasic acid (E1) having a main skeleton of a hydrocarbon group having 14 to 46 carbon atoms, a diol compound (F), The polyester polyurethane polyol (A) obtained by reacting the diisocyanate compound (G) as an essential component is contained as an essential component.
前記ポリエステルポリウレタンポリオール（Ａ）は、炭素原子数が１４〜４６の範囲である炭化水素基を主骨格とする二塩基酸（Ｅ１）を必須の原料成分として用いることにより、エステル結合部位が少なく、疎水性の高い分子構造とすることができる。このようなポリエステルポリウレタンポリオール（Ａ）を含有する樹脂組成物は、湿熱条件下であっても膨潤せず、高い基材接着性を維持することができる。前記二塩基酸（Ｅ１）を構成する炭化水素基の炭素原子数が１４未満の場合には、ポリエステルポリウレタンポリオール（Ａ）の疎水性が低下し、湿熱条件下での接着性も低下する。また、炭素原子数が４６を超える場合には、ポリエステルポリウレタンポリオール（Ａ）の構造が柔軟になりすぎるため、塗膜強度が低下する。中でも、湿熱条件下での接着性に優れ、かつ、高強度の塗膜が得られる接着剤となることから、炭素原子数が２２〜４２の範囲である炭化水素基を主骨格とする二塩基酸がより好ましく、炭素原子数が２８〜３８の範囲である炭化水素基を主骨格とする二塩基酸が特に好ましい。 The polyester polyurethane polyol (A) has few ester bond sites by using, as an essential raw material component, a dibasic acid (E1) whose main skeleton is a hydrocarbon group having 14 to 46 carbon atoms, The molecular structure can be highly hydrophobic. The resin composition containing such a polyester polyurethane polyol (A) does not swell even under wet heat conditions, and can maintain high substrate adhesion. When the number of carbon atoms of the hydrocarbon group constituting the dibasic acid (E1) is less than 14, the hydrophobicity of the polyester polyurethane polyol (A) is lowered, and the adhesiveness under wet heat conditions is also lowered. On the other hand, when the number of carbon atoms exceeds 46, the structure of the polyester polyurethane polyol (A) becomes too flexible, and the coating film strength decreases. Among them, a dibasic base having a hydrocarbon group having a carbon atom number in the range of 22 to 42 as a main skeleton because it is an adhesive that has excellent adhesiveness under wet heat conditions and provides a high-strength coating film. An acid is more preferable, and a dibasic acid having a main skeleton of a hydrocarbon group having 28 to 38 carbon atoms is particularly preferable.
前記二塩基酸（Ｅ１）は、その主骨格が、炭素原子数が１４〜４６の範囲であるものであれば特に限定されないが、例えば、炭素原子数が８〜２４の範囲である不飽和脂肪酸を二量化させて得られる二塩基酸が挙げられる。該炭素原子数が８〜２４の範囲である不飽和脂肪酸を二量化させて得られる二塩基酸は、高い基材接着強度を有し、湿熱条件下でも接着力が低下しない、耐湿熱性に優れる接着剤が得られることから好ましい。 The dibasic acid (E1) is not particularly limited as long as the main skeleton thereof is in the range of 14 to 46 carbon atoms. For example, the unsaturated fatty acid in the range of 8 to 24 carbon atoms. The dibasic acid obtained by dimerizing can be mentioned. A dibasic acid obtained by dimerizing an unsaturated fatty acid having 8 to 24 carbon atoms has a high base material adhesive strength, and does not decrease the adhesive strength even under wet heat conditions, and is excellent in wet heat resistance. It is preferable because an adhesive is obtained.
前記不飽和脂肪酸は、例えば、オクテン酸、ノネン酸、デセン酸（慣用名：カプロレイン酸）、ウンデセン酸、ドデセン酸（慣用名：リンデル酸、トウハク酸、ラウロレイン酸）、トリデセン酸、テトラデセン酸（慣用名：ミリストレイン酸）、ペンタデセン酸、ヘキサデセン酸（慣用名：パルミトレイン酸）、ヘプタデセン酸（炭素原子数１７）、オクタデセン酸（慣用名：ペトロセリン酸、オレイン酸、エライジン酸、バセニン酸）、ノナデセン酸、エイコセン酸（炭素原子数２０）、ドコセン酸（炭素原子数２２）、セラコレイン酸（炭素原子数２４）等のモノ不飽和脂肪酸；オクタデカジエン酸（慣用名：リノール酸、リノエライジン酸）等のジ不飽和脂肪酸；オクタデカトリエン酸（慣用名：エレオステアリン酸、リノレン酸、パリナリン酸）等のトリ不飽和脂肪酸；これら不飽和脂肪酸の混合物であるトール油脂肪酸、大豆油脂肪酸、パーム油脂肪酸、亜麻仁油脂肪酸、米糠油脂肪酸、綿実油脂肪酸等が挙げられる。これらはそれぞれ単独で用いても良いし、二種類以上を併用しても良い。 Examples of the unsaturated fatty acid include octenoic acid, nonenoic acid, decenoic acid (common name: caproleic acid), undecenoic acid, dodecenoic acid (common names: Linderic acid, succinic acid, lauroleic acid), tridecenoic acid, tetradecenoic acid (commonly used) Name: myristoleic acid), pentadecenoic acid, hexadecenoic acid (common name: palmitoleic acid), heptadecenoic acid (17 carbon atoms), octadecenoic acid (common names: petroceric acid, oleic acid, elaidic acid, basenic acid), nonadecenoic acid Monounsaturated fatty acids such as eicosenoic acid (20 carbon atoms), docosenoic acid (22 carbon atoms), ceracoleic acid (24 carbon atoms); octadecadienoic acid (common names: linoleic acid, linoelaidic acid), etc. Di-unsaturated fatty acids; octadecatrienoic acid (common names: eleostearic acid, linolenic acid, Nalin acid) tri-unsaturated fatty acids, such as, tall oil fatty acid mixtures of these unsaturated fatty acids, soybean oil fatty acid, palm oil fatty acid, linseed oil fatty acid, rice bran oil fatty acids, cottonseed oil fatty acids. These may be used alone or in combination of two or more.
このうち、前記二塩基酸（Ｅ１）のより好ましいものとして記載した前記炭素原子数が２２〜４２の範囲である炭化水素基を主骨格とする二塩基酸は、炭素原子数が１２〜２２の範囲である不飽和脂肪酸を用いることにより得ることができる。また、前記二塩基酸（Ｅ１）の特に好ましいものとして記載した前記炭素原子数が２８〜３８の範囲である炭化水素基を主骨格とする二塩基酸は、炭素原子数が１５〜２０の範囲である二塩基酸を用いることにより得ることができる。 Among these, the dibasic acid having a main skeleton of a hydrocarbon group having a carbon number in the range of 22 to 42 described as a more preferable one of the dibasic acid (E1) has a carbon number of 12 to 22. It can be obtained by using an unsaturated fatty acid in the range. The dibasic acid having a main skeleton of a hydrocarbon group having 28 to 38 carbon atoms described as a particularly preferable dibasic acid (E1) has 15 to 20 carbon atoms. It can obtain by using the dibasic acid which is.
また、前記二塩基酸（Ｅ１）は、より耐水性に優れる樹脂組成物が得られる点で、その一部乃至全部が分子構造中に環構造を有するものであることが好ましい。 The dibasic acid (E1) preferably has a ring structure in part or all of its molecular structure in that a resin composition with better water resistance can be obtained.
前記ポリエステルポリウレタンポリオール（Ａ）の原料である多塩基酸（Ｅ）は、前記二塩基酸（Ｅ１）の他、炭素原子数が２１〜６９の範囲である炭化水素基を主骨格とする三塩基酸（Ｅ２）や、二塩基酸（Ｅ１）又は三塩基酸（Ｅ２）以外の多塩基酸（Ｅ３）、一塩基酸（Ｅ４）を含有していても良い。 The polybasic acid (E) which is a raw material of the polyester polyurethane polyol (A) is a tribasic main chain having a hydrocarbon group having 21 to 69 carbon atoms in addition to the dibasic acid (E1). It may contain acid (E2), polybasic acid (E3) other than dibasic acid (E1) or tribasic acid (E2), or monobasic acid (E4).
多塩基酸（Ｅ）が三塩基酸（Ｅ２）、多塩基酸（Ｅ３）又は一塩基酸（Ｅ４）を含有する場合、湿熱条件下での接着強度及び塗膜強度に優れる樹脂組成物が得られることから、多塩基酸（Ｅ）１００質量部中に占める前記二塩基酸（Ｅ１）の割合が５〜４０質量部の範囲であることが好ましく、７〜３６質量部であることがより好ましく、１０〜３２質量部の範囲であることが特に好ましい。 When the polybasic acid (E) contains a tribasic acid (E2), a polybasic acid (E3) or a monobasic acid (E4), a resin composition excellent in adhesive strength and coating film strength under wet heat conditions is obtained. Therefore, the proportion of the dibasic acid (E1) in 100 parts by mass of the polybasic acid (E) is preferably in the range of 5 to 40 parts by mass, more preferably 7 to 36 parts by mass. The range of 10 to 32 parts by mass is particularly preferable.
前記三塩基酸（Ｅ２）は、炭素原子数が２１〜６９の範囲である炭化水素基を主骨格とするものであることにより、湿熱条件下での接着性と、塗膜強度とに優れる樹脂組成物が得られる。中でも、炭素原子数が３３〜６３の範囲である炭化水素基を主骨格とする三塩基酸が好ましく、炭素原子数が４２〜５７の範囲である炭化水素基を主骨格とする三塩基酸が特に好ましい。 The tribasic acid (E2) is a resin that has a hydrocarbon group having 21 to 69 carbon atoms as a main skeleton, and thus has excellent adhesion under wet heat conditions and coating strength. A composition is obtained. Among these, a tribasic acid having a main skeleton of a hydrocarbon group having 33 to 63 carbon atoms is preferable, and a tribasic acid having a main skeleton of a hydrocarbon group having 42 to 57 carbon atoms is preferable. Particularly preferred.
前記三塩基酸（Ｅ２）は、その主骨格が、炭素原子数が２１〜６９の範囲であるものであれば特に限定されないが、例えば、炭素原子数が８〜２４の範囲である不飽和脂肪酸を三量化させて得られる三塩基酸が挙げられる。該炭素原子数が８〜２４の範囲である不飽和脂肪酸を三量化させて得られる三塩基酸は、高い基材接着強度を有し、湿熱条件下でも接着力が低下しない、耐湿熱性に優れる接着剤が得られることから好ましい。この場合、三塩基酸（Ｅ２）の原料となる不飽和脂肪酸は、前記二塩基酸（Ｅ１）の原料として挙げた各種の不飽和脂肪酸が挙げられる。 The tribasic acid (E2) is not particularly limited as long as its main skeleton is in the range of 21 to 69 carbon atoms. For example, the unsaturated fatty acid in the range of 8 to 24 carbon atoms. The tribasic acid obtained by trimerizing can be mentioned. The tribasic acid obtained by trimerizing the unsaturated fatty acid having 8 to 24 carbon atoms has a high base material adhesive strength and does not decrease the adhesive strength even under wet heat conditions, and has excellent wet heat resistance. It is preferable because an adhesive is obtained. In this case, the unsaturated fatty acid used as the raw material of the tribasic acid (E2) includes various unsaturated fatty acids mentioned as the raw material of the dibasic acid (E1).
このうち、前記二塩基酸（Ｅ２）のより好ましいものとして記載した前記炭素原子数が３３〜６３の範囲である炭化水素基を主骨格とする二塩基酸は、炭素原子数が１２〜２２の範囲である不飽和脂肪酸を用いることにより得ることができる。また、前記二塩基酸（Ｅ２）の特に好ましいものとして記載した前記炭素原子数が４２〜５７の範囲である炭化水素基を主骨格とする二塩基酸は、炭素原子数が１５〜２０の範囲である二塩基酸を用いることにより得ることができる。 Among these, the dibasic acid having a main skeleton of a hydrocarbon group having a carbon number in the range of 33 to 63 described as a more preferable one of the dibasic acid (E2) has 12 to 22 carbon atoms. It can be obtained by using an unsaturated fatty acid in the range. The dibasic acid having a main skeleton of a hydrocarbon group having a carbon atom number in the range of 42 to 57 described as a particularly preferable dibasic acid (E2) has a carbon atom number in the range of 15 to 20. It can obtain by using the dibasic acid which is.
また、前記三塩基酸（Ｅ２）は、より耐水性に優れる樹脂組成物が得られる点で、その一部乃至全部が分子構造中に環構造を有するものであることが好ましい。 The tribasic acid (E2) preferably has a ring structure in part or all of its molecular structure in that a resin composition with better water resistance can be obtained.
前記二塩基酸（Ｅ１）又は三塩基酸（Ｅ２）以外の多塩基酸（Ｅ３）は、例えば、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ウンデカン二酸、ドデカン二酸、トリデカン二酸、テトラデカン二酸、ペンタデカン二酸等の炭素原子数が４〜１５の範囲である脂肪族二塩基酸；テトラヒドロフタル酸、マレイン酸、無水マレイン酸、フマル酸、シトラコン酸、イタコン酸、グルタコン酸等の炭素原子数が４〜１５の範囲である脂肪族不飽和二塩基酸及びその無水物；ヘキサヒドロフタル酸、１，４−シクロヘキサンジカルボン酸等の炭素原子数が４〜１５の範囲である脂環族二塩基酸；フタル酸、無水フタル酸、テレフタル酸、イソフタル酸、オルソフタル酸等の炭素原子数が４〜１５の範囲である芳香族二塩基酸及びその無水物；１，２，５−ヘキサントリカルボン酸、１，２，４−シクロヘキサントリカルボン酸等の炭素原子数が４〜１５の範囲である脂肪族三塩基酸；トリメリット酸、無水トリメリット酸、１，２，５−ベンゼントリカルボン酸、２，５，７−ナフタレントリカルボン酸等の炭素原子数が４〜１５の範囲である芳香族三塩基酸及びその無水物などが挙げられる。これらはそれぞれ単独で用いても良いし、二種類以上を併用しても良い。 Examples of the polybasic acid (E3) other than the dibasic acid (E1) or the tribasic acid (E2) include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, Aliphatic dibasic acids having 4 to 15 carbon atoms such as undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid; tetrahydrophthalic acid, maleic acid, maleic anhydride, fumarate Aliphatic unsaturated dibasic acid having 4 to 15 carbon atoms such as acid, citraconic acid, itaconic acid and glutaconic acid and anhydride thereof; carbon such as hexahydrophthalic acid and 1,4-cyclohexanedicarboxylic acid Alicyclic dibasic acid having 4 to 15 atoms; phthalic acid, phthalic anhydride, terephthalic acid, isophthalic acid, orthophthalic acid, etc. having 4 to 1 carbon atoms An aromatic dibasic acid and its anhydride; 1,3,5-hexanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, etc., an aliphatic tribasic having 4 to 15 carbon atoms Acid; aromatic tribasic acid having 4 to 15 carbon atoms such as trimellitic acid, trimellitic anhydride, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, and the like An anhydride etc. are mentioned. These may be used alone or in combination of two or more.
前記多塩基酸（Ｅ３）の中でも、湿熱条件下での基材接着性に優れる樹脂組成物が得られる点で、脂肪族多塩基酸と、芳香族多塩基酸とを併用することが好ましい。また、湿熱条件下での基材接着性により優れる樹脂組成物となる点で、前記脂肪族多塩基酸は、スベリン酸、アゼライン酸、セバシン酸、ウンデカン二酸、ドデカン二酸、トリデカン二酸、１，２，５−ヘキサントリカルボン酸、１，２，４−シクロヘキサントリカルボン酸等、炭素原子数が８〜１３の範囲であるものが好ましい。 Among the polybasic acids (E3), it is preferable to use an aliphatic polybasic acid and an aromatic polybasic acid in combination in that a resin composition having excellent substrate adhesion under wet heat conditions can be obtained. In addition, the aliphatic polybasic acid is suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, in that it becomes a resin composition that is more excellent in substrate adhesion under wet heat conditions. Those having 8 to 13 carbon atoms are preferred, such as 1,2,5-hexanetricarboxylic acid and 1,2,4-cyclohexanetricarboxylic acid.
前記一塩基酸（Ｅ４）は、例えば、前記二塩基酸（Ｅ１）の原料として挙げた各種の不飽和脂肪酸や、メタン酸、エタン酸、プロパン酸、ブタン酸、ペンタン酸、ヘキサン酸、ヘプタン酸、オクタン酸、ノナン酸、デカン酸、ドデカン酸、テトラデカン酸、ヘキサデカン酸、ヘプタデカン酸、オクタデカン酸、安息香酸等が挙げられる。これらはそれぞれ単独で用いても良いし、二種類以上を併用しても良い。 The monobasic acid (E4) is, for example, various unsaturated fatty acids mentioned as raw materials for the dibasic acid (E1), methanoic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid. , Octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, benzoic acid and the like. These may be used alone or in combination of two or more.
本願発明の多塩基酸（Ｅ）は、前記二塩基酸（Ｅ１）と合わせて前記三塩基酸（Ｅ２）を含有することが好ましい。ポリエスエルポリウレタンポリオール（Ａ）の原料として前記三塩基酸（Ｅ２）を用いることにより分子内に分岐構造が導入され、これにより、得られる接着剤の湿熱条件下での接着性をより高めることができる。 The polybasic acid (E) of the present invention preferably contains the tribasic acid (E2) together with the dibasic acid (E1). By using the tribasic acid (E2) as a raw material for the polyester polyurethane polyol (A), a branched structure is introduced into the molecule, thereby further improving the adhesiveness of the resulting adhesive under wet heat conditions. it can.
この場合、湿熱条件下での接着強度及び塗膜強度に優れる樹脂組成物が得られることから、多塩基酸（Ｅ）１００質量部中に占める前記三塩基（Ｅ２）の割合が０．５〜１５質量部の範囲であることが好ましく、１〜１０質量部の範囲であることがより好ましく、１．５〜７質量部の範囲であることが特に好ましい。 In this case, since the resin composition excellent in adhesive strength and coating film strength under wet heat conditions is obtained, the proportion of the tribasic (E2) in 100 parts by mass of the polybasic acid (E) is 0.5 to The range is preferably 15 parts by mass, more preferably 1 to 10 parts by mass, and particularly preferably 1.5 to 7 parts by mass.
前記二塩基酸（Ｅ１）及び前記三塩基酸（Ｅ３）は、前述した通り、不飽和脂肪酸の二量体、三量体をそれぞれ個別に用いても良いが、不飽和脂肪酸を粘土触媒の存在下で重合させることにより、不飽和脂肪酸の単量体、二量体、三量体等の多塩基酸組成物として得ることもできる。 As described above, the dibasic acid (E1) and the tribasic acid (E3) may be used separately as dimers and trimers of unsaturated fatty acids, respectively. It can also be obtained as a polybasic acid composition such as an unsaturated fatty acid monomer, dimer or trimer by polymerization under the following conditions.
前記二塩基酸（Ｅ１）及び三塩基酸（Ｅ２）を含有する多塩基酸組成物の市販品は、例えば、ハリマ化成社製「ハリダイマー」シリーズ、クローダジャパン社製「プリポール」シリーズ、築野食品工業社製「ツノダイム」シリーズ等が挙げられる。 Commercially available products of polybasic acid compositions containing the dibasic acid (E1) and tribasic acid (E2) include, for example, “Haridimer” series, Harima Kasei Co., Ltd., “Pripol” series, Croda Japan Co., Ltd. An example is the “Tsunodaim” series manufactured by Kogyo Co., Ltd.
前記ポリエステルポリウレタンポリオール（Ａ）の原料であるジオール化合物（Ｆ）は、例えば、エチレングリコール、ジエチレングリコール、プロピレングリコール、１，３−プロパンジオール、１，２，２−トリメチル−１，３−プロパンジオール、２，２−ジメチル−３−イソプロピル−１，３−プロパンジオール、１，４−ブタンジオール、１，３−ブタンジオール、３−メチル−１，３−ブタンジオール、１，５−ペンタンジオール、３−メチル１，５−ペンタンジオール、ネオペンチルグリコール、１，６−ヘキサンジオール、１，４−ビス（ヒドロキシメチル）シクロヘサン、２，２，４−トリメチル−１，３−ペンタンジオール等の脂肪族ジオール； Examples of the diol compound (F) that is a raw material of the polyester polyurethane polyol (A) include ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,2,2-trimethyl-1,3-propanediol, 2,2-dimethyl-3-isopropyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 3 -Aliphatic diols such as methyl 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,4-bis (hydroxymethyl) cyclohesane, 2,2,4-trimethyl-1,3-pentanediol ;
ポリオキシエチレングリコール、ポリオキシプロピレングリコール等のエーテルグリコール； Ether glycols such as polyoxyethylene glycol and polyoxypropylene glycol;
前記脂肪族ジオールと、エチレンオキシド、プロピレンオキシド、テトラヒドロフラン、エチルグリシジルエーテル、プロピルグリシジルエーテル、ブチルグリシジルエーテル、フェニルグリシジルエーテル、アリルグリシジルエーテル等の種々の環状エーテル結合含有化合物との開環重合によって得られる変性ポリエーテルジオール； Modification obtained by ring-opening polymerization of the aliphatic diol with various cyclic ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether Polyether diols;
前記脂肪族ジオールと、ε−カプロラクトン等の種々のラクトン類との重縮合反応によって得られるラクトン系ポリエステルポリオール； A lactone polyester polyol obtained by a polycondensation reaction between the aliphatic diol and various lactones such as ε-caprolactone;
ビスフェノールＡ、ビスフェノールＦ等のビスフェノール； Bisphenols such as bisphenol A and bisphenol F;
ビスフェノールＡ、ビスフェノールＦ等のビスフェノールにエチレンオキサイド、プロプレンオキサイド等を付加して得られるビスフェノールのアルキレンオキサイド付加物などが挙げられる。 Examples thereof include alkylene oxide adducts of bisphenol obtained by adding ethylene oxide, propylene oxide and the like to bisphenols such as bisphenol A and bisphenol F.
これらジオール化合物（Ｆ）はそれぞれ単独で用いても良いし、二種類以上を併用しても良い。中でも、塗工性に優れる樹脂組成物となる点で、全ジオール化合物（Ｆ）中に占める前記脂肪族ジオールの含有量が５０モル％以上であることが好ましく、８０モル％以上であることがより好ましい。 These diol compounds (F) may be used alone or in combination of two or more. Among them, the content of the aliphatic diol in the total diol compound (F) is preferably 50 mol% or more and 80 mol% or more in that the resin composition is excellent in coatability. More preferred.
前記ポリエステルポリウレタンポリオール（Ａ）の原料であるジイソシアネート化合物（Ｇ）は、例えば、ブタン−１，４−ジイソシアネート、ヘキサメチレンジイソシアネート、２，２，４−トリメチルヘキサメチレンジイソシアネート、２，４，４−トリメチルヘキサメチレンジイソシアネート、キシリレンジイソシアネート、ｍ−テトラメチルキシリレンジイソシアネート等の脂肪族ジイソシアネート； Examples of the diisocyanate compound (G) that is a raw material of the polyester polyurethane polyol (A) include butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethyl. Aliphatic diisocyanates such as hexamethylene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate;
シクロヘキサン−１，４−ジイソシアネート、イソホロンジイソシアネート、リジンジイソシアネート、ジシクロヘキシルメタン−４，４′−ジイソシアネート、１，３−ビス（イソシアネートメチル）シクロヘキサン、メチルシクロヘキサンジイソシアネート、イソプロピリデンジシクロヘキシル−４，４´−ジイソシアネート、ノルボルナンジイソシアネート等の脂環族ジイソシアネート； Cyclohexane-1,4-diisocyanate, isophorone diisocyanate, lysine diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, methylcyclohexane diisocyanate, isopropylidene dicyclohexyl-4,4′-diisocyanate, Alicyclic diisocyanates such as norbornane diisocyanate;
１，５−ナフチレンジイソシアネート、４，４′−ジフェニルメタンジイソシアネート、４，４′−ジフェニルジメチルメタンジイソシアネート、４，４′−ジベンジルジイソシアネート、ジアルキルジフェニルメタンジイソシアネート、テトラアルキルジフェニルメタンジイソシアネート、１，３−フェニレンジイソシアネート、１，４−フェニレンジイソシアネート、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、テトラメチルキシリレンジイソシアネート等の芳香族ジイソシアネートが挙げられる。 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl diisocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate , 1,4-phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate and the like.
これらジイソシアネート化合物（Ｇ）は、それぞれ単独で用いても良いし、二種類以上を併用しても良い。中でも、樹脂組成物を塗工に適した粘度に調節することが容易となる点で、前記脂肪族ジイソシアネート又は脂環族ジイソシアネートが好ましい。 These diisocyanate compounds (G) may be used alone or in combination of two or more. Especially, the said aliphatic diisocyanate or alicyclic diisocyanate is preferable at the point which adjusts the resin composition to the viscosity suitable for coating easily.
前記ポリエステルポリウレタンポリオール（Ａ）を製造する方法は、例えば、前記多塩基酸（Ｅ）と、前記ジオール化合物（Ｆ）とを、エステル化触媒の存在下１５０〜２７０℃の温度範囲で反応させてポリエステルポリオールを得た後、該ポリエステルポリオールと前記ジイソシアネート化合物（Ｇ）とを、ウレタン化触媒の存在下５０〜１００℃の温度範囲で反応させる方法などが挙げられる。 In the method for producing the polyester polyurethane polyol (A), for example, the polybasic acid (E) and the diol compound (F) are reacted in a temperature range of 150 to 270 ° C. in the presence of an esterification catalyst. Examples thereof include a method of reacting the polyester polyol and the diisocyanate compound (G) in the temperature range of 50 to 100 ° C. in the presence of a urethanization catalyst after obtaining the polyester polyol.
このようにして得られるポリエステルポリウレタンポリオール（Ａ）の重量平均分子量（Ｍｗ）は、初期の接着強度に優れ、かつ、塗膜強度の高い樹脂組成物が得られることから、２０，０００〜１００，０００の範囲であることが好ましい。中でも、湿熱条件下での基材接着性にも優れる樹脂組成物が得られることから、重量平均分子量（Ｍｗ）が４０，０００〜９０，０００の範囲であることが好ましい。 The polyester polyurethane polyol (A) thus obtained has a weight average molecular weight (Mw) of 20,000 to 100,000 because a resin composition having excellent initial adhesive strength and high coating strength can be obtained. A range of 000 is preferred. Especially, since the resin composition which is excellent also in the base-material adhesiveness on wet heat conditions is obtained, it is preferable that a weight average molecular weight (Mw) is the range of 40,000-90,000.
前記ポリエステルポリウレタンポリオール（Ａ）の分子量分布（Ｍｗ／Ｍｎ）は、低分子量成分に起因した基材との密着性が向上する効果と、高分子量成分に起因した硬化物が高強度となる効果が同時に発揮されることにより、湿熱条件下での基材接着性に優れ、初期の接着強度が高い樹脂組成物となることから、３〜１５の範囲であることが好ましく、４〜１２の範囲であることがより好ましい。 The molecular weight distribution (Mw / Mn) of the polyester polyurethane polyol (A) has the effect of improving the adhesion to the substrate due to the low molecular weight component and the effect of increasing the strength of the cured product due to the high molecular weight component. It is preferably in the range of 3 to 15 because it is excellent in substrate adhesion under wet heat conditions and becomes a resin composition having high initial adhesive strength by being exhibited simultaneously, preferably in the range of 4 to 12 More preferably.
また、前記ポリエステルポリウレタンポリオール（Ａ）の数平均分子量（Ｍｎ）は、湿熱条件下での基材接着性に優れ、塗工に適した粘度の樹脂組成物となる点で、３，０００〜２０，０００の範囲であることが好ましく、５，０００〜１２，０００の範囲であることがより好ましい。 Moreover, the number average molecular weight (Mn) of the said polyester polyurethane polyol (A) is excellent in the base-material adhesiveness in wet heat conditions, and becomes a resin composition of the viscosity suitable for coating, 3000-20 Is preferably in the range of 5,000, more preferably in the range of 5,000 to 12,000.
尚、本願発明において、重量平均分子量（Ｍｗ）及び数平均分子量（Ｍｎ）は、下記条件のゲルパーミアーションクロマトグラフィー（ＧＰＣ）により測定される値である。 In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values measured by gel permeation chromatography (GPC) under the following conditions.
測定装置 ；東ソー株式会社製 ＨＬＣ−８２２０ＧＰＣ
カラム ；東ソー株式会社製 ＴＳＫ−ＧＵＡＲＤＣＯＬＵＭＮ ＳｕｐｅｒＨＺ−Ｌ
＋東ソー株式会社製 ＴＳＫ−ＧＥＬ ＳｕｐｅｒＨＺＭ−Ｍ×４
検出器 ；ＲＩ（示差屈折計）
データ処理；東ソー株式会社製 マルチステーションＧＰＣ−８０２０ｍｏｄｅｌＩＩ
測定条件 ；カラム温度 ４０℃
溶媒 テトラヒドロフラン
流速 ０．３５ｍｌ／分
標準 ；単分散ポリスチレン
試料 ；樹脂固形分換算で０．２質量％のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの（１００μｌ）
Measuring device: HLC-8220GPC manufactured by Tosoh Corporation
Column: TSK-GUARDCOLUMN SuperHZ-L manufactured by Tosoh Corporation
+ Tosoh Corporation TSK-GEL SuperHZM-M x 4
Detector: RI (differential refractometer)
Data processing: Multi-station GPC-8020 model II manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow rate: 0.35 ml / min Standard: Monodispersed polystyrene Sample: Filtered 0.2% by mass tetrahydrofuran solution in terms of resin solids with a microfilter (100 μl)
また、前記ポリエステルポリウレタンポリオール（Ａ）の水酸基価は、湿熱条件下での基材接着性に優れる樹脂組成物が得られる点で、１〜１０ｍｇＫＯＨ／ｇの範囲であることが好ましい。 Moreover, it is preferable that the hydroxyl value of the said polyester polyurethane polyol (A) is the range of 1-10 mgKOH / g at the point from which the resin composition which is excellent in the base-material adhesiveness on wet heat conditions is obtained.
本発明の樹脂組成物は、ビスフェノール型エポキシ樹脂（Ｂ）を含有することにより、一般に接着性の低いＰＶＦフィルムやＰＶＤＦフィルム等のフッ素系基材に対しても、高い接着性を発現することができる。該ビスフェノール型エポキシ樹脂（Ｂ）は、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＢ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂等が挙げられる。これらはそれぞれ単独で用いても良いし、二種類以上を併用しても良い。これらの中でも、湿熱条件下での基材接着性及び初期の接着強度に優れる樹脂組成物が得られる点で、ビスフェノールＡ型のエポキシ樹脂が好ましい。 The resin composition of the present invention can exhibit high adhesiveness to fluorine-based substrates such as PVF films and PVDF films generally having low adhesiveness by containing the bisphenol type epoxy resin (B). it can. Examples of the bisphenol type epoxy resin (B) include bisphenol A type epoxy resin, bisphenol B type epoxy resin, and bisphenol F type epoxy resin. These may be used alone or in combination of two or more. Among these, a bisphenol A type epoxy resin is preferable in that a resin composition excellent in substrate adhesion under wet heat conditions and initial adhesive strength can be obtained.
前記ビスフェノール型エポキシ樹脂（Ｂ）のエポキシ当量は、前記フッ素系基材等への接着性により優れる樹脂組成物が得られることから、１５０〜２，５００ｇ／ｅｑの範囲であることが好ましく、１７０〜１，０００ｇ／ｅｑの範囲であることがより好ましく、２００〜６００ｇ／ｅｑの範囲であることが特に好ましい。また、同様の理由から、前記エポキシ樹脂（Ｂ）の数平均分子量（Ｍｎ）は３００〜５，０００の範囲であることが好ましく、３４０〜２，０００の範囲であることがより好ましく、４００〜１，２００の範囲であることが特に好ましい。 The epoxy equivalent of the bisphenol-type epoxy resin (B) is preferably in the range of 150 to 2,500 g / eq since a resin composition that is more excellent in adhesiveness to the fluorine-based substrate or the like can be obtained. More preferably, it is in the range of ˜1,000 g / eq, and particularly preferably in the range of 200 to 600 g / eq. For the same reason, the number average molecular weight (Mn) of the epoxy resin (B) is preferably in the range of 300 to 5,000, more preferably in the range of 340 to 2,000, A range of 1,200 is particularly preferred.
また、前記ビスフェノール型エポキシ樹脂（Ｂ）は、より硬化性に優れる樹脂組成物が得られることから、分子構造中に水酸基を有していることが好ましい。中でも、水酸基価が３０〜１５０ｍｇＫＯＨ／ｇの範囲であることが好ましい。 The bisphenol-type epoxy resin (B) preferably has a hydroxyl group in the molecular structure because a resin composition with better curability can be obtained. Especially, it is preferable that a hydroxyl value is the range of 30-150 mgKOH / g.
本発明の樹脂組成物は、ポリカーボネート樹脂（Ｃ）を含有することにより、湿熱条件下での基材接着性に優れる樹脂組成物となる。中でも、湿熱条件下での基材接着性に優れる樹脂組成物が得られることから、数平均分子量（Ｍｎ）が３００〜３，０００の範囲であることが好ましく、４００〜２，０００の範囲であるものがより好ましい。 By containing polycarbonate resin (C), the resin composition of this invention turns into a resin composition excellent in the base-material adhesiveness in wet heat conditions. Especially, since the resin composition which is excellent in the base-material adhesiveness on wet heat conditions is obtained, it is preferable that a number average molecular weight (Mn) is the range of 300-3,000, and is the range of 400-2,000. Some are more preferred.
前記水酸基含有ポリカーボネート樹脂（Ｃ）は、より硬化性に優れる樹脂組成物となることから水酸基を含有していることが好ましい。中でも、水酸基価が２０〜３００ｍｇＫＯＨ／ｇの範囲であるものが好ましく、４０〜２５０ｍｇＫＯＨ／ｇの範囲であるものがより好ましい。また、湿熱条件下での基材接着性に優れる点で、ポリカーボネートジオールであることが好ましい。 The hydroxyl group-containing polycarbonate resin (C) preferably contains a hydroxyl group because it becomes a resin composition with more excellent curability. Among these, those having a hydroxyl value in the range of 20 to 300 mgKOH / g are preferable, and those having a hydroxyl value in the range of 40 to 250 mgKOH / g are more preferable. Moreover, it is preferable that it is polycarbonate diol at the point which is excellent in the base-material adhesiveness on wet heat conditions.
前記水酸基含有ポリカーボネート樹脂（Ｃ）は、例えば、多価アルコールとカルボニル化剤とを重縮合反応させる方法により製造することができる。 The hydroxyl group-containing polycarbonate resin (C) can be produced, for example, by a method of polycondensation reaction between a polyhydric alcohol and a carbonylating agent.
前記水酸基含有ポリカーボネート樹脂（Ｃ）の製造で用いる多価アルコールは、例えば、前記多価アルコール（Ｆ）として例示した各種の多価アルコールが挙げられる。多価アルコールはそれぞれ単独で用いても良いし、二種類以上を併用しても良い。 Examples of the polyhydric alcohol used in the production of the hydroxyl group-containing polycarbonate resin (C) include various polyhydric alcohols exemplified as the polyhydric alcohol (F). Polyhydric alcohols may be used alone or in combination of two or more.
前記水酸基含有ポリカーボネート樹脂（Ｃ）の製造で用いるカルボニル化剤は、例えば、エチレンカーボネート、プロピレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、ジブチルカーボネート、ジフェニルカーボネート等を挙げることができる。これらはそれぞれ単独で用いても良いし、二種類以上を併用しても良い。 Examples of the carbonylating agent used in the production of the hydroxyl group-containing polycarbonate resin (C) include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, diphenyl carbonate, and the like. These may be used alone or in combination of two or more.
本発明の樹脂組成物は、前記ポリエステルポリウレタンポリオール（Ａ）と、前記ビスフェノール型エポキシ樹脂（Ｂ）と、前記ポリカーボネート樹脂（Ｃ）とを、前記ポリエステルポリウレタンポリオール（Ａ）１００質量部に対し、前記ビスフェノール型エポキシ樹脂（Ｂ）が５〜２０質量部の範囲となり、かつ、前記ポリカーボネート樹脂（Ｃ）が５〜２０質量部の範囲となる割合で含有することにより、種々の基材に対する接着性に優れ、湿熱条件下であっても高い基材接着性を維持できる樹脂組成物となる。 The resin composition of the present invention comprises the polyester polyurethane polyol (A), the bisphenol-type epoxy resin (B), and the polycarbonate resin (C) with respect to 100 parts by mass of the polyester polyurethane polyol (A). By containing the bisphenol-type epoxy resin (B) in the range of 5 to 20 parts by mass and the polycarbonate resin (C) in the range of 5 to 20 parts by mass, the adhesiveness to various substrates can be obtained. It becomes the resin composition which is excellent and can maintain high base-material adhesiveness even under wet heat conditions.
本発明の樹脂組成物における前記ポリイソシアネート（Ｄ）は、前記ポリエステルポリウレタンポリオール（Ａ）、前記エポキシ樹脂（Ｂ）及び前記ポリカーボネート樹脂（Ｃ）が含有する水酸基と反応させる硬化剤として働く。該ポリイソシアネート（Ｄ）は、例えば、前記ポリイソシアネート（Ｇ）として列記した種々のポリイソシアネートが挙げられる。これらポリイソシアネート（Ｄ）は一種類を単独で用いても良いし、二種類以上を併用しても良い。 The polyisocyanate (D) in the resin composition of the present invention serves as a curing agent that reacts with the hydroxyl groups contained in the polyester polyurethane polyol (A), the epoxy resin (B), and the polycarbonate resin (C). Examples of the polyisocyanate (D) include various polyisocyanates listed as the polyisocyanate (G). These polyisocyanate (D) may be used individually by 1 type, and may use 2 or more types together.
これらポリイソシアネート（Ｄ）の中でも、接着剤塗膜が黄変し難い点では、前記脂肪族ジイソシアネート化合物が好ましい。また、湿熱条件下での基材密着性に優れる点では、前記ヌレート型ポリイソシアネート化合物が好ましい。 Among these polyisocyanates (D), the aliphatic diisocyanate compound is preferable in that the adhesive coating film is hardly yellowed. Moreover, the said nurate type | mold polyisocyanate compound is preferable at the point which is excellent in the base-material adhesiveness on wet heat conditions.
本願発明の樹脂組成物は、前記ポリエステルポリウレタンポリオール（Ａ）と、前記エポキシ樹脂（Ｂ）と、前記ポリカーボネート樹脂（Ｃ）と、ポリイソシアネート（Ｄ）とを必須の成分として含有する。本発明では、前記ポリエステルポリウレタンポリオール（Ａ）、前記エポキシ樹脂（Ｂ）及び前記ポリカーボネート樹脂（Ｃ）に含まれる水酸基の合計モル数［ＯＨ］と、前記ポリイソシアネート化合物（Ｄ）に含まれるイソシアネート基のモル数［ＮＣＯ］との比［ＯＨ］／［ＮＣＯ］を１／１〜１／３の範囲とすることにより、硬化性に優れる樹脂組成物となる。中でも、［ＯＨ］／［ＮＣＯ］が１／１．０５〜１／１．５の範囲であることが好ましい。 The resin composition of the present invention contains the polyester polyurethane polyol (A), the epoxy resin (B), the polycarbonate resin (C), and the polyisocyanate (D) as essential components. In the present invention, the total number of moles [OH] of hydroxyl groups contained in the polyester polyurethane polyol (A), the epoxy resin (B) and the polycarbonate resin (C), and the isocyanate group contained in the polyisocyanate compound (D). By setting the ratio [OH] / [NCO] to the number of moles [NCO] of 1/1 to 1/3, a resin composition having excellent curability is obtained. Among them, [OH] / [NCO] is preferably in the range of 1 / 1.05 to 1 / 1.5.
本願発明の樹脂組成物は、更に、各種の溶剤を含有していても良い。前記溶媒は、例えば、例えば、アセトン、メチルエチルケトン（ＭＥＫ）、メチルイソブチルケトン等のケトン系化合物、テトラヒドロフラン（ＴＨＦ）、ジオキソラン等の環状エーテル系化合物、酢酸メチル、酢酸エチル、酢酸ブチル等のエステル系化合物、トルエン、キシレン等の芳香族系化合物、カルビトール、セロソルブ、メタノール、イソプロパノール、ブタノール、プロピレングリコールモノメチルエーテルなどのアルコール系化合物が挙げられる。これらは単独で使用しても二種類以上を併用しても良い。 The resin composition of the present invention may further contain various solvents. Examples of the solvent include ketone compounds such as acetone, methyl ethyl ketone (MEK) and methyl isobutyl ketone, cyclic ether compounds such as tetrahydrofuran (THF) and dioxolane, and ester compounds such as methyl acetate, ethyl acetate and butyl acetate. Aromatic compounds such as toluene and xylene, and alcohol compounds such as carbitol, cellosolve, methanol, isopropanol, butanol, and propylene glycol monomethyl ether. These may be used alone or in combination of two or more.
本発明の樹脂組成物は、更に、紫外線吸収剤、酸化防止剤、シリコン系添加剤、フッ素系添加剤、レオロジーコントロール剤、脱泡剤、帯電防止剤、防曇剤等の各種添加剤を含有しても良い。 The resin composition of the present invention further contains various additives such as an ultraviolet absorber, an antioxidant, a silicon-based additive, a fluorine-based additive, a rheology control agent, a defoaming agent, an antistatic agent, and an antifogging agent. You may do it.
本願発明の樹脂組成物は、種々のプラスチックフィルムを接着する為の２液型ラミネート用接着剤として好適に用いることができる。 The resin composition of the present invention can be suitably used as a two-component laminating adhesive for bonding various plastic films.
前記種々のプラスチックフィルムは、例えば、ポリカーボネート、ポリエチレンテレフタレート、ポリメチルメタクリレート、ポリスチレン、ポリエステル、ポリオレフィン、エポキシ樹脂、メラミン樹脂、トリアセチルセルロース樹脂、ポリビニルアルコール、ＡＢＳ樹脂、ノルボルネン系樹脂、環状オレフィン系樹脂、ポリイミド樹脂、ポリフッ化ビニル樹脂、ポリフッ化ビニリデン樹脂等からなるフィルムが挙げられる。本願発明の２液型ラミネート用接着剤は、上記各種フィルムの中でも特に接着が難しいポリフッ化ビニル樹脂やポリフッ化ビニリデン樹脂からなるフィルムに対しても高い接着性を示す。 The various plastic films include, for example, polycarbonate, polyethylene terephthalate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, polyvinyl alcohol, ABS resin, norbornene resin, cyclic olefin resin, Examples include films made of polyimide resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, and the like. The two-pack type laminating adhesive of the present invention exhibits high adhesion to films made of polyvinyl fluoride resin or polyvinylidene fluoride resin, which are particularly difficult to bond among the various films.
前記各種フィルム同士を接着する際、本願発明の２液型ラミネート用接着剤の使用量は、２〜１０ｇ／ｍ２の範囲であることが好ましい。 When the various films are bonded to each other, the amount of the two-component laminating adhesive of the present invention is preferably in the range of 2 to 10 g / m 2 .
本願発明の２液型ラミネート用接着剤を用い、複数のフィルムを接着して得られる積層フィルムは、湿熱条件下でも高い接着性を有し、フィルム同士が剥がれ難い特徴がある。従って、本願発明の２液型ラミネート用接着剤は、屋外等の厳しい環境下で用いる積層フィルム用途に好適に用いることができ、このような用途としては、例えば、太陽電池のバックシートを製造する際の接着剤などが挙げられる。 A laminated film obtained by adhering a plurality of films using the two-component laminating adhesive of the present invention has high adhesiveness even under wet heat conditions, and has a characteristic that the films are difficult to peel off. Accordingly, the two-component laminating adhesive of the present invention can be suitably used for laminated film applications used in harsh environments such as outdoors, and as such applications, for example, a solar cell backsheet is manufactured. For example, an adhesive may be used.
以下に本発明を具体的な合成例、実施例を挙げてより詳細に説明するが、本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to specific synthesis examples and examples, but the present invention is not limited to these examples.
尚、本願実施例では、数平均分子量（Ｍｎ）及び重量平均分子量（Ｍｗ）は、下記条件のゲルパーミアーションクロマトグラフィー（ＧＰＣ）により測定した。 In Examples of the present application, the number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured by gel permeation chromatography (GPC) under the following conditions.
測定装置 ；東ソー株式会社製 ＨＬＣ−８２２０ＧＰＣ
カラム ；東ソー株式会社製 ＴＳＫ−ＧＵＡＲＤＣＯＬＵＭＮ ＳｕｐｅｒＨＺ−Ｌ
＋東ソー株式会社製 ＴＳＫ−ＧＥＬ ＳｕｐｅｒＨＺＭ−Ｍ×４
検出器 ；ＲＩ（示差屈折計）
データ処理；東ソー株式会社製 マルチステーションＧＰＣ−８０２０ｍｏｄｅｌＩＩ
測定条件 ；カラム温度 ４０℃
溶媒 テトラヒドロフラン
流速 ０．３５ｍｌ／分
標準 ；単分散ポリスチレン
試料 ；樹脂固形分換算で０．２質量％のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの（１００μｌ）
Measuring device: HLC-8220GPC manufactured by Tosoh Corporation
Column: TSK-GUARDCOLUMN SuperHZ-L manufactured by Tosoh Corporation
+ Tosoh Corporation TSK-GEL SuperHZM-M x 4
Detector: RI (differential refractometer)
Data processing: Multi-station GPC-8020 model II manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Solvent tetrahydrofuran
Flow rate: 0.35 ml / min Standard: Monodispersed polystyrene Sample: Filtered 0.2% by mass tetrahydrofuran solution in terms of resin solids with a microfilter (100 μl)
製造例１
ポリエステルポリウレタンポリオール（Ａ１）溶液の製造
攪拌棒、温度センサー、精留管を有するフラスコに、ネオペンチルグリコール３２９質量部、１，６−ヘキサンジオール２１０質量部、多塩基酸組成物（築野食品工業株式会社製「ツノダイム２２８」組成：炭素原子数１７の炭化水素基を主骨格とする一塩基酸を５質量％、炭素原子数３４の炭化水素基を主骨格とする二塩基酸を８０．８質量％、炭素原子数５１の炭化水素基を主骨格とする三塩基酸を１４．２質量％）２７０質量部、アジピン酸１３５質量部、イソフタル酸２４０質量部、テレフタル酸３１５質量部及び有機チタン化合物０．１質量部を仕込み、乾燥窒素をフラスコ内にフローさせ攪拌しながら２４０〜２５０℃に加熱しエステル化反応を行った。酸価が１．０ｍｇＫＯＨ／ｇ以下となったところで反応を停止し、１００℃まで冷却した後、酢酸エチルで固形分が６０質量％になるように希釈した。次いで、イソホロンジイソシアネート５６質量部を仕込み、乾燥窒素をフラスコ内にフローさせ攪拌しながら７０〜８０℃に加熱しウレタン化反応を行った。イソシアネート含有率０．３％以下となったところで反応を停止し、酢酸エチルで固形分が５０質量％になるように希釈して、ポリエステルポリウレタンポリオール（Ａ１）溶液を得た。ポリエステルポリウレタンポリオール（Ａ１）の数平均分子量（Ｍｎ）は８，０００、重量平均分子量（Ｍｗ）は５０，０００、分子量分布（Ｍｗ／Ｍｎ）は６．３、固形分の水酸基価は３．２ｍｇＫＯＨ／ｇであった。
Production Example 1
Manufacture of Polyester Polyurethane Polyol (A1) Solution In a flask having a stirring bar, a temperature sensor, and a rectifying tube, 329 parts by weight of neopentyl glycol, 210 parts by weight of 1,6-hexanediol, a polybasic acid composition (Tsukuno Food Industry) “Tsunodaim 228” manufactured by Co., Ltd. Composition: 5% by mass of a monobasic acid having a hydrocarbon group having 17 carbon atoms as a main skeleton and 80.8% of a dibasic acid having a hydrocarbon group having 34 carbon atoms as a main skeleton 270 parts by weight, 135 parts by weight of adipic acid, 240 parts by weight of isophthalic acid, 315 parts by weight of terephthalic acid, and organic titanium 0.1 parts by mass of the compound was charged, and dry nitrogen was allowed to flow into the flask and heated to 240 to 250 ° C. while stirring to conduct an esterification reaction. The reaction was stopped when the acid value became 1.0 mgKOH / g or less, and after cooling to 100 ° C., it was diluted with ethyl acetate so that the solid content became 60% by mass. Next, 56 parts by mass of isophorone diisocyanate was charged, and dry nitrogen was allowed to flow into the flask and heated to 70 to 80 ° C. while stirring to conduct a urethanization reaction. The reaction was stopped when the isocyanate content became 0.3% or less, and diluted with ethyl acetate to a solid content of 50% by mass to obtain a polyester polyurethane polyol (A1) solution. The number average molecular weight (Mn) of the polyester polyurethane polyol (A1) is 8,000, the weight average molecular weight (Mw) is 50,000, the molecular weight distribution (Mw / Mn) is 6.3, and the hydroxyl value of the solid content is 3.2 mgKOH. / G.
製造例２
ポリエステルポリウレタンポリオール（Ａ２）溶液の製造
攪拌棒、温度センサー、精留管を有するフラスコに、ジエチレングリコール１０５質量部、ネオペンチルグリコール３２１質量部、１，６−ヘキサンジオール１５０質量部、前記多塩基酸組成物（築野食品工業株式会社製「ツノダイム２２８」組成：炭素原子数１７の炭化水素基を主骨格とする一塩基酸を５質量％、炭素原子数３４の炭化水素基を主骨格とする二塩基酸を８０．８質量％、炭素原子数５１の炭化水素基を主骨格とする三塩基酸を１４．２質量％）１５０部、アジピン酸２６０質量部、イソフタル酸２７８質量部、テレフタル酸２３３質量部及び有機チタン化合物０．１質量部を仕込み、乾燥窒素をフラスコ内にフローさせ攪拌しながら２４０〜２５０℃に加熱しエステル化反応を行った。酸価が１．０ｍｇＫＯＨ／ｇ以下となったところで反応を停止し、１００℃まで冷却した後、酢酸エチルで固形分が６０質量％になるように希釈した。次いで、イソホロンジイソシアネート６０質量部を仕込み、乾燥窒素をフラスコ内にフローさせ攪拌しながら７０〜８０℃に加熱しウレタン化反応を行った。イソシアネート含有率０．３％以下となったところで反応を停止し、酢酸エチルで固形分が５０質量％になるように希釈して、ポリエステルポリウレタンポリオール（Ａ２）溶液を得た。ポリエステルポリウレタンポリオール（Ａ２）の数平均分子量（Ｍｎ）は９，３００、重量平均分子量（Ｍｗ）は６３，０００、分子量分布（Ｍｗ／Ｍｎ）は６．８、固形分の水酸基価は２．０ｍｇＫＯＨ／ｇであった。
Production Example 2
Production of Polyester Polyurethane Polyol (A2) Solution In a flask having a stirring bar, a temperature sensor, and a rectifying tube, 105 parts by mass of diethylene glycol, 321 parts by mass of neopentyl glycol, 150 parts by mass of 1,6-hexanediol, the polybasic acid composition (Tsunodim 228 manufactured by Tsukino Food Industries Co., Ltd.) composition: 5% by mass of a monobasic acid having a hydrocarbon group having 17 carbon atoms as a main skeleton and a hydrocarbon group having 34 carbon atoms as a main skeleton 150 parts by weight of basic acid (80.8% by weight, tribasic acid having a hydrocarbon group having 51 carbon atoms as the main skeleton, 14.2% by weight), 260 parts by weight of adipic acid, 278 parts by weight of isophthalic acid, 233 parts of terephthalic acid A mass part and 0.1 part by mass of an organic titanium compound are charged, dry nitrogen is allowed to flow into the flask, and heated to 240 to 250 ° C. with stirring. A tellurization reaction was performed. The reaction was stopped when the acid value became 1.0 mgKOH / g or less, and after cooling to 100 ° C., it was diluted with ethyl acetate so that the solid content became 60% by mass. Next, 60 parts by mass of isophorone diisocyanate was charged, and dry nitrogen was allowed to flow into the flask and heated to 70 to 80 ° C. while stirring to conduct a urethanization reaction. The reaction was stopped when the isocyanate content became 0.3% or less, and diluted with ethyl acetate to a solid content of 50% by mass to obtain a polyester polyurethane polyol (A2) solution. The number average molecular weight (Mn) of the polyester polyurethane polyol (A2) is 9,300, the weight average molecular weight (Mw) is 63,000, the molecular weight distribution (Mw / Mn) is 6.8, and the hydroxyl value of the solid content is 2.0 mgKOH. / G.
製造例３
ポリエステルポリウレタンポリオール（Ａ３）溶液の製造
攪拌棒、温度センサー、精留管を有するフラスコに、エチレングリコール１０５質量部、ネオペンチルグリコール２７６質量部、１，６−ヘキサンジオール１５０質量部、前記多塩基酸組成物（築野食品工業株式会社製「ツノダイム２２８」組成：炭素原子数１７の炭化水素基を主骨格とする一塩基酸を５質量％、炭素原子数３４の炭化水素基を主骨格とする二塩基酸を８０．８質量％、炭素原子数５１の炭化水素基を主骨格とする三塩基酸を１４．２質量％）１５０質量部、アジピン酸２６０質量部、イソフタル酸２７８質量部、テレフタル酸２７８質量部及び有機チタン化合物０．１質量部を仕込み、乾燥窒素をフラスコ内にフローさせ攪拌しながら２４０〜２５０℃に加熱しエステル化反応を行った。酸価が１．０ｍｇＫＯＨ／ｇ以下となったところで反応を停止し、１００℃まで冷却後、酢酸エチルで固形分が６０質量％になるように希釈した。次いで、イソホロンジイソシアネート５６質量部を仕込み、乾燥窒素をフラスコ内にフローさせ攪拌しながら７０〜８０℃に加熱しウレタン化反応を行った。イソシアネート含有率０．３％以下となったところで反応を停止し、酢酸エチルで固形分が５０質量％になるように希釈して、ポリエステルポリウレタンポリオール（Ａ３）溶液を得た。ポリエステルポリウレタンポリオール（Ａ３）の数平均分子量（Ｍｎ）は１０，０００、重量平均分子量（Ｍｗ）は６０，０００、分子量分布（Ｍｗ／Ｍｎ）は６．０、固形分の水酸基価は４．１ｍｇＫＯＨ／ｇであった。
Production Example 3
Production of Polyester Polyurethane Polyol (A3) Solution In a flask having a stirrer, a temperature sensor, and a rectifying tube, 105 parts by mass of ethylene glycol, 276 parts by mass of neopentyl glycol, 150 parts by mass of 1,6-hexanediol, the polybasic acid Composition (“Tsunodaim 228” manufactured by Tsukino Food Industries Co., Ltd.) Composition: 5% by mass of a monobasic acid having a hydrocarbon group having 17 carbon atoms as a main skeleton and a hydrocarbon group having 34 carbon atoms as a main skeleton 150 parts by mass of dibasic acid, 80.8% by mass, 14.2% by mass of tribasic acid having 51 carbon atoms as the main skeleton, 260 parts by mass of adipic acid, 278 parts by mass of isophthalic acid, terephthalic acid 278 parts by weight of an acid and 0.1 part by weight of an organic titanium compound are charged, dry nitrogen is flowed into the flask, and heated to 240 to 250 ° C. with stirring. Stealization reaction was performed. The reaction was stopped when the acid value became 1.0 mgKOH / g or less, and after cooling to 100 ° C., the mixture was diluted with ethyl acetate so that the solid content became 60% by mass. Next, 56 parts by mass of isophorone diisocyanate was charged, and dry nitrogen was allowed to flow into the flask and heated to 70 to 80 ° C. while stirring to conduct a urethanization reaction. The reaction was stopped when the isocyanate content became 0.3% or less, and diluted with ethyl acetate to a solid content of 50% by mass to obtain a polyester polyurethane polyol (A3) solution. The number average molecular weight (Mn) of the polyester polyurethane polyol (A3) is 10,000, the weight average molecular weight (Mw) is 60,000, the molecular weight distribution (Mw / Mn) is 6.0, and the hydroxyl value of the solid content is 4.1 mgKOH. / G.
製造例４
ポリエステルポリウレタンポリオール（Ａ４）溶液の製造
攪拌棒、温度センサー、精留管を有するフラスコに、エチレングリコール７５質量部、ネオペンチルグリコール２４９質量部、１，６−ヘキサンジオール１５０質量部、前記多塩基酸組成物（築野食品工業株式会社製「ツノダイム２２８」組成：炭素原子数１７の炭化水素基を主骨格とする一塩基酸を５質量％、炭素原子数３４の炭化水素基を主骨格とする二塩基酸を８０．８質量％、炭素原子数５１の炭化水素基を主骨格とする三塩基酸を１４．２質量％）３７５質量部、アジピン酸７５質量部、イソフタル酸２７８質量部、テレフタル酸２９８質量部及び有機チタン化合物０．１質量部を仕込み、乾燥窒素をフラスコ内にフローさせ攪拌しながら２４０〜２５０℃に加熱しエステル化反応を行った。酸価が１．０ｍｇＫＯＨ／ｇ以下となったところで反応を停止し、１００℃まで冷却後、酢酸エチルで固形分が６０質量％になるように希釈した。次いで、ヘキサメチレンジイソシアネート４０質量部を仕込み、乾燥窒素をフラスコ内にフローさせ攪拌しながら７０〜８０℃に加熱しウレタン化反応を行った。イソシアネート含有率０．３％以下となったところで反応を停止し、酢酸エチルで固形分が５０質量％になるように希釈して、ポリエステルポリウレタンポリオール（Ａ４）溶液を得た。ポリエステルポリウレタンポリオール（Ａ４）の数平均分子量（Ｍｎ）は１１，０００、重量平均分子量（Ｍｗ）は６４，０００、分子量分布（Ｍｗ／Ｍｎ）は５．８、固形分の水酸基価は２．８ｍｇＫＯＨ／ｇであった。
Production Example 4
Production of Polyester Polyurethane Polyol (A4) Solution In a flask having a stirring bar, a temperature sensor, and a rectifying tube, 75 parts by mass of ethylene glycol, 249 parts by mass of neopentyl glycol, 150 parts by mass of 1,6-hexanediol, the polybasic acid Composition (“Tsunodaim 228” manufactured by Tsukino Food Industries Co., Ltd.) Composition: 5% by mass of a monobasic acid having a hydrocarbon group having 17 carbon atoms as a main skeleton and a hydrocarbon group having 34 carbon atoms as a main skeleton 375 parts by mass of dibasic acid, 80.8% by mass of dibasic acid, and 14.2% by mass of tribasic acid having a hydrocarbon group having 51 carbon atoms as main skeleton), 75 parts by mass of adipic acid, 278 parts by mass of isophthalic acid, terephthalic acid 298 parts by weight of an acid and 0.1 part by weight of an organic titanium compound are charged, dry nitrogen is flowed into the flask and heated to 240 to 250 ° C. with stirring. The reaction was carried out. The reaction was stopped when the acid value became 1.0 mgKOH / g or less, and after cooling to 100 ° C., the mixture was diluted with ethyl acetate so that the solid content became 60% by mass. Next, 40 parts by mass of hexamethylene diisocyanate was charged, and dry nitrogen was allowed to flow into the flask and heated to 70 to 80 ° C. while stirring to conduct a urethanization reaction. The reaction was stopped when the isocyanate content became 0.3% or less, and diluted with ethyl acetate to a solid content of 50% by mass to obtain a polyester polyurethane polyol (A4) solution. The number average molecular weight (Mn) of the polyester polyurethane polyol (A4) is 11,000, the weight average molecular weight (Mw) is 64,000, the molecular weight distribution (Mw / Mn) is 5.8, and the hydroxyl value of the solid content is 2.8 mgKOH. / G.
製造例５
ポリエステルポリウレタンポリオール（Ａ５）溶液の製造
攪拌棒、温度センサー、精留管を有するフラスコに、エチレングリコール１０６質量部、ネオペンチルグリコール２８９質量部、１，６−ヘキサンジオール１５０質量部、前記多塩基酸組成物（築野食品工業株式会社製「ツノダイム２２８」組成：炭素原子数１７の炭化水素基を主骨格とする一塩基酸を５質量％、炭素原子数３４の炭化水素基を主骨格とする二塩基酸を８０．８質量％、炭素原子数５１の炭化水素基を主骨格とする三塩基酸を１４．２質量％）１５０質量部、アジピン酸２４８質量部、イソフタル酸２７８質量部、無水フタル酸２７８質量部及び有機チタン化合物０．１質量部を仕込み、乾燥窒素をフラスコ内にフローさせ攪拌しながら２４０〜２５０℃に加熱しエステル化反応を行った。酸価が１．０ｍｇＫＯＨ／ｇ以下となったところで反応を停止し、１００℃まで冷却後、酢酸エチルで固形分が６０質量％になるように希釈した。次いで、ジシクロヘキシルメタン4,4'-ジイソシアナート６０質量部を仕込み、乾燥窒素をフラスコ内にフローさせ攪拌しながら７０〜８０℃に加熱しウレタン化反応を行った。イソシアネート含有率０．３％以下となったところで反応を停止し、酢酸エチルで固形分が５０質量％になるように希釈して、ポリエステルポリウレタンポリオール（Ａ５）溶液を得た。ポリエステルポリウレタンポリオール（Ａ５）の数平均分子量（Ｍｎ）は１０，８００、重量平均分子量（Ｍｗ）は５５，０００、分子量分布（Ｍｗ／Ｍｎ）は５．１、固形分の水酸基価は３．２ｍｇＫＯＨ／ｇであった。
Production Example 5
Production of Polyester Polyurethane Polyol (A5) Solution In a flask having a stirrer, a temperature sensor, and a rectifying tube, 106 parts by mass of ethylene glycol, 289 parts by mass of neopentyl glycol, 150 parts by mass of 1,6-hexanediol, the polybasic acid Composition (“Tsunodaim 228” manufactured by Tsukino Food Industries Co., Ltd.) Composition: 5% by mass of a monobasic acid having a hydrocarbon group having 17 carbon atoms as a main skeleton and a hydrocarbon group having 34 carbon atoms as a main skeleton 150 parts by mass of dibasic acid (80.8% by mass, tribasic acid having a hydrocarbon group of 51 carbon atoms as the main skeleton, 14.2% by mass), 248 parts by mass of adipic acid, 278 parts by mass of isophthalic acid, anhydrous 278 parts by weight of phthalic acid and 0.1 part by weight of an organic titanium compound are charged, and dry nitrogen is flowed into the flask and heated to 240 to 250 ° C. with stirring. Stealization reaction was performed. The reaction was stopped when the acid value became 1.0 mgKOH / g or less, and after cooling to 100 ° C., the mixture was diluted with ethyl acetate so that the solid content became 60% by mass. Next, 60 parts by mass of dicyclohexylmethane 4,4′-diisocyanate was charged, and dry nitrogen was flowed into the flask and heated to 70 to 80 ° C. with stirring to conduct a urethanization reaction. The reaction was stopped when the isocyanate content became 0.3% or less, and diluted with ethyl acetate to a solid content of 50% by mass to obtain a polyester polyurethane polyol (A5) solution. The number average molecular weight (Mn) of the polyester polyurethane polyol (A5) is 10,800, the weight average molecular weight (Mw) is 55,000, the molecular weight distribution (Mw / Mn) is 5.1, and the hydroxyl value of the solid content is 3.2 mgKOH. / G.
製造例６
ポリエステルポリウレタンポリオール（Ａ６）溶液の製造
攪拌棒、温度センサー、精留管を有するフラスコに、トリメチロールプロパン１５質量部、ネオペンチルグリコール３００質量部、１，６−ヘキサンジオール２４１質量部、前記多塩基酸組成物（築野食品工業株式会社製「ツノダイム２２８」組成：炭素原子数１７の炭化水素基を主骨格とする一塩基酸を５質量％、炭素原子数３４の炭化水素基を主骨格とする二塩基酸を８０．８質量％、炭素原子数５１の炭化水素基を主骨格とする三塩基酸を１４．２質量％）２２５質量部、アジピン酸１５０質量部、イソフタル酸３００質量部、無水フタル酸２６９質量部及び有機チタン化合物０．１質量部を仕込み、乾燥窒素をフラスコ内にフローさせ攪拌しながら２４０〜２５０℃に加熱しエステル化反応を行った。酸価が１．０ｍｇＫＯＨ／ｇ以下となったところで反応を停止し、１００℃まで冷却後、酢酸エチルで固形分が６０質量％になるように希釈した。次いで、イソホロンジイソシアネート５６質量部を仕込み、乾燥窒素をフラスコ内にフローさせ攪拌しながら７０〜８０℃に加熱しウレタン化反応を行った。イソシアネート含有率０．３％以下となったところで反応を停止し、酢酸エチルで固形分が５０質量％になるように希釈して、ポリエステルポリウレタンポリオール（Ａ６）溶液を得た。ポリエステルポリウレタンポリオール（Ａ６）の数平均分子量（Ｍｎ）は７，１００、重量平均分子量（Ｍｗ）は８２，０００、分子量分布（Ｍｗ／Ｍｎ）は１１．５、固形分の水酸基価は４．７ｍｇＫＯＨ／ｇであった。
Production Example 6
Manufacture of Polyester Polyurethane Polyol (A6) Solution In a flask having a stirring bar, a temperature sensor, and a rectifying tube, 15 parts by mass of trimethylolpropane, 300 parts by mass of neopentyl glycol, 241 parts by mass of 1,6-hexanediol, the polybasic Acid composition (“Tsunodaim 228” manufactured by Tsukino Food Industry Co., Ltd.) composition: 5% by mass of a monobasic acid having a hydrocarbon group having 17 carbon atoms as the main skeleton and a hydrocarbon group having 34 carbon atoms as the main skeleton 80.8% by mass of dibasic acid, 14.2% by mass of tribasic acid having a hydrocarbon group having 51 carbon atoms as the main skeleton) 225 parts by mass, 150 parts by mass of adipic acid, 300 parts by mass of isophthalic acid, Charge 269 parts by weight of phthalic anhydride and 0.1 part by weight of an organic titanium compound, flow dry nitrogen into the flask and heat to 240 to 250 ° C. with stirring. An esterification reaction was performed. The reaction was stopped when the acid value became 1.0 mgKOH / g or less, and after cooling to 100 ° C., the mixture was diluted with ethyl acetate so that the solid content became 60% by mass. Next, 56 parts by mass of isophorone diisocyanate was charged, and dry nitrogen was allowed to flow into the flask and heated to 70 to 80 ° C. while stirring to conduct a urethanization reaction. The reaction was stopped when the isocyanate content became 0.3% or less, and diluted with ethyl acetate to a solid content of 50% by mass to obtain a polyester polyurethane polyol (A6) solution. The number average molecular weight (Mn) of the polyester polyurethane polyol (A6) is 7,100, the weight average molecular weight (Mw) is 82,000, the molecular weight distribution (Mw / Mn) is 11.5, and the hydroxyl value of the solid content is 4.7 mgKOH. / G.
比較製造例１
ポリエステルポリウレタンポリオール（ａ１）の製造
攪拌棒、温度センサー、精留管を有するフラスコに、ネオペンチルグリコール２８２．６質量部、１，６−ヘキサンジオール２７５．１質量部、エチレングリコール１１２．８質量部、イソフタル酸６３４．５質量部、セバシン酸３６８．７質量部及びエステル化触媒として有機チタン化合物０．０２質量部を仕込み、乾燥窒素をフラスコ内にフローさせ攪拌しながら２３０〜２５０℃に加熱しエステル化反応を行った。酸価が１．０ｍｇＫＯＨ／ｇ以下となったところで反応を停止し、１００℃まで冷却した後、酢酸エチルで固形分が８０質量％になるように希釈した。次いで、イソホロンジイソシアネート６８．７質量部を仕込み、乾燥窒素をフラスコ内にフローさせ攪拌しながら８０〜９０℃に加熱してウレタン化反応を行った。イソシアネート含有率が０．３％以下となったところで反応を停止し、重量平均分子量が３７，０００、数平均分子量（Ｍｎ）８，０００、分子量分布（Ｍｗ／Ｍｎ）４．６、水酸基価が１０ｍｇＫＯＨ／ｇのポリエステルポリウレタンポリオール（ａ１）を得た。これを酢酸エチルで固形分が６２質量％になるように希釈し、ポリエステルポリウレタンポリオール（ａ１）溶液とした。
Comparative production example 1
Manufacture of polyester polyurethane polyol (a1) In a flask having a stirrer, a temperature sensor, and a rectifying tube, 282.6 parts by mass of neopentyl glycol, 275.1 parts by mass of 1,6-hexanediol, and 112.8 parts by mass of ethylene glycol , 634.5 parts by mass of isophthalic acid, 368.7 parts by mass of sebacic acid, and 0.02 part by mass of an organic titanium compound as an esterification catalyst, and heated to 230-250 ° C. while stirring and flowing dry nitrogen into the flask An esterification reaction was performed. The reaction was stopped when the acid value became 1.0 mgKOH / g or less, and after cooling to 100 ° C., it was diluted with ethyl acetate so that the solid content became 80% by mass. Next, 68.7 parts by mass of isophorone diisocyanate was charged, and dry nitrogen was flowed into the flask and heated to 80 to 90 ° C. with stirring to conduct a urethanization reaction. The reaction was stopped when the isocyanate content became 0.3% or less, the weight average molecular weight was 37,000, the number average molecular weight (Mn) was 8,000, the molecular weight distribution (Mw / Mn) was 4.6, and the hydroxyl value was A 10 mg KOH / g polyester polyurethane polyol (a1) was obtained. This was diluted with ethyl acetate to a solid content of 62% by mass to obtain a polyester polyurethane polyol (a1) solution.
本発明の実施例及び比較例で用いたエポキシ樹脂（Ｂ）を以下に示す。
・エポキシ樹脂（Ｂ１）：数平均分子量（Ｍｎ）４７０、エポキシ当量２４５ｇ／ｅｑ、水酸基価５４ｍｇＫＯＨ／ｇのビスフェノールＡ型エポキシ樹脂（ＤＩＣ株式会社製「エピクロン８６０」）
・エポキシ樹脂（Ｂ２）：数平均分子量（Ｍｎ）９００、エポキシ当量４７５ｇ／ｅｑ、水酸基価１２５ｍｇＫＯＨ／ｇのビスフェノールＡ型エポキシ樹脂（三菱化学社製「ＪＥＲ１００１」）
The epoxy resin (B) used in Examples and Comparative Examples of the present invention is shown below.
Epoxy resin (B1): bisphenol A type epoxy resin having a number average molecular weight (Mn) of 470, an epoxy equivalent of 245 g / eq, and a hydroxyl value of 54 mgKOH / g (“Epiclon 860” manufactured by DIC Corporation)
Epoxy resin (B2): bisphenol A type epoxy resin having a number average molecular weight (Mn) of 900, an epoxy equivalent of 475 g / eq, and a hydroxyl value of 125 mgKOH / g (“JER1001” manufactured by Mitsubishi Chemical Corporation)
本発明の実施例及び比較例で用いたポリカーボネート樹脂（Ｃ）を以下に示す。
・ポリカーボネートポリオール（Ｃ１）：数平均分子量（Ｍｎ）１，０００、水酸基価１１０ｍｇＫＯＨ／ｇのポリカーボネートジオール（ダイセル化学社製「プラクセルＣＤ２１０」）
The polycarbonate resin (C) used in Examples and Comparative Examples of the present invention is shown below.
Polycarbonate polyol (C1): polycarbonate diol having a number average molecular weight (Mn) of 1,000 and a hydroxyl value of 110 mgKOH / g (“Placcel CD210” manufactured by Daicel Chemical Industries)
本発明の実施例及び比較例で用いたポリイソシアネート（Ｄ）を以下に示す。
・ポリイソシアネート（Ｄ１）：ヘキサメチレンジイソシアネートのヌレート変性体（住友バイエルウレタン社製「スミジュールＮ３３００」）
・ポリイソシアネート（Ｄ２）：ヘキサメチレンジイソシアネート（ＤＩＣ株式会社製「バーノックＤＮ９５５Ｓ」）
The polyisocyanate (D) used in Examples and Comparative Examples of the present invention is shown below.
-Polyisocyanate (D1): a hexamethylene diisocyanate nurate modified product ("Sumijour N3300" manufactured by Sumitomo Bayer Urethane Co., Ltd.)
Polyisocyanate (D2): Hexamethylene diisocyanate (“Bernock DN955S” manufactured by DIC Corporation)
実施例１
前記製造例１で得たポリエステルポリウレタンポリオール（Ａ１）溶液１００質量部、前記エポキシ樹脂（Ｂ１）１０質量部、前記ポリカーボネートポリオール（Ｃ１）１５質量部及び前記ポリイソシアネート（Ｄ１）１０質量部を混合し、酢酸エチルで固形分が５０％になるように調子して樹脂組成物を得、下記の要領で評価サンプルを作成し、以下に示す方法で評価を行った。結果を表１に示す。
Example 1
100 parts by mass of the polyester polyurethane polyol (A1) solution obtained in Production Example 1, 10 parts by mass of the epoxy resin (B1), 15 parts by mass of the polycarbonate polyol (C1) and 10 parts by mass of the polyisocyanate (D1) are mixed. The solid content was adjusted to 50% with ethyl acetate to obtain a resin composition. An evaluation sample was prepared in the following manner and evaluated by the following method. The results are shown in Table 1.
評価サンプルの作成
１２５μｍ厚のＰＥＴフィルム（東レ株式会社製「ルミラーＸ１０Ｓ」）を基材とし、上記実施例１で得た樹脂組成物を、溶剤乾燥後の固形分の質量が５〜６ｇ／ｍ２の範囲となるように塗装した後、２５μｍ厚のフッ素フィルム（旭硝子株式会社製「アフレックス２５ＰＷ」）を貼合して積層フィルムを得た。これを、５０℃で７２時間エージングし、評価サンプルを得た。
Preparation of Evaluation Sample Using a 125 μm-thick PET film (“Lumirror X10S” manufactured by Toray Industries, Inc.) as a base material, the resin composition obtained in Example 1 above has a solid mass of 5 to 6 g / m after solvent drying. After coating so as to be in the range of 2 , a 25 μm-thick fluorine film (“Aflex 25PW” manufactured by Asahi Glass Co., Ltd.) was bonded to obtain a laminated film. This was aged at 50 ° C. for 72 hours to obtain an evaluation sample.
評価１：接着力の測定
前記方法で作成した評価サンプルについて、引っ張り試験機（ＳＨＩＭＡＤＺＵ社製「ＡＧＳ５００ＮＧ」）を用い、１５ｍｍ幅、剥離速度３００ｍｍ／ｍｉｎにて１８０°剥離試験を行い、その強度を接着力として評価した。評価サンプルの初期の接着力と、１２１℃、湿度１００％環境下で２５時間、５０時間、７５時間暴露した後のそれぞれのサンプルの接着力を測定した。
Evaluation 1: Measurement of adhesive strength Using an tensile tester (“AGS500NG” manufactured by SHIMADZU), an evaluation sample prepared by the above method is subjected to a 180 ° peel test at a width of 15 mm and a peel speed of 300 mm / min. The adhesive strength was evaluated. The initial adhesive strength of the evaluation sample and the adhesive strength of each sample after exposure for 25 hours, 50 hours, and 75 hours in an environment of 121 ° C. and 100% humidity were measured.
評価２：耐湿熱性の評価
前記評価１で測定した評価サンプルの初期の接着力と、１２１℃、湿度１００％環境下で７５時間暴露した後のサンプルの接着力とを比較し、暴露後の接着力が初期の接着力の６０％以上であったものを○、４０％以上６０％未満であったものを△、４０％未満であったものを×として評価した。
Evaluation 2: Evaluation of heat-and-moisture resistance The initial adhesion force of the evaluation sample measured in the above-mentioned evaluation 1 was compared with the adhesion force of the sample after exposure for 75 hours in an environment of 121 ° C. and 100% humidity. The case where the force was 60% or more of the initial adhesive force was evaluated as ◯, the case where the force was 40% or more and less than 60% was evaluated as Δ, and the case where it was less than 40% was evaluated as ×.
実施例２〜１０
樹脂組成物の配合を表１に示したように変えた以外は、実施例１と同様にして評価サンプルを作成し、評価した。評価結果を表１に示す。
Examples 2-10
An evaluation sample was prepared and evaluated in the same manner as in Example 1 except that the composition of the resin composition was changed as shown in Table 1. The evaluation results are shown in Table 1.
比較例１
樹脂組成物の配合を表２に示したように変えた以外は、実施例１と同様にして評価サンプルを作成し、評価した。評価結果を表２に示す。
Comparative Example 1
An evaluation sample was prepared and evaluated in the same manner as in Example 1 except that the composition of the resin composition was changed as shown in Table 2. The evaluation results are shown in Table 2.
Claims (13)
ビスフェノール型エポキシ樹脂（Ｂ）と、
ポリカーボネート樹脂（Ｃ）と、
ポリイソシアネート化合物（Ｄ）とを必須の成分として含有することを特徴とする樹脂組成物。 Essentially, a polybasic acid (E) containing a dibasic acid (E1) having a hydrocarbon group having a carbon number of 14 to 46 as a main skeleton, a diol compound (F), and a diisocyanate compound (G) Polyester polyurethane polyol (A) obtained by reacting as a component of
A bisphenol type epoxy resin (B);
Polycarbonate resin (C);
A resin composition comprising a polyisocyanate compound (D) as an essential component.
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| JP2015003950A (en) * | 2013-06-19 | 2015-01-08 | Dic株式会社 | Novel polyester polyurethane polyol, polyol agent for two-liquid type laminate adhesive, resin composition, curable resin composition, adhesive for two-liquid type laminate and back sheet for solar cell |
| JP2015063579A (en) * | 2013-09-24 | 2015-04-09 | Dic株式会社 | Moisture-curable polyurethane hot-melt resin composition, adhesive agent and laminate |
| JP6170211B1 (en) * | 2016-07-15 | 2017-07-26 | 株式会社フジクラ | Thermosetting adhesive composition, coverlay film, adhesive film, metal-clad laminate and flexible printed wiring board |
| WO2018193957A1 (en) * | 2017-04-21 | 2018-10-25 | Dic株式会社 | Urethane-modified polyisocyanate compound, curing agent for two-part curable urethane adhesive agent, adhesive agent, and back sheet for solar cell |
| CN111057213A (en) * | 2019-12-31 | 2020-04-24 | 北京市市政工程研究院 | Latent curing polyurethane material for maintaining hinge joint of fabricated concrete hollow slab bridge and preparation method thereof |
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| JP2015003950A (en) * | 2013-06-19 | 2015-01-08 | Dic株式会社 | Novel polyester polyurethane polyol, polyol agent for two-liquid type laminate adhesive, resin composition, curable resin composition, adhesive for two-liquid type laminate and back sheet for solar cell |
| JP2015063579A (en) * | 2013-09-24 | 2015-04-09 | Dic株式会社 | Moisture-curable polyurethane hot-melt resin composition, adhesive agent and laminate |
| JP6170211B1 (en) * | 2016-07-15 | 2017-07-26 | 株式会社フジクラ | Thermosetting adhesive composition, coverlay film, adhesive film, metal-clad laminate and flexible printed wiring board |
| JP2018009122A (en) * | 2016-07-15 | 2018-01-18 | 株式会社フジクラ | Thermosetting adhesive composition, coverlay film, adhesive film, metal-clad laminate and flexible printed wiring board |
| WO2018193957A1 (en) * | 2017-04-21 | 2018-10-25 | Dic株式会社 | Urethane-modified polyisocyanate compound, curing agent for two-part curable urethane adhesive agent, adhesive agent, and back sheet for solar cell |
| JP6795079B1 (en) * | 2019-12-03 | 2020-12-02 | 東洋インキＳｃホールディングス株式会社 | Adhesive composition and adhesive sheet |
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| JP2021088631A (en) * | 2019-12-03 | 2021-06-10 | 東洋インキＳｃホールディングス株式会社 | Adhesive composition and adhesive sheet |
| CN111057213A (en) * | 2019-12-31 | 2020-04-24 | 北京市市政工程研究院 | Latent curing polyurethane material for maintaining hinge joint of fabricated concrete hollow slab bridge and preparation method thereof |
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