JP6680074B2 - Alicyclic epoxy compound, resin composition and cured product - Google Patents
Alicyclic epoxy compound, resin composition and cured product Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims description 66
- 239000004593 Epoxy Substances 0.000 title claims description 26
- 125000002723 alicyclic group Chemical group 0.000 title claims description 19
- 239000011342 resin composition Substances 0.000 title claims 6
- 239000000203 mixture Substances 0.000 claims description 47
- 229920005862 polyol Polymers 0.000 claims description 22
- 150000003077 polyols Chemical class 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 229920000515 polycarbonate Polymers 0.000 claims description 11
- 239000004417 polycarbonate Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 3
- 150000002009 diols Chemical class 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 description 25
- 229920000647 polyepoxide Polymers 0.000 description 25
- -1 Diaryl carbonate Chemical compound 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- TZTRNALMVOGNSM-UHFFFAOYSA-N cyclohex-2-en-1-ylmethanol Chemical compound OCC1CCCC=C1 TZTRNALMVOGNSM-UHFFFAOYSA-N 0.000 description 2
- VEIYJWQZNGASMA-UHFFFAOYSA-N cyclohex-3-en-1-ylmethanol Chemical compound OCC1CCC=CC1 VEIYJWQZNGASMA-UHFFFAOYSA-N 0.000 description 2
- ILUAAIDVFMVTAU-UHFFFAOYSA-N cyclohex-4-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CC=CCC1C(O)=O ILUAAIDVFMVTAU-UHFFFAOYSA-N 0.000 description 2
- NZNMSOFKMUBTKW-UHFFFAOYSA-M cyclohexanecarboxylate Chemical compound [O-]C(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-M 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 229920005906 polyester polyol Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- SDUZNEIVCAVWSH-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptane-3,4-dicarboxylic acid Chemical compound C1C(C(O)=O)C(C(=O)O)CC2OC21 SDUZNEIVCAVWSH-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N C1CC2OC2CC1 Chemical compound C1CC2OC2CC1 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- OFHFTWINYTYOOE-UHFFFAOYSA-N O=C(C(CC1)C2OC2C1C(OCC1C(C2)OC2CC1)=O)OCC1C2OC2CCC1 Chemical compound O=C(C(CC1)C2OC2C1C(OCC1C(C2)OC2CC1)=O)OCC1C2OC2CCC1 OFHFTWINYTYOOE-UHFFFAOYSA-N 0.000 description 1
- KNLVHCLFAUOMMM-UHFFFAOYSA-N OC(C(CC1)CC2OC2CC1C(OCCC1CC2OC2CC1)=O)=O Chemical compound OC(C(CC1)CC2OC2CC1C(OCCC1CC2OC2CC1)=O)=O KNLVHCLFAUOMMM-UHFFFAOYSA-N 0.000 description 1
- FQCJBRVTYJVAEF-UHFFFAOYSA-N OCC1C(CO)CC=CC1 Chemical compound OCC1C(CO)CC=CC1 FQCJBRVTYJVAEF-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910018286 SbF 6 Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 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 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004650 carbonic acid diesters Chemical class 0.000 description 1
- 150000004651 carbonic acid esters Chemical class 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- MQNAWGURFBPDMW-UHFFFAOYSA-N cyclohex-2-en-1-yl acetate Chemical compound CC(=O)OC1CCCC=C1 MQNAWGURFBPDMW-UHFFFAOYSA-N 0.000 description 1
- IHLIVAHFDOAPFC-UHFFFAOYSA-N cyclohex-2-ene-1,4-dicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)C=C1 IHLIVAHFDOAPFC-UHFFFAOYSA-N 0.000 description 1
- YVWBQGFBSVLPIK-UHFFFAOYSA-N cyclohex-2-ene-1-carboxylic acid Chemical compound OC(=O)C1CCCC=C1 YVWBQGFBSVLPIK-UHFFFAOYSA-N 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Chemical class 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Epoxy Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
Description
本発明は、硬化性のエポキシ化合物に関する。本発明の脂環式エポキシ化合物を使用した組成物は、耐熱性、耐候性、柔軟性、耐水性などの性能が必要な様々な分野で有用である。 The present invention relates to a curable epoxy compound. The composition using the alicyclic epoxy compound of the present invention is useful in various fields in which performance such as heat resistance, weather resistance, flexibility and water resistance is required.
エポキシ樹脂は、ビスフェノールタイプ、フェノールタイプ、クレゾールタイプ、脂環式タイプなどの主剤と、アミン／ポリアミン／ポリアミド、酸無水物、ポリメルカプタン系、ＵＶ系などの硬化剤とからなるもので、その硬化物は一般に機械強度、電気絶縁性、耐薬品性、接着性に優れる。 Epoxy resin consists of a main agent such as bisphenol type, phenol type, cresol type, alicyclic type, etc. and a curing agent such as amine / polyamine / polyamide, acid anhydride, polymercaptan type, UV type, etc. Materials generally have excellent mechanical strength, electrical insulation, chemical resistance, and adhesiveness.
特に脂環式エポキシ樹脂は、塗料などのコーティング材料から接着剤、光学部材まで幅広い用途で使用されているが、無色透明で機械強度、耐熱性、耐光性、耐水性に優れ、更に柔軟性も備えた硬化物を与えるものはこれまで無かった。 In particular, alicyclic epoxy resins are used in a wide range of applications from coating materials such as paints to adhesives and optical components, but they are colorless and transparent and have excellent mechanical strength, heat resistance, light resistance, water resistance, and also flexibility. Until now, no one has provided a cured product.
例えば、特許文献１に記載のエポキシ樹脂組成物では、無色透明で機械強度に優れる硬化膜が得られるものの、柔軟性が十分ではなく、耐水性も十分ではなかった。また、特許文献２に記載のエポキシ樹脂組成物では、機械強度に優れ、耐水性の良い硬化膜が得られるものの、柔軟性が十分ではなく、わずかに着色が見られる。 For example, with the epoxy resin composition described in Patent Document 1, a cured film that is colorless and transparent and has excellent mechanical strength can be obtained, but the flexibility and water resistance were not sufficient. Further, with the epoxy resin composition described in Patent Document 2, although a cured film having excellent mechanical strength and good water resistance can be obtained, flexibility is not sufficient and slight coloring is observed.
脂環式エポキシ樹脂とポリオール成分で無色透明な機械強度の高い硬化膜を得る場合、使用するポリオール成分によって物性が左右される傾向がある。ポリエステルポリオールを使用した場合は耐水性が悪く、ポリエーテルポリオールを使用した場合は耐熱性、耐候性が悪く、ポリカーボネートポリオールを使用した場合は柔軟性が悪くなる。したがって、脂環式エポキシ樹脂とポリオール成分を用いて、無色透明で、機械強度がよく、耐熱性、耐光性、耐水性に優れ、更に柔軟性のある硬化物を作ることは困難であった。 When a colorless and transparent cured film having high mechanical strength is obtained from an alicyclic epoxy resin and a polyol component, the physical properties tend to be influenced by the polyol component used. Water resistance is poor when a polyester polyol is used, heat resistance and weather resistance are poor when a polyether polyol is used, and flexibility is poor when a polycarbonate polyol is used. Therefore, it has been difficult to produce a cured product which is colorless and transparent, has good mechanical strength, is excellent in heat resistance, light resistance and water resistance, and is flexible, using an alicyclic epoxy resin and a polyol component.
これらの問題を鑑みて、本発明は、無色透明で、機械強度がよく、耐熱性、耐光性、耐水性に優れ、更に柔軟性のある硬化物が得られる脂環式エポキシ化合物を提供する。また、本発明は、ポリカーボネートポリオールを使用した組成物でも柔軟性が発揮できるエポキシ樹脂組成物を提供する。 In view of these problems, the present invention provides an alicyclic epoxy compound which is colorless and transparent, has good mechanical strength, is excellent in heat resistance, light resistance, and water resistance, and can obtain a cured product having flexibility. The present invention also provides an epoxy resin composition that can exhibit flexibility even in a composition using a polycarbonate polyol.
本発明の脂環式エポキシ化合物は、一般式（１）あるいは（２）で表される２種以上の化合物の混合物からなるものである。 The alicyclic epoxy compound of the present invention comprises a mixture of two or more compounds represented by the general formula (1) or (2).
本発明のエポキシ樹脂組成物は、上記一般式（１）あるいは（２）で表される２種以上の化合物の混合物からなる脂環式エポキシ化合物とポリオールと硬化剤とを含有するものである。 The epoxy resin composition of the present invention contains an alicyclic epoxy compound composed of a mixture of two or more compounds represented by the general formula (1) or (2), a polyol and a curing agent.
本発明のエポキシ樹脂組成物は、上記一般式（１）あるいは（２）で表される２種以上の化合物の混合物からなる脂環式エポキシ化合物とポリオールと光酸発生剤とを含有するものである。 The epoxy resin composition of the present invention contains an alicyclic epoxy compound consisting of a mixture of two or more compounds represented by the general formula (1) or (2), a polyol, and a photoacid generator. is there.
本発明のエポキシ樹脂組成物において、ポリオールが、ポリカーボネートジオールであることが好ましい。 In the epoxy resin composition of the present invention, the polyol is preferably polycarbonate diol.
本発明におけるエポキシ化合物及びこれを用いたエポキシ樹脂組成物は、無色透明で機械強度がよく、耐熱性、耐光性、耐水性に優れ、柔軟性のある硬化物を得ることができるため、塗料などのコーティング材料から接着剤、光学部材として最適である。 The epoxy compound and the epoxy resin composition using the same in the present invention are colorless and transparent, have good mechanical strength, excellent heat resistance, light resistance, water resistance, and a flexible cured product can be obtained. It is most suitable for coating materials, adhesives, and optical members.
本実施形態におけるエポキシ化合物およびエポキシ樹脂組成物は、塗料などのコーティング材料から接着剤、光学部材として利用されるものであり、鋭意研究を重ねた結果、これらの硬化物には、無色透明で、機械強度がよく、耐熱性、耐光性、耐水性に優れ、柔軟性が必要という結論に達した。本発明は、無色透明で機械強度がよく、耐熱性、耐光性、耐水性に優れ、更に柔軟性のある硬化物が得られる脂環式エポキシ化合物を提供するものであり、また、その硬化物を与えるエポキシ樹脂組成物を提供するものである。 The epoxy compound and the epoxy resin composition in the present embodiment are used as an adhesive, an optical member, from a coating material such as a paint, and as a result of intensive studies, these cured products are colorless and transparent, It was concluded that good mechanical strength, heat resistance, light resistance, water resistance, and flexibility are required. The present invention provides an alicyclic epoxy compound which is colorless and transparent, has good mechanical strength, is excellent in heat resistance, light resistance, and water resistance, and is a flexible cured product, and the cured product thereof. The present invention provides an epoxy resin composition that gives
具体的に、本実施形態に係る脂環式エポキシ化合物は、下記一般式（１）あるいは（２）で表されるものである。 Specifically, the alicyclic epoxy compound according to this embodiment is represented by the following general formula (1) or (2).
本実施形態における一般式（１）の脂環式エポキシ化合物は、既存の合成法から容易に合成できるが、例えば、構造式（３）の化合物を酸化して構造式（４）の化合物を合成し、構造式（３）と構造式（４）の化合物を反応させて構造式（５）の化合物を合成する。その後、構造式（５）の化合物に酸素付加することによって、一般式（１）に含まれる構造式（６）の化合物を合成することが可能である。 The alicyclic epoxy compound of the general formula (1) in the present embodiment can be easily synthesized by an existing synthesis method. For example, the compound of the structural formula (3) is oxidized to synthesize the compound of the structural formula (4). Then, the compound of structural formula (3) is reacted with the compound of structural formula (4) to synthesize the compound of structural formula (5). Then, by adding oxygen to the compound of structural formula (5), the compound of structural formula (6) included in general formula (1) can be synthesized.
同様に、例えば、構造式（７）の化合物を酸化して構造式（８）の化合物を合成し、構造式（３）と構造式（８）の化合物を反応させて構造式（９）の化合物を合成する。その後、構造式（９）の化合物に酸素付加することによって、一般式（１）に含まれる構造式（１０）の化合物を合成することが可能である。 Similarly, for example, the compound of the structural formula (7) is oxidized to synthesize the compound of the structural formula (8), and the compound of the structural formula (3) is reacted with the compound of the structural formula (8) to obtain the compound of the structural formula (9). The compound is synthesized. Then, the compound of structural formula (9) contained in the general formula (1) can be synthesized by adding oxygen to the compound of structural formula (9).
さらには、構造式（７）の化合物を酸化して構造式（７）と構造式（８）の混合物を調製し、構造式（３）と構造式（７）と構造式（８）の化合物を反応させて構造式（９）と構造式（１１）の混合物を調製する。その後、構造式（９）と構造式（１１）の化合物混合物に酸素付加することによって、一般式（１）に含まれる構造式（１０）と構造式（１２）の混合物を合成することが可能である。 Furthermore, the compound of structural formula (7) is oxidized to prepare a mixture of structural formula (7) and structural formula (8), and the compound of structural formula (3), structural formula (7) and structural formula (8) is obtained. To prepare a mixture of structural formulas (9) and (11). Then, oxygen is added to the compound mixture of the structural formulas (9) and (11) to synthesize a mixture of the structural formulas (10) and (12) included in the general formula (1). Is.
本実施形態における一般式（２）の脂環式エポキシ化合物は、既存の合成法から容易に合成できるが、例えば、構造式（１３）の化合物を酸化して構造式（１４）の化合物を合成し、構造式（３）と構造式（１４）の化合物を反応させて構造式（１５）の化合物を合成する。その後、構造式（１５）の化合物に酸素付加することによって、一般式（２）に含まれる構造式（１６）の化合物を合成することが可能である。 The alicyclic epoxy compound of the general formula (2) in the present embodiment can be easily synthesized by an existing synthesis method. For example, the compound of the structural formula (13) is oxidized to synthesize the compound of the structural formula (14). Then, the compound of structural formula (3) is reacted with the compound of structural formula (14) to synthesize the compound of structural formula (15). Then, by adding oxygen to the compound of structural formula (15), the compound of structural formula (16) included in general formula (2) can be synthesized.
同様に、例えば、構造式（１７）の化合物を酸化して構造式（１８）の化合物を合成し、構造式（７）と構造式（１８）の化合物を反応させて構造式（１９）の化合物を合成する。その後、構造式（１９）の化合物に酸素付加することによって、一般式（２）に含まれる構造式（２０）の化合物を合成することが可能である。 Similarly, for example, the compound of the structural formula (17) is oxidized to synthesize the compound of the structural formula (18), and the compound of the structural formula (7) is reacted with the compound of the structural formula (18) to obtain the compound of the structural formula (19). The compound is synthesized. Then, oxygen can be added to the compound of structural formula (19) to synthesize the compound of structural formula (20) included in general formula (2).
さらには、構造式（３）と構造式（７）の化合物と構造式（１８）と構造式（２１）の化合物を反応させて、構造式（１９）と構造式（２２）と構造式（２３）と構造式（２４）と構造式（２５）と構造式（２６）の混合物を調製する。その後、構造式（１９）と構造式（２２）と構造式（２３）と構造式（２４）と構造式（２５）と構造式（２６）の化合物混合物に酸素付加することによって、一般式（２）に含まれる構造式（２０）と構造式（２７）と構造式（２８）と構造式（２９）と構造式（３０）と構造式（３１）の化合物混合物を合成することが可能である。 Furthermore, the compounds of structural formula (3) and structural formula (7) are reacted with the compounds of structural formula (18) and structural formula (21) to produce structural formula (19), structural formula (22), and structural formula (22). A mixture of 23), structural formula (24), structural formula (25) and structural formula (26) is prepared. Then, oxygen is added to the compound mixture of the structural formula (19), the structural formula (22), the structural formula (23), the structural formula (24), the structural formula (25), and the structural formula (26) to give the general formula ( It is possible to synthesize a compound mixture of structural formula (20), structural formula (27), structural formula (28), structural formula (29), structural formula (30) and structural formula (31) contained in 2). is there.
本発明で使用されるポリオールは、アルコール性水酸基を複数個有する多価アルコールなら何でも使用できるが、無色透明で耐光性のよい膜を得るためには、芳香環を有さない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などが望ましい。その中でも特に、耐熱性と耐水性に優れるポリカーボネートポリオールであることが望ましい。 The polyol used in the present invention may be any polyhydric alcohol having a plurality of alcoholic hydroxyl groups, but in order to obtain a colorless and transparent film having good light resistance, a polyester polyol or polyether having no aromatic ring is used. Polyol and polycarbonate polyol are preferable. Among them, a polycarbonate polyol having excellent heat resistance and water resistance is particularly preferable.
本発明で使用されるポリカーボネートポリオールは、ポリオール成分と炭酸ジエステルを用いてエステル交換反応で容易に作成することが可能で、使用できるポリオール成分は直鎖でも分岐でも特に制限は無いが、ジエチレングリコール、プロピレングリコール、１，４−ブタンジオール、１，５−ペンタンジオール、１，６−ヘキサンジオール、１，８−オクタンジオール、グリセリン、トリメチロールプロパン、ペンタエリスリトールなどが望ましく、炭酸エステルとしては、ジアルキルカーボネート、ジアリールカーボネート、アルキレンカーボネートなどが利用でき、エチレンカーボネート、ジフェニルカーボネートが望ましい。 The polycarbonate polyol used in the present invention can be easily prepared by a transesterification reaction using a polyol component and a carbonic acid diester, and the polyol component that can be used is not particularly limited, either linear or branched, but diethylene glycol, propylene. Glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, glycerin, trimethylolpropane, pentaerythritol and the like are desirable, and the carbonic acid ester is dialkyl carbonate, Diaryl carbonate, alkylene carbonate and the like can be used, and ethylene carbonate and diphenyl carbonate are preferable.
ただし、ポリカーボネートポリオールは、三価以上の多価アルコールを用いると得られるポリカーボネートポリオールの流動性が悪くなるため、ポリカーボネートジオールが一般的に使用されることが多い。 However, when a polyhydric alcohol having a valence of 3 or more is used as the polycarbonate polyol, the fluidity of the obtained polycarbonate polyol is deteriorated, so that the polycarbonate diol is generally used in many cases.
本発明で使用されるエポキシ樹脂硬化剤には特に制限は無く、脂肪族アミン、芳香族アミン、変性アミン、二級アミン、三級アミンなどのアミン系硬化剤、ポリアミド樹脂系硬化剤、イミダゾール系硬化剤、ポリメルカプタンやポリスルフィドなどのポリメルカプタン硬化剤、酸無水物系硬化剤、潜在性硬化剤、紫外線硬化剤などが使用できる。 The epoxy resin curing agent used in the present invention is not particularly limited, and amine-based curing agents such as aliphatic amines, aromatic amines, modified amines, secondary amines and tertiary amines, polyamide resin-based curing agents, imidazole-based curing agents. A curing agent, a polymercaptan curing agent such as polymercaptan or polysulfide, an acid anhydride curing agent, a latent curing agent, and an ultraviolet curing agent can be used.
本発明で使用されるエポキシ樹脂用光酸発生剤には特に制限は無く、スルホニウム塩系とヨードニウム塩系が存在するが光の吸収効率の部分でスルホニウム塩系が有利であり、スルホニウム塩系にはモノスルホニウム塩系とジスルホニウム塩系があり、アニオン部は、ＰＦ６、ＳｂＦ６などが一般に使用されていて、これらのものは全て使用可能である。 There is no particular limitation on the photo-acid generator for the epoxy resin used in the present invention, and there are sulfonium salt-based and iodonium salt-based, but the sulfonium salt-based is advantageous in the part of the light absorption efficiency, and the sulfonium salt-based is used. Includes a monosulfonium salt type and a disulfonium salt type, and PF 6 , SbF 6 and the like are generally used for the anion portion, and all of these can be used.
本発明では、光増感剤、界面活性剤およびレベリング剤、無機化合物などの添加剤、溶剤などの使用にも制限は無い。 In the present invention, there is no limitation on the use of photosensitizers, surfactants and leveling agents, additives such as inorganic compounds, solvents and the like.
以上、本発明に使用できる主な構成を示したが、次に、紫外線硬化塗膜の製造方法を例に挙げて使用方法を説明する。 The main constitutions that can be used in the present invention have been described above. Next, the method of use will be described taking the method for producing an ultraviolet-curing coating film as an example.
基材となるシート及びフィルム、ガラス、成形体などは任意のものが使用できるが、本発明のエポキシ化合物を含むエポキシ樹脂組成物は、ロールコーター、リバースロールコーター、グラビアコーター、ナイフコーター、バーコーター等により基材に塗工し、必要に応じて加熱乾燥した後、塗工面には、必要に応じてＰＥＴ（ポリエチレンテレフタレート）、ＰＥＮ（ポリエチレンナフタレート）、ＰＥ（ポリエチレン）、ＰＰ（ポリプロピレン）、Ｎｙ（ナイロン）などの保護フィルムを使用することもできる。 Any material such as a sheet and a film as a base material, glass, or a molded product can be used, but an epoxy resin composition containing the epoxy compound of the present invention is a roll coater, a reverse roll coater, a gravure coater, a knife coater, a bar coater. Etc., and then heat-dried if necessary, and then the coated surface has PET (polyethylene terephthalate), PEN (polyethylene naphthalate), PE (polyethylene), PP (polypropylene), A protective film such as Ny (nylon) can also be used.
本発明のエポキシ化合物を含むエポキシ樹脂組成物は、紫外線で硬化するが、紫外線を使用する場合は、高圧水銀灯、低圧水銀灯、超高圧水銀灯、メタルハライドランプ、カーボンアーク、キセノンアーク等の光源が利用でき、高圧水銀灯やメタルハライドランプが望ましい。 The epoxy resin composition containing the epoxy compound of the present invention is cured by ultraviolet rays, but when using ultraviolet rays, a light source such as a high pressure mercury lamp, a low pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a carbon arc or a xenon arc can be used. High pressure mercury lamps and metal halide lamps are desirable.
以下、本発明を実施例及び比較例をあげて具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
（実施例１）
２−シクロヘキセン−１−メタノールの２２．４ｇと３−シクロヘキセン−１−メタノールの２２．４ｇと２−シクロヘキセン−１−カルボン酸の１２.６ｇを濃硫酸下でエステル化し、２−シクロヘキセン−１−カルボン酸（２−シクロヘキセニル）メチル、２−シクロヘキセン−１−カルボン酸（３−シクロヘキセニル）メチルの混合物を１９.８ｇ得た（収率９０％）。ついで、酸素雰囲気下で処理し、２’，３’−エポキシシクロヘキシルメチル（２，３−エポキシ）シクロヘキサンカルボキシレート、３’，４’−エポキシシクロヘキシルメチル（２，３−エポキシ）シクロヘキサンカルボキシレートの混合物（エポキシ化合物混合物１）を２２.７ｇ得た（収率１００％）。
(Example 1)
22.4 g of 2-cyclohexene-1-methanol, 22.4 g of 3-cyclohexene-1-methanol and 12.6 g of 2-cyclohexene-1-carboxylic acid were esterified under concentrated sulfuric acid to give 2-cyclohexene-1- 19.8 g of a mixture of (2-cyclohexenyl) methyl carboxylate and (3-cyclohexenyl) methyl 2-cyclohexene-1-carboxylate was obtained (yield 90%). Then, the mixture is treated under an oxygen atmosphere, and a mixture of 2 ', 3'-epoxycyclohexylmethyl (2,3-epoxy) cyclohexanecarboxylate and 3', 4'-epoxycyclohexylmethyl (2,3-epoxy) cyclohexanecarboxylate. 22.7 g of (epoxy compound mixture 1) was obtained (yield 100%).
得られたエポキシ化合物混合物１を７０重量部、プラクセルＣＤ２０５ＰＬ（株式会社ダイセル）を３０重量部、オプトマーＳＰ−１７０（株式会社ＡＤＥＫＡ）を１重量部混合し、実施例１のエポキシ樹脂組成物を得た。 70 parts by weight of the obtained epoxy compound mixture 1, 30 parts by weight of Praxel CD205PL (Daicel Corporation) and 1 part by weight of Optomer SP-170 (ADEKA Corporation) were mixed to obtain an epoxy resin composition of Example 1. It was
（実施例２）
２−シクロヘキセン−１−メタノールの４４.８ｇと３−シクロヘキセン−１−メタノールの４４.８ｇと２−シクロヘキセン−１，４−ジカルボン酸の８.５ｇと４−シクロヘキセン−１，２−ジカルボン酸の８.５ｇを濃硫酸下でエステル化し、２−シクロヘキセン−１，４−ジカルボン酸ジ（２−シクロヘキセニル）メチル、２−シクロヘキセン−１，４−ジカルボン酸ジ（３−シクロヘキセニル）メチル、２−シクロヘキセン−１，４−ジカルボン酸モノ（２−シクロヘキセニル）メチルモノ（３−シクロヘキセニル）メチル、４−シクロヘキセン−１，２−ジカルボン酸ジ（２−シクロヘキセニル）メチル、４−シクロヘキセン−１，２−ジカルボン酸ジ（３−シクロヘキセニル）メチル、４−シクロヘキセン−１，２−ジカルボン酸モノ（２−シクロヘキセニル）メチルモノ（３−シクロヘキセニル）メチルの混合物を３０.４ｇ得た（収率８５％）。ついで、酸素雰囲気下で処理し、２，３−エポキシシクロヘキサン−１，４−ジカルボン酸ジ（２，３−エポキシシクロヘキシル）メチル、２，３−エポキシシクロヘキサン−１，４−ジカルボン酸ジ（３，４−エポキシシクロヘキシル）メチル、２，３−エポキシシクロヘキサン−１，４−ジカルボン酸モノ（２，３−エポキシシクロヘキシル）メチルモノ（３，４−エポキシシクロヘキシル）メチル、４，５−エポキシシクロヘキサン−１，２−ジカルボン酸ジ（２，３−エポキシシクロヘキシル）メチル、４，５−エポキシシクロヘキサン−１，２−ジカルボン酸ジ（３，４−エポキシシクロヘキシル）メチル、４，５−エポキシシクロヘキサン−１，２−ジカルボン酸モノ（２，３−エポキシシクロヘキシル）メチルモノ（３，４−エポキシシクロヘキシル）メチルの混合物（エポキシ化合物混合物２）を３４.５ｇ得た（収率１００％）。
(Example 2)
44.8 g of 2-cyclohexene-1-methanol, 44.8 g of 3-cyclohexene-1-methanol, 8.5 g of 2-cyclohexene-1,4-dicarboxylic acid and 4-cyclohexene-1,2-dicarboxylic acid Esterification of 8.5 g under concentrated sulfuric acid gave di (2-cyclohexenyl) methyl 2-cyclohexene-1,4-dicarboxylate, di (3-cyclohexenyl) methyl 2-cyclohexene-1,4-dicarboxylate, 2 -Cyclohexene-1,4-dicarboxylate mono (2-cyclohexenyl) methyl mono (3-cyclohexenyl) methyl, 4-cyclohexene-1,2-dicarboxylate di (2-cyclohexenyl) methyl, 4-cyclohexene-1, 2-dicarboxylic acid di (3-cyclohexenyl) methyl, 4-cyclohexene-1,2-dicarboxylic acid 30.4 g of a mixture of non- (2-cyclohexenyl) methyl mono (3-cyclohexenyl) methyl was obtained (yield 85%). Then, it is treated in an oxygen atmosphere to di (2,3-epoxycyclohexyl) methyl 2,3-epoxycyclohexane-1,4-dicarboxylate and di (3,2,3-epoxycyclohexane-1,4-dicarboxylic acid). 4-epoxycyclohexyl) methyl, 2,3-epoxycyclohexane-1,4-dicarboxylic acid mono (2,3-epoxycyclohexyl) methyl mono (3,4-epoxycyclohexyl) methyl, 4,5-epoxycyclohexane-1,2 -Di (2,3-epoxycyclohexyl) methyl dicarboxylate, 4,5-epoxycyclohexane-1,2-dicarboxylic acid di (3,4-epoxycyclohexyl) methyl, 4,5-epoxycyclohexane-1,2-dicarboxylic acid Acid mono (2,3-epoxycyclohexyl) methyl mono (3,4- Po carboxymethyl cyclohexyl) mixture of methyl (the epoxy compound mixture 2) to give 34.5 g (100% yield).
得られたエポキシ化合物混合物２を７０重量部、プラクセルＣＤ２０５ＰＬ（株式会社ダイセル）を３０重量部、オプトマーＳＰ−１７０（株式会社ＡＤＥＫＡ）を１重量部混合し、実施例２のエポキシ樹脂組成物を得た。 70 parts by weight of the obtained epoxy compound mixture 2, 30 parts by weight of Praxel CD205PL (Daicel Corporation) and 1 part by weight of Optomer SP-170 (ADEKA Corporation) were mixed to obtain an epoxy resin composition of Example 2. It was
（比較例１）
セロキサイド２０２１Ｐ（株式会社ダイセル）を７０重量部、プラクセル３０５（株式会社ダイセル）を３０重量部、オプトマーＳＰ−１７０（株式会社ＡＤＥＫＡ）を１重量部混合し、比較例１のエポキシ樹脂組成物を得た。
(Comparative Example 1)
70 parts by weight of Celoxide 2021P (Daicel Corporation), 30 parts by weight of Praxel 305 (Daicel Corporation) and 1 part by weight of Optomer SP-170 (ADEKA Corporation) were mixed to obtain an epoxy resin composition of Comparative Example 1. It was
（比較例２）
セロキサイド２０２１Ｐ（株式会社ダイセル）を７０重量部、プラクセルＣＤ２０５ＰＬ（株式会社ダイセル）を３０重量部、オプトマーＳＰ−１７０（株式会社ＡＤＥＫＡ）を１重量部混合し、比較例２のエポキシ樹脂組成物を得た。
(Comparative example 2)
70 parts by weight of Celoxide 2021P (Daicel Corporation), 30 parts by weight of Placcel CD205PL (Daicel Corporation), and 1 part by weight of Optomer SP-170 (ADEKA Corporation) were mixed to obtain an epoxy resin composition of Comparative Example 2. It was
各組成物は、ＰＥＴ（東レ（株）製ルミラーＳ１０）−７５μｍ上にバーコーターで約１００μｍ厚で塗工し、メタルハライドランプで２００ｍＪ／ｃｍ２照射して硬化させ、ＰＥＴフィルム上から硬化膜を回収した。 Each composition was coated on PET (Lumirror S10 manufactured by Toray Industries, Inc.)-75 μm with a bar coater to a thickness of about 100 μm and irradiated with a metal halide lamp to cure it at 200 mJ / cm 2 to form a cured film on the PET film. Recovered.
（透明性）
各組成物の硬化物を幅１０ｍｍ、長さ３０ｍｍの短冊状の試験片とし、紫外可視分光光度計ＵＶ−２６００（（株）島津製作所製）にて、４００−７００ｎｍの全光線透過率を測定し、９５％以上のものを○とした。
(transparency)
A cured product of each composition was used as a strip-shaped test piece having a width of 10 mm and a length of 30 mm, and the total light transmittance at 400-700 nm was measured with an ultraviolet-visible spectrophotometer UV-2600 (manufactured by Shimadzu Corporation). However, those with 95% or more were rated as ◯.
（耐水性）
各組成物の硬化物を幅１０ｍｍ、長さ３０ｍｍの短冊状の試験片とし、２３℃−２４hrの浸漬試験後に紫外可視分光光度計ＵＶ−２６００（（株）島津製作所製）にて、４００−７００ｎｍの全光線透過率を測定し、９５％以上のものを○とした。
(water resistant)
A cured product of each composition was used as a strip-shaped test piece having a width of 10 mm and a length of 30 mm, and after a dipping test at 23 ° C. for 24 hours, a UV-visible spectrophotometer UV-2600 (manufactured by Shimadzu Corporation) was used to measure 400- The total light transmittance at 700 nm was measured, and a light transmittance of 95% or more was evaluated as ◯.
（柔軟性）
各組成物の硬化物を幅１０ｍｍ、長さ１００ｍｍの短冊状の試験片とし、テンシロン万能材料試験機（株）エー・アンド・デイ製ＲＴＣ−１２１０Ａにて、チャック間距離５０ｍｍ、引張速度５００ｍｍ／ｍｉｎ、温度２３℃（相対湿度５５％）の条件下で測定し、膜としての機械強度を保持した上で、破断強度が２００ＭＰａ以下、３００％モジュラスが４０ＭＰａ以下のものを○とした。
(Flexibility)
A cured product of each composition was used as a strip-shaped test piece having a width of 10 mm and a length of 100 mm, and a distance between chucks was 50 mm and a pulling speed was 500 mm with an RTC-1210A manufactured by Tensilon Universal Material Testing Machine Co., Ltd. It was measured under the conditions of a min temperature of 23 ° C. (55% relative humidity), the mechanical strength of the film was maintained, and the breaking strength was 200 MPa or less, and the 300% modulus was 40 MPa or less was marked with ◯.
表１から明らかなように、本発明は、無色透明で、機械強度がよく、耐熱性、耐光性、耐水性に優れる柔軟性のある硬化物が得られる脂環式エポキシ化合物を提供できることが明らかになった。また、ポリカーボネートポリオールを使用した組成物でも柔軟性が発揮できるエポキシ樹脂組成物を提供できることが明らかになった。 As is clear from Table 1, it is clear that the present invention can provide an alicyclic epoxy compound which is colorless and transparent, has good mechanical strength, and is a flexible cured product having excellent heat resistance, light resistance, and water resistance. Became. It has also been clarified that an epoxy resin composition that can exhibit flexibility can be provided even with a composition using a polycarbonate polyol.
本発明は、巻き取り可能な自立フィルムを提供できるため、光学シートの基材に使用できる。また、本発明は、エポキシ樹脂組成物、例えば、塗料やコーティング材料のエポキシ樹脂組成物、ＬＥＤ等の発光素子を封止するためのエポキシ樹脂組成物に利用できる。 INDUSTRIAL APPLICABILITY Since the present invention can provide a self-supporting film that can be wound up, it can be used as a base material for an optical sheet. Further, the present invention can be applied to an epoxy resin composition, for example, an epoxy resin composition of a paint or a coating material, an epoxy resin composition for sealing a light emitting element such as an LED.
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