JP6198480B2 - Curing agent composition and cured product of epoxy resin using the same - Google Patents
Curing agent composition and cured product of epoxy resin using the same Download PDFInfo
- Publication number
- JP6198480B2 JP6198480B2 JP2013133665A JP2013133665A JP6198480B2 JP 6198480 B2 JP6198480 B2 JP 6198480B2 JP 2013133665 A JP2013133665 A JP 2013133665A JP 2013133665 A JP2013133665 A JP 2013133665A JP 6198480 B2 JP6198480 B2 JP 6198480B2
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- Prior art keywords
- group
- curing agent
- carbon atoms
- alkyl group
- hydroxyl group
- Prior art date
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- 239000003795 chemical substances by application Substances 0.000 title claims description 132
- 239000000203 mixture Substances 0.000 title claims description 73
- 239000003822 epoxy resin Substances 0.000 title description 46
- 229920000647 polyepoxide Polymers 0.000 title description 46
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 46
- 125000004432 carbon atom Chemical group C* 0.000 claims description 45
- 229920000768 polyamine Polymers 0.000 claims description 39
- 125000000217 alkyl group Chemical group 0.000 claims description 38
- 150000001491 aromatic compounds Chemical class 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 16
- 125000003277 amino group Chemical group 0.000 claims description 14
- 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 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 14
- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-UHFFFAOYSA-N 0.000 claims description 12
- 125000001931 aliphatic group Chemical group 0.000 claims description 12
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 12
- 125000003884 phenylalkyl group Chemical group 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 5
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 claims description 5
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 4
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 3
- XDESGXRLUIHEJT-UHFFFAOYSA-N 2,3,4-tribenzylphenol Chemical compound C=1C=CC=CC=1CC1=C(CC=2C=CC=CC=2)C(O)=CC=C1CC1=CC=CC=C1 XDESGXRLUIHEJT-UHFFFAOYSA-N 0.000 claims description 3
- CDMGNVWZXRKJNS-UHFFFAOYSA-N 2-benzylphenol Chemical compound OC1=CC=CC=C1CC1=CC=CC=C1 CDMGNVWZXRKJNS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- PGEBXGLGFFYYFX-UHFFFAOYSA-N 2,3-dibenzylphenol Chemical compound C=1C=CC=CC=1CC=1C(O)=CC=CC=1CC1=CC=CC=C1 PGEBXGLGFFYYFX-UHFFFAOYSA-N 0.000 claims description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 2
- GIMGBSVLYMNIMB-UHFFFAOYSA-N 3-amino-2-benzylphenol Chemical compound NC=1C(=C(C=CC1)O)CC1=CC=CC=C1 GIMGBSVLYMNIMB-UHFFFAOYSA-N 0.000 claims description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052705 radium Inorganic materials 0.000 claims description 2
- 229960004889 salicylic acid Drugs 0.000 claims description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims 2
- 238000001723 curing Methods 0.000 description 126
- 235000019645 odor Nutrition 0.000 description 53
- 150000001412 amines Chemical class 0.000 description 25
- -1 mensendiamine Chemical compound 0.000 description 21
- 239000000654 additive Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 14
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- 239000011347 resin Substances 0.000 description 13
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 12
- 238000002156 mixing Methods 0.000 description 11
- 238000000576 coating method Methods 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 230000000704 physical effect Effects 0.000 description 10
- 230000000996 additive effect Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000010276 construction Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000004593 Epoxy Substances 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- 239000000123 paper Substances 0.000 description 6
- 230000001629 suppression Effects 0.000 description 5
- 239000001993 wax Substances 0.000 description 5
- 230000002087 whitening effect Effects 0.000 description 5
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 235000019445 benzyl alcohol Nutrition 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000001953 sensory effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 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 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 239000002734 clay mineral Substances 0.000 description 3
- 229930003836 cresol Natural products 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- XMGQYMWWDOXHJM-JTQLQIEISA-N (+)-α-limonene Chemical compound CC(=C)[C@@H]1CCC(C)=CC1 XMGQYMWWDOXHJM-JTQLQIEISA-N 0.000 description 2
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- ZVDSMYGTJDFNHN-UHFFFAOYSA-N 2,4,6-trimethylbenzene-1,3-diamine Chemical compound CC1=CC(C)=C(N)C(C)=C1N ZVDSMYGTJDFNHN-UHFFFAOYSA-N 0.000 description 2
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 description 2
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical compound CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-UHFFFAOYSA-N 0.000 description 2
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- 229920002545 silicone oil Polymers 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Treating Waste Gases (AREA)
- Epoxy Resins (AREA)
Description
本発明は、硬化剤組成物、及びそれを用いたエポキシ樹脂の硬化物、並びにエポキシ樹脂硬化物の製造方法に関する。 The present invention relates to a curing agent composition, a cured product of an epoxy resin using the same, and a method for producing a cured epoxy resin.
エポキシ樹脂は、二官能性のエポキシ化合物と、ジアミンの重付加反応により得られる樹脂であり、当該エポキシ樹脂を硬化剤で硬化させた硬化物は、耐熱性、耐薬品性、電気特性、機械特性等が優れている。そのため、硬化前のエポキシ樹脂(プレポリマー)を塗料、接着剤、及び各種成形材料等として用い、成形、加工、施工後、エポキシ樹脂を硬化させることで、所望の物性に応じた幅広い、分野、用途において適用することができる。 An epoxy resin is a resin obtained by polyaddition reaction of a bifunctional epoxy compound and a diamine. A cured product obtained by curing the epoxy resin with a curing agent has heat resistance, chemical resistance, electrical properties, and mechanical properties. Etc. are excellent. Therefore, the epoxy resin (prepolymer) before curing is used as a paint, an adhesive, and various molding materials, etc., and after molding, processing, and construction, the epoxy resin is cured, and a wide range of fields according to desired physical properties, It can be applied in use.
エポキシ樹脂を硬化させるために用いる硬化剤は、主成分としてポリアミンや、ポリメルカプタン等が含まれていることが知られている。 It is known that a curing agent used for curing an epoxy resin contains polyamine, polymercaptan, or the like as a main component.
硬化剤の主成分として用いられるポリアミンやポリメルカプタンは、強い刺激性、及び臭気を伴うものが多く、個人差があるが感作性があり、カブレ、発疹等の症状を引き起こすことが認められる。また、硬化剤の強い臭気は、エポキシ樹脂硬化物を得るための成形、加工、施工時の作業効率の大幅な低減をもたらすばかりでなく、周辺の壁、設備、衣服等に臭気が移行し、当該臭気が種々の問題を引き起こす。 Polyamines and polymercaptans used as the main component of the curing agent are often accompanied by strong irritation and odor, and there are sensitizing properties although there are differences among individuals, and it is recognized that they cause symptoms such as rash and rash. In addition, the strong odor of the curing agent not only brings about a significant reduction in work efficiency during molding, processing and construction to obtain a cured epoxy resin, but also the odor migrates to the surrounding walls, equipment, clothes, etc. The odor causes various problems.
このような硬化剤由来の臭気を抑えるために、主成分である硬化剤の変性化が試みられている。 In order to suppress such an odor derived from the curing agent, attempts have been made to modify the curing agent as the main component.
例えば、特許文献1〜3では、硬化剤であるアミン系硬化剤をフェノールとホルムアルデヒド等のアルデヒドにより反応(マンニッヒ反応)させ、変性させることや、アミン系硬化剤にエポキシ化合物を付加させ、変性化させることにより、アミン系硬化剤を高分子化させ、アミン系硬化剤の蒸散による臭気を抑制させる方法が開示されている。 For example, in Patent Documents 1 to 3, an amine curing agent that is a curing agent is reacted with phenol and an aldehyde such as formaldehyde (Mannich reaction) and modified, or an epoxy compound is added to the amine curing agent and modified. Thus, a method for polymerizing an amine curing agent to suppress odor due to transpiration of the amine curing agent is disclosed.
このようにアミン系硬化剤を変性することで、蒸散の防止を図っているが、一部の残存する遊離のポリアミンにより、未だ臭気抑制の改善が十分に対応できていないのが現状である。 In this way, the amine-based curing agent is modified to prevent transpiration, but the present situation is that odor suppression cannot be sufficiently improved by some remaining free polyamines.
また、特許文献1〜3のように、アミン系硬化剤の蒸散による臭気を抑制のために添加されるフェノールは、未反応のものが硬化剤組成物に一部残存し、当該フェノール由来の臭気が問題ともなる。 In addition, as in Patent Documents 1 to 3, the phenol added to suppress the odor due to the transpiration of the amine curing agent remains partially unreacted in the curing agent composition, and the phenol-derived odor Is also a problem.
本発明は、硬化剤の臭気を低減することができる硬化剤組成物、及び当該硬化剤組成物を用いたエポキシ樹脂の硬化物を提供することを目的とする。 An object of this invention is to provide the hardening | curing agent composition which can reduce the odor of a hardening | curing agent, and the hardened | cured material of the epoxy resin using the said hardening | curing agent composition.
本発明者らは、かかる現状に鑑み、上記課題を解決すべく鋭意検討を行なった結果、硬化剤に対して、特定の水酸基含有芳香族化合物をさらに含有させることにより、硬化剤特有の臭気を大幅に低減することができることを見出した。 In view of the present situation, the present inventors have conducted extensive studies to solve the above problems, and as a result, the curing agent further contains a specific hydroxyl group-containing aromatic compound, thereby producing a odor peculiar to the curing agent. It has been found that it can be greatly reduced.
本発明は、かかる知見に基づき、更に検討を加えて完成されたものであり、以下の項1〜項6に係る硬化剤組成物、エポキシ樹脂の硬化物、及びエポキシ樹脂硬化物の製造方法を提供するものである。 The present invention has been completed on the basis of such findings, and has been completed. The curing agent composition according to the following items 1 to 6, the cured product of the epoxy resin, and the method for producing the cured epoxy resin: It is to provide.
項1.ポリアミン、及びポリメルカプタンよりなる群から選ばれる少なくとも1種の硬化剤(A)、並びに
一般式(1):
Item 1. At least one curing agent (A) selected from the group consisting of polyamines and polymercaptans, and general formula (1):
(式(1)中、nは1〜3の整数であり、
R1は、
炭素数1〜10のアルキル基、カルボキシル基、フェニル基、ヒドロキシル基、及び炭素数1〜6のアルキル基を置換していてもよいアミノ基よりなる群から選ばれる少なくとも1種の置換基を有していてもよいフェニルアルキル基;
炭素数1〜6のアルキル基;
カルボキシル基;
ヒドロキシル基;
炭素数1〜6のアルキル基を有していてもよいフェニル基;又は
炭素数1〜6のアルキル基を置換していてもよいアミノ基
であり、
nが2以上の場合、R1は同一であっても異なっていてもよい)、又は
一般式(2):
(In Formula (1), n is an integer of 1-3,
R 1 is
It has at least one substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group, a hydroxyl group, and an amino group that may be substituted with an alkyl group having 1 to 6 carbon atoms. An optionally substituted phenylalkyl group;
An alkyl group having 1 to 6 carbon atoms;
Carboxyl group;
A hydroxyl group;
A phenyl group optionally having an alkyl group having 1 to 6 carbon atoms; or an amino group which may be substituted with an alkyl group having 1 to 6 carbon atoms;
when n is 2 or more, R 1 may be the same or different), or the general formula (2):
(式(2)中、nは1〜3の整数であり、
R2は、
水素原子;
炭素数1〜10のアルキル基、カルボキシル基、フェニル基、ヒドロキシル基、及び炭素数1〜6のアルキル基を置換していてもよいアミノ基よりなる群から選ばれる少なくとも1種の置換基を有していてもよいフェニルアルキル基;
炭素数1〜6のアルキル基;
カルボキシル基;
ヒドロキシル基;
炭素数1〜6のアルキル基を有していてもよいフェニル基;又は
炭素数1〜6のアルキル基を置換していてもよいアミノ基であり、
nが2以上の場合、R2は同一であっても異なっていてもよい)
で表される水酸基含有芳香族化合物(B)
を含む硬化剤組成物。
(In formula (2), n is an integer of 1 to 3,
R 2 is
Hydrogen atom;
It has at least one substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group, a hydroxyl group, and an amino group that may be substituted with an alkyl group having 1 to 6 carbon atoms. An optionally substituted phenylalkyl group;
An alkyl group having 1 to 6 carbon atoms;
Carboxyl group;
A hydroxyl group;
A phenyl group optionally having an alkyl group having 1 to 6 carbon atoms; or an amino group which may be substituted with an alkyl group having 1 to 6 carbon atoms;
When n is 2 or more, R 2 may be the same or different)
Hydroxyl group-containing aromatic compound (B)
A curing agent composition comprising:
項2.硬化剤(A)100重量部に対して、水酸基含有芳香族化合物(B)を5〜2000重量部含む項1に記載の硬化剤組成物。 Item 2. Item 2. The curing agent composition according to item 1, comprising 5-2000 parts by weight of the hydroxyl group-containing aromatic compound (B) with respect to 100 parts by weight of the curing agent (A).
項3.ポリアミンが、鎖状脂肪族ポリアミン、環状脂肪族ポリアミン、芳香族ポリアミン、及びポリアミドよりなる群から選ばれる少なくとも1種のポリアミンである項1又は2に記載の硬化剤組成物。 Item 3. Item 3. The curing agent composition according to Item 1 or 2, wherein the polyamine is at least one polyamine selected from the group consisting of a chain aliphatic polyamine, a cycloaliphatic polyamine, an aromatic polyamine, and a polyamide.
項4.エポキシ樹脂の硬化に用いられる項1〜3のいずれかに記載の硬化剤組成物。 Item 4. Item 4. The curing agent composition according to any one of Items 1 to 3, which is used for curing an epoxy resin.
項5.項1〜4のいずれかに記載の硬化剤組成物、及び
エポキシ樹脂(C)
を混合し、硬化することにより得られるエポキシ樹脂の硬化物。
Item 5. The hardening | curing agent composition in any one of claim | item 1-4, and an epoxy resin (C)
A cured product of an epoxy resin obtained by mixing and curing.
項6.項1〜4のいずれかに記載の硬化剤組成物と、エポキシ樹脂(C)を混合し、硬化する工程を含むエポキシ樹脂硬化物の製造方法。 Item 6. Item 5. A method for producing a cured epoxy resin product comprising a step of mixing the curing agent composition according to any one of Items 1 to 4 and an epoxy resin (C) and curing the mixture.
本発明の硬化剤組成物によると、硬化剤に対して特定の水酸基含有芳香族化合物をさらに含有することにより、硬化剤由来の臭気を飛躍的に減少させることができる。特に、飲食店等の店舗の施工等において、硬化剤由来の臭気が内装等に移行することが低減できるため、施工後の換気等の時間を大幅に減らすことができる。 According to the hardening | curing agent composition of this invention, the odor derived from a hardening | curing agent can be drastically reduced by further containing a specific hydroxyl-containing aromatic compound with respect to a hardening | curing agent. In particular, in construction of restaurants such as restaurants, it is possible to reduce the transfer of odor derived from the curing agent to the interior, etc., so that time such as ventilation after construction can be significantly reduced.
また、従来の一般的な硬化剤は、長期間経過すると、時間の変化に伴い、容器の中で硬化剤が化学的に変化し、臭気が増加する傾向がある。それに対し、本願発明の硬化剤組成物によると、継続的に臭気の抑制を維持することができる。よって、本発明の硬化剤組成物は、貯蔵安定性に優れる。 In addition, when a conventional general curing agent passes for a long period of time, the curing agent chemically changes in the container with time, and the odor tends to increase. On the other hand, according to the hardening | curing agent composition of this invention, suppression of an odor can be maintained continuously. Therefore, the curing agent composition of the present invention is excellent in storage stability.
さらに、上記の硬化剤組成物を用いて得られるエポキシ樹脂の硬化物は、当該組成物に含まれる水酸基含有芳香族化合物の配合によっても機械的強度が損なわれることがなく、従来のエポキシ樹脂の硬化物と同様の機械的強度を有している。 Furthermore, the epoxy resin cured product obtained by using the above-described curing agent composition is not impaired in mechanical strength by the blending of the hydroxyl group-containing aromatic compound contained in the composition, It has the same mechanical strength as the cured product.
1.硬化剤組成物
本発明の硬化剤組成物は、硬化剤(A)、及び水酸基含有芳香族化合物(B)を含む。以下、各成分について、詳細に説明する。
1. Curing Agent Composition The curing agent composition of the present invention includes a curing agent (A) and a hydroxyl group-containing aromatic compound (B). Hereinafter, each component will be described in detail.
1−1.硬化剤(成分(A))
硬化剤(A)は、ポリアミン、及びポリメルカプタンよりなる群から選ばれる少なくとも1種である。
1-1. Curing agent (component (A))
The curing agent (A) is at least one selected from the group consisting of polyamines and polymercaptans.
ポリアミンとしては、2価以上、好ましくは2〜6価の多価アミンが挙げられ、鎖状脂肪族ポリアミン、環状脂肪族ポリアミン、芳香族ポリアミン、及びポリアミドよりなる群から選ばれる少なくとも1種のポリアミンが挙げられる。 Examples of the polyamine include divalent or higher, preferably 2 to 6 polyvalent amines, and at least one polyamine selected from the group consisting of chain aliphatic polyamines, cyclic aliphatic polyamines, aromatic polyamines, and polyamides. Is mentioned.
鎖状脂肪族ポリアミンとしては、メチレンジアミン、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ポリオキシプロピレンジアミン、ポリオキシプロピレントリアミン、ジプロピレンジアミン、ジプロピレントリアミン、ジエチルアミノプロピルアミン、1,2−ジアミノプロパン、トリプロピレンテトラミン、トリメチルヘキサメチレンジアミン等が挙げられる。 Examples of chain aliphatic polyamines include methylenediamine, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, polyoxypropylenediamine, polyoxypropylenetriamine, dipropylenediamine, dipropylenetriamine, diethylaminopropylamine, 1,2- Examples include diaminopropane, tripropylenetetramine, and trimethylhexamethylenediamine.
環状脂肪族ポリアミンとしては、N−アミノエチルピペラジン、ビス(4−アミノ−3−メチルジシクロヘキシル)メタン、イソホロンジアミン、メンセンジアミン、ジアミノジシクロヘキシルメタン、ビス(アミノメチル)シクロヘキサン、3,9−ビス(3−アミノプロピル)−2,4,8,10−テトラオキサスピロ(5.5)ウンデカン、1,4−シクロヘキサンジアミン、4,4’−メチレンビスシクロヘキシルアミン、4,4’−イソプロピリデンビスシクロヘキシルアミン、ノルボルナジアミン、ビス(アミノメチル)シクロヘキサン、ジアミノジシクロヘキシルメタン等が挙げられる。 Cycloaliphatic polyamines include N-aminoethylpiperazine, bis (4-amino-3-methyldicyclohexyl) methane, isophoronediamine, mensendiamine, diaminodicyclohexylmethane, bis (aminomethyl) cyclohexane, 3,9-bis ( 3-aminopropyl) -2,4,8,10-tetraoxaspiro (5.5) undecane, 1,4-cyclohexanediamine, 4,4′-methylenebiscyclohexylamine, 4,4′-isopropylidenebiscyclohexyl Amine, norbornadiamine, bis (aminomethyl) cyclohexane, diaminodicyclohexylmethane and the like can be mentioned.
芳香族ポリアミンとしては、o−キシリレンジアミン、m−キシリレンジアミン、p−キシリレンジアミン、ビス(アミノアルキル)ベンゼン、ビス(アミノアルキル)ナフタレン、m−フェニレンジアミン、p−フェニレンジアミン、トリレン−2,4−ジアミン、トリレン−2,6−ジアミン、メシチレン−2,4−ジアミン、メシチレン−2,6−ジアミン、3,5−ジエチルトリレン−2,4−ジアミン、3,5−ジエチルトリレン−2,6−ジアミン、ビフェニレンジアミン、4,4−ジアミノジフェニルメタン、ジアミノジエチルフェニルメタン、2,2−ビス(4−アミノフェニル)プロパン、2,5−ナフチレンジアミン、2,6−ナフチレンジアミン、4,4’−ジアミノジフェニルエーテル、4,4’−ジアミノベンゾフェノン、4,4’−ジアミノジフェニルエーテル、4,4’−ジアミノジフェニルスルホン、2,2’−ジメチル−4,4’−ジアミノジフェニルメタン、2,4’−ジアミノビフェニル、2,3’−ジメチル−4,4’−ジアミノビフェニル、3,3’−ジメトキシ−4,4’−ジアミノビフェニル、ビス(アミノメチル)ナフタレン、ビス(アミノエチル)ナフタレン等が挙げられる。 As aromatic polyamines, o-xylylenediamine, m-xylylenediamine, p-xylylenediamine, bis (aminoalkyl) benzene, bis (aminoalkyl) naphthalene, m-phenylenediamine, p-phenylenediamine, tolylene- 2,4-diamine, tolylene-2,6-diamine, mesitylene-2,4-diamine, mesitylene-2,6-diamine, 3,5-diethyltolylene-2,4-diamine, 3,5-diethyltri Ren-2,6-diamine, biphenylenediamine, 4,4-diaminodiphenylmethane, diaminodiethylphenylmethane, 2,2-bis (4-aminophenyl) propane, 2,5-naphthylenediamine, 2,6-naphthylene Amine, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzo Enone, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 2,2'-dimethyl-4,4'-diaminodiphenylmethane, 2,4'-diaminobiphenyl, 2,3'-dimethyl-4 , 4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, bis (aminomethyl) naphthalene, bis (aminoethyl) naphthalene and the like.
ポリアミドとしては、ジカルボン酸とポリアミンの縮合反応により生成される、分子中に反応性のモノアミン、及びジアミンを有するものが挙げられる。 Examples of the polyamide include those having a reactive monoamine and diamine in the molecule produced by a condensation reaction of a dicarboxylic acid and a polyamine.
ジカルボン酸の具体例としては、重合脂肪酸、単量体脂肪酸、エポキシ化不飽和脂肪酸、アルケニルコハク酸、二塩基性シクロヘキサン環置換化合物等が挙げられる。また、ポリアミンの具体例としては、ポリエチレンポリアミン:エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン、ポリオキシアルキレンポリアミン、メタキシレンジアミン等が挙げられる。 Specific examples of the dicarboxylic acid include polymerized fatty acid, monomeric fatty acid, epoxidized unsaturated fatty acid, alkenyl succinic acid, dibasic cyclohexane ring substituted compound and the like. Specific examples of the polyamine include polyethylene polyamine: ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, polyoxyalkylenepolyamine, metaxylenediamine, and the like.
ポリメルカプタンとしては、分子中に少なくとも2個のチオール基を有する化合物であり、特に限定されるものではないが、例えば、ポリオキシプロピレンポリ2−ハイドロオキシチオール、エチレングリコール型ジ(ポリ)ハイドロオキシチオール、リモネンジハイドロオキシチオール、ビスフェノールA型ジハイドロオキシチオール、ビスフェノールF型ジハイドロオキシチオール等のエーテル型ポリメルカプタンやフタル酸エステル型ジメルカプタン、トリメチロールプロパンポリメルカプトプロピオネート、ペンタエリスリトールポリメルカプトプロピオネート等のエステル型ポリメルカプタン等が挙げられる。 Polymercaptan is a compound having at least two thiol groups in the molecule and is not particularly limited. For example, polyoxypropylene poly-2-hydroxythiol, ethylene glycol di (poly) hydroxyl Ether type polymercaptan, phthalate type dimercaptan, trimethylolpropane polymercaptopropionate, pentaerythritol polymercapto such as thiol, limonene dihydroxythiol, bisphenol A type dihydroxythiol, bisphenol F type dihydrooxythiol Examples include ester type polymercaptans such as propionate.
これらの硬化剤(A)は、市販品として入手することができ、例えば、株式会社アデカ製のアデカハードナーEH−451N、EH−479A、EH−6024、EH−6028;エアープロダクツ社製のアンカミン2702、2706、2730;大都産業(株)製のダイトクラールX1777A、FH;(株)T&K TOKA製のフジキュアー、トーマイド等が挙げられる。 These curing agents (A) can be obtained as commercial products, for example, ADEKA HARDNER EH-451N, EH-479A, EH-6024, EH-6028 manufactured by ADEKA CORPORATION; Ancamine 2702 manufactured by Air Products. 2706, 2730; Daito Sangaku Co., Ltd. Daitokural X1777A, FH; T & K TOKA Co., Ltd. Fuji Cure, tomide, etc. are mentioned.
また前記硬化剤(A)は、ポリアミン、又はポリメルカプタンにおける骨格の一部が変性されたものであってもよく、例えば、ジアミノジフェニルメタン等により変性された変性ポリアミン等であってもよい。 The curing agent (A) may be a polyamine or a part of the skeleton of polymercaptan modified, for example, a modified polyamine modified with diaminodiphenylmethane or the like.
これらの硬化剤(A)は、単独で使用してもよく、また、2種以上の混合物として使用してもよい。 These curing agents (A) may be used alone or as a mixture of two or more.
これらの硬化剤(A)の中で、水酸基含有芳香族化合物(B)との反応性が優れるという観点から、脂肪族ポリアミン、環状脂肪族ポリアミン、及びこれらの混合物が好ましい。 Among these curing agents (A), aliphatic polyamines, cycloaliphatic polyamines, and mixtures thereof are preferable from the viewpoint of excellent reactivity with the hydroxyl group-containing aromatic compound (B).
1−2.水酸基含有芳香族化合物(成分(B))
水酸基含有芳香族化合物(B)としては、一般式(1)又は一般式(2)で表される化合物である。
一般式(1):
1-2. Hydroxyl group-containing aromatic compound (component (B))
As a hydroxyl-containing aromatic compound (B), it is a compound represented by General formula (1) or General formula (2).
General formula (1):
における式(1)中のnは1〜3の整数であって、また、nの数が異なる水酸基含有芳香族化合物の混合物であってもよい。 In the formula (1), n is an integer of 1 to 3, and may be a mixture of hydroxyl group-containing aromatic compounds having different numbers of n.
R1は、炭素数1〜10(好ましくは、炭素数1〜6)のアルキル基、カルボキシル基、フェニル基、ヒドロキシル基、及び炭素数1〜6のアルキル基を置換していてもよいアミノ基よりなる群から選ばれる少なくとも1種の置換基を有していてもよいフェニルアルキル基;炭素数1〜6のアルキル基;カルボキシル基;ヒドロキシル基;炭素数1〜6のアルキル基を有していてもよいフェニル基;又は炭素数1〜6のアルキル基を置換していてもよいアミノ基であり、nが2以上の場合、R1は同一であっても異なっていてもよい。 R 1 is an amino group which may be substituted for an alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a carboxyl group, a phenyl group, a hydroxyl group, or an alkyl group having 1 to 6 carbon atoms. A phenylalkyl group optionally having at least one substituent selected from the group consisting of: an alkyl group having 1 to 6 carbon atoms; a carboxyl group; a hydroxyl group; an alkyl group having 1 to 6 carbon atoms. A phenyl group which may be substituted; or an amino group which may be substituted with an alkyl group having 1 to 6 carbon atoms, and when n is 2 or more, R 1 may be the same or different.
上記のR1の中で、R1が上記置換基を有していてもよいフェニルアルキル基である場合のフェニル基に置換されるアルキル基としては、炭素数1〜6、好ましくは炭素数1〜4である。また、より具体的な化合物としては、式(1’): Among the above R 1, the alkyl group substituted by the phenyl group when R 1 is a phenylalkyl group which may have the above substituent, has 1 to 6 carbon atoms, preferably 1 carbon atom. ~ 4. Further, as a more specific compound, the formula (1 ′):
(式(1’)中、n’は1〜3の整数であり、n’の数が異なる化合物の混合物であってもよい。Ra及びRbは、同一又は異なり、水素原子、又は炭素数1〜6(好ましくは炭素数1〜4)のアルキル基である。Rcは、水素原子、炭素数1〜6(好ましくは炭素数1〜4)のアルキル基、ヒドロキシル基、炭素数1〜6(好ましくは炭素数1〜4)のアルキル基を置換していてもよいアミノ基である)である。 (In the formula (1 ′), n ′ is an integer of 1 to 3 and may be a mixture of compounds having different numbers of n ′. Ra and Rb are the same or different and are a hydrogen atom or a carbon number of 1; Rc is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms), a hydroxyl group, 1 to 6 carbon atoms (preferably having 1 to 4 carbon atoms). Preferably, it is an amino group which may be substituted with an alkyl group having 1 to 4 carbon atoms).
一般式(2): General formula (2):
における式(2)中のnは1〜3の整数であって、また、nの数が異なる水酸基含有芳香族化合物の混合物であってもよい。 In the formula (2), n is an integer of 1 to 3, and may be a mixture of hydroxyl group-containing aromatic compounds having different numbers of n.
R2は、炭素数1〜10(好ましくは、炭素数1〜6)のアルキル基、カルボキシル基、フェニル基、ヒドロキシル基、及び炭素数1〜6(好ましくは炭素数1〜4)のアルキル基を置換していてもよいアミノ基よりなる群から選ばれる少なくとも1種の置換基を有していてもよいフェニルアルキル基;水素原子;炭素数1〜6のアルキル基;カルボキシル基;ヒドロキシル基;炭素数1〜6のアルキル基を有していてもよいフェニル基;又は炭素数1〜6(好ましくは炭素数1〜4)のアルキル基を置換していてもよいアミノ基であり、nが2以上の場合、R2は同一であっても異なっていてもよい。 R 2 is an alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a carboxyl group, a phenyl group, a hydroxyl group, and an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms). A phenylalkyl group optionally having at least one substituent selected from the group consisting of amino groups optionally substituted; a hydrogen atom; an alkyl group having 1 to 6 carbon atoms; a carboxyl group; a hydroxyl group; A phenyl group which may have an alkyl group having 1 to 6 carbon atoms; or an amino group which may substitute an alkyl group having 1 to 6 carbon atoms (preferably 1 to 4 carbon atoms), and n is In the case of 2 or more, R 2 may be the same or different.
前記一般式(1)及び(2)で表される水酸基含有芳香族化合物のより具体的な例としては、
一般式(1”):
As more specific examples of the hydroxyl group-containing aromatic compound represented by the general formulas (1) and (2),
General formula (1 "):
(式(1”)中、n’は1〜3の整数であり、n’の数が異なる化合物の混合物であってもよい。)
で表されるスチレン化フェノール;
ベンジルフェノール;ジベンジルフェノール;トリベンジルフェノール;ビスフェノールF;フェニルフェノール;サリチル酸;ヒドロキノン;ビスフェノールA、フェニルフェノール、tert−ブチルフェノール;アミノベンジルフェノール;アミノフェノール;ナフトール等が挙げられる。
(In the formula (1 ″), n ′ is an integer of 1 to 3, and a mixture of compounds having different numbers of n ′ may be used.)
A styrenated phenol represented by:
Benzylphenol; dibenzylphenol; tribenzylphenol; bisphenol F; phenylphenol; salicylic acid; hydroquinone; bisphenol A, phenylphenol, tert-butylphenol; aminobenzylphenol; aminophenol;
なお、一般式(1)において、R1の位置は、オルト位、メタ位、パラ位のいずれの位置に置換されていてもよい。 In the general formula (1), the position of R 1 may be substituted at any position of ortho position, meta position, and para position.
これらの水酸基含有芳香族化合物(B)は、常温で液体であっても固体であってもよいが、液体の水酸基含有芳香族化合物(B)は硬化剤へ混合するのみで使用可能であるため、簡便に硬化剤組成物を調製できる点で好ましい。また、固体の水酸基含有芳香族化合物(B)であっても、硬化剤(A)と均一に混合することが可能であれば、そのまま使用することができ、また、あらかじめ溶剤に固体の水酸基含有芳香族化合物(B)を溶解させて、硬化剤(A)と混合し、硬化剤組成物を調製することもできる。前記溶剤としては、固体の水酸基含有芳香族化合物(B)を溶解できる溶剤であり、本発明の効果を損なわないものであれば、特に限定されるものではなく、例えば、後述の溶剤、希釈剤等が挙げられる。 These hydroxyl group-containing aromatic compounds (B) may be liquid or solid at room temperature, but the liquid hydroxyl group-containing aromatic compound (B) can be used only by mixing with a curing agent. It is preferable in that a curing agent composition can be easily prepared. Moreover, even if it is a solid hydroxyl-containing aromatic compound (B), if it can mix uniformly with a hardening | curing agent (A), it can be used as it is, and a solid hydroxyl-containing aromatic compound is previously contained in a solvent. The aromatic compound (B) can be dissolved and mixed with the curing agent (A) to prepare a curing agent composition. The solvent is not particularly limited as long as it is a solvent capable of dissolving the solid hydroxyl group-containing aromatic compound (B) and does not impair the effects of the present invention. Etc.
上記の観点から、スチレン化フェノール、及びベンジルフェノールは、液体の水酸基含有芳香族化合物(B)であり、前記の溶剤を用いなくとも硬化剤(A)と均一に混合できる点から好ましい。また、フェニルフェノール、tert−ブチルフェノール、ビスフェノールA、ナフトール等のような固体の水酸基含有芳香族化合物(B)であっても、上記の溶剤を用いて硬化剤(A)と混合した場合に、均一に混合することができる。いずれの形態においても、硬化剤由来の臭気を充分に抑制することができる。 From the above viewpoint, styrenated phenol and benzylphenol are liquid hydroxyl group-containing aromatic compounds (B), and are preferable because they can be uniformly mixed with the curing agent (A) without using the solvent. Moreover, even if it is a solid hydroxyl group-containing aromatic compound (B) such as phenylphenol, tert-butylphenol, bisphenol A, naphthol, etc., it is uniform when mixed with the curing agent (A) using the above solvent. Can be mixed. In any form, the odor derived from the curing agent can be sufficiently suppressed.
これらの水酸基含有芳香族化合物(B)は、単独で使用してもよく、また、2種以上の混合物として使用してもよい。 These hydroxyl group-containing aromatic compounds (B) may be used alone or as a mixture of two or more.
水酸基含有芳香族化合物(B)の含有量は、硬化剤(A)100重量部に対して、2000重量部以下が好ましく、1500重量部以下がより好ましく、1300重量部以下がさらに好ましく、500重量部以下が一層好ましく、400重量部以下がより一層好ましく、300重量部以下がさらに一層好ましく、250重量部以下がさらにまた一層好ましく、100重量部程度が特に好ましく、60重量部以下が最も好ましい。また、水酸基含有芳香族化合物(B)の含有量は、5重量部以上が好ましく、10重量部以上がより好ましく、30重量部以上がさらに好ましい。水酸基含有芳香族化合物(B)の含有量を上記の範囲に設定することにより、硬化剤由来の臭気を抑制することができる。 The content of the hydroxyl group-containing aromatic compound (B) is preferably 2000 parts by weight or less, more preferably 1500 parts by weight or less, still more preferably 1300 parts by weight or less, with respect to 100 parts by weight of the curing agent (A). Parts by weight or less, more preferably 400 parts by weight or less, still more preferably 300 parts by weight or less, still more preferably 250 parts by weight or less, still more preferably about 100 parts by weight, most preferably 60 parts by weight or less. Moreover, 5 weight part or more is preferable, as for content of a hydroxyl-containing aromatic compound (B), 10 weight part or more is more preferable, and 30 weight part or more is further more preferable. By setting the content of the hydroxyl group-containing aromatic compound (B) within the above range, the odor derived from the curing agent can be suppressed.
なお、後述の得られる硬化剤組成物によりエポキシ樹脂を硬化した場合、硬化物の機械的強度等の特性を発揮することができるという観点からは、水酸基含有芳香族化合物(B)の含有量を1300重量部以下に設定することが好ましい。 In addition, when an epoxy resin is hardened | cured with the hardening | curing agent composition obtained later, from a viewpoint that characteristics, such as mechanical strength of hardened | cured material, can be exhibited, content of a hydroxyl-containing aromatic compound (B) is shown. It is preferable to set it to 1300 parts by weight or less.
1−3.その他の成分
本発明の硬化剤組成物は、さらに、溶剤、フィラー、レベリング剤、消泡剤、粘度調整剤、希釈剤、硬化促進剤、可塑剤、染料、顔料、酸化防止剤、紫外線吸収剤、光安定剤、難燃剤、たれ止剤等の任意の成分を含有させることができる。これらの任意の成分の含有量としては、本発明の所定の効果に影響を及ぼさない限り特に限定されるものではなく、所望の範囲で適用される。これらの任意成分は、硬化剤組成物として、また、後述の硬化剤において、本発明の効果が損なわれない範囲で適宜設定して配合される。
1-3. Other components The curing agent composition of the present invention further includes a solvent, a filler, a leveling agent, an antifoaming agent, a viscosity modifier, a diluent, a curing accelerator, a plasticizer, a dye, a pigment, an antioxidant, and an ultraviolet absorber. , Optional components such as a light stabilizer, a flame retardant, and an anti-sagging agent can be contained. The contents of these optional components are not particularly limited as long as they do not affect the predetermined effects of the present invention, and are applied within a desired range. These optional components are appropriately set and blended as a curing agent composition and in the curing agent described later as long as the effects of the present invention are not impaired.
溶剤としては、テトラヒドロフラン、1,2−ジメトキシエタン、1,2−ジエトキシエタン等のエーテル;イソ−又はn−ブタノール、イソ−又はn−プロパノール、アミルアルコール、ベンジルアルコール、フルフリルアルコール、テトラヒドロフルフリルアルコール等のアルコール;メチルエチルケトン、メチルアミルケトン、ジエチルケトン、アセトン、メチルイソプロピルケトン、メチルブチルケトン、プロピレングリコールモノメチルエーテルアセテート、シクロヘキサノン等のケトン;酢酸エチル、酢酸n−ブチル等のエステル;ベンゼン、トルエン、キシレン等の芳香族炭化水素;テレピン油、D−リモネン、ピネン等のテルペン系炭化水素油;高沸点パラフィン系溶剤;アニリン;トリエチルアミン;ピリジン;ジオキサン;アセトニトリル等が挙げられる。 Solvents include ethers such as tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane; iso- or n-butanol, iso- or n-propanol, amyl alcohol, benzyl alcohol, furfuryl alcohol, tetrahydrofur Alcohols such as furyl alcohol; ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl butyl ketone, propylene glycol monomethyl ether acetate, cyclohexanone; esters such as ethyl acetate and n-butyl acetate; benzene, toluene , Xylene and other aromatic hydrocarbons; terpene hydrocarbon oils such as turpentine oil, D-limonene and pinene; high-boiling paraffinic solvents; aniline; triethylamine; pyridine; ; Acetonitrile.
フィラーとしては、アルミニウム;亜酸化鉛;水和アルミナ;珪藻土;亜鉛;
炭酸カルシウム;炭酸バリウム;硫酸バリウム;ガラス繊維;ガラスビーズ;ガラスマイクロバルーン;炭素繊維;セルロース;ケイ砂;セメント;カオリン;クレー;水酸化アルミニウム;ベントナイト;シリカ;二酸化チタン;カーボンブラック;グラファイト;酸化鉄;瀝青物質;ウォラストナイト;パイロフィライト等の含水ケイ酸アルミニウム系粘土鉱物;タルク等の含水ケイ酸マグネシウム系粘土鉱物等が挙げられる。これらのフィラーの形状は、特に限定されず、繊維状、(微)粉末状、粒状、フレーク状、板状、棒状等いずれの形状であってもよい。
As filler, aluminum; lead oxide; hydrated alumina; diatomaceous earth; zinc;
Calcium carbonate; Barium carbonate; Barium sulfate; Glass fiber; Glass bead; Glass microballoon; Carbon fiber; Cellulose; Silica sand; Cement; Kaolin; Clay; Aluminum hydroxide; Iron; bituminous substance; wollastonite; hydrous aluminum silicate clay minerals such as pyrophyllite; hydrous magnesium silicate clay minerals such as talc. The shape of these fillers is not particularly limited, and may be any shape such as fibrous, (fine) powder, granular, flake, plate, or rod.
レベリング剤及び消泡剤としては、アクリル酸エステル、アクリル酸エステルとビニル系化合物の共重合体、脂肪族多価カルボン酸等のアクリル系レベリング剤;イソパラフィン;流動パラフィン;シリコーンオイル;ポリシロキサン系オリゴマー;フッ素系化合物等が挙げられる。 Leveling agents and antifoaming agents include acrylic ester, acrylic ester-vinyl copolymer, acrylic polyhydric carboxylic acid leveling agent, isoparaffin, liquid paraffin, silicone oil, polysiloxane oligomer A fluorine-based compound and the like.
粘度調整剤としては、合成シリカ;アマイドワックス等のワックス;ベントナイト等の粘土鉱物;コロイド炭酸カルシウム等が挙げられる。 Examples of the viscosity modifier include synthetic silica; wax such as amide wax; clay mineral such as bentonite; colloidal calcium carbonate.
希釈剤としては、キシレン樹脂;ジオクチルフタレート;ジブチルフタレート;ベンジルアルコール;メチルイソブチルケトン、メチルエチルケトン等のケトン;ブタノール等のアルコール;キシレン等の芳香族炭化水素;エチレンジクロライド;アクリロニトリル;メチルtert−ブチルエーテル、プロピレングリコールモノメチルエーテル等のエーテル等が挙げられる。 Diluent phthalate; dibutyl phthalate; benzyl alcohol; ketones such as methyl isobutyl ketone and methyl ethyl ketone; alcohols such as butanol; aromatic hydrocarbons such as xylene; ethylene dichloride; acrylonitrile; methyl tert-butyl ether, propylene And ethers such as glycol monomethyl ether.
さらに、熱可塑性樹脂として塩化ゴム、塩素化ポリエチレン、塩素化ポリプロピレン等の塩素化ポリオレフィン;(メタ)アクリル酸メチル系共重合体、(メタ)アクリル酸エチル系共重合体、(メタ)アクリル酸プロピル系共重合体、(メタ)アクリル酸ブチル系共重合体、(メタ)アクリル酸シクロヘキシル系共重合体等のアクリル系樹脂;塩化ビニル−酢酸ビニル共重合体、塩化ビニル−プロピオン酸ビニル共重合体、塩化ビニル−イソブチルビニルエーテル共重合体、塩化ビニル−イソプロピルビニルエーテル共重合体、塩化ビニル−エチルビニルエーテル共重合体等の塩化ビニル系樹脂(塩化ビニル共重合体);スチレン系樹脂;芳香族系石油樹脂;脂肪族系石油樹脂;尿素アルデヒド縮合系樹脂;ケトン系樹脂等やベンジルアルコール等も挙げられる。 Further, chlorinated polyolefins such as chlorinated rubber, chlorinated polyethylene and chlorinated polypropylene as thermoplastic resins; (meth) methyl acrylate copolymers, (meth) ethyl acrylate copolymers, (meth) propyl acrylate Copolymer, acrylic resin such as (meth) butyl acrylate copolymer, (meth) cyclohexyl cyclohexyl copolymer; vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl propionate copolymer , Vinyl chloride-isobutyl vinyl ether copolymer, vinyl chloride-isopropyl vinyl ether copolymer, vinyl chloride-ethyl vinyl ether copolymer, and other vinyl chloride resins (vinyl chloride copolymers); styrene resins; aromatic petroleum resins Aliphatic petroleum resin; Urea aldehyde condensation resin; Ketone resin and benzyl alcohol Lumpur and the like can be used as well.
硬化促進剤としては、例えば、トリメチルアミン、エチルジメチルアミン、プロピルジメチルアミン、N,N’−ジメチルピペラジン、ピリジン、ピコリン、1,8−ジアザビスシクロ(5,4,0)ウンデセン−1(DBU)、ベンジルジメチルアミン、2−(ジメチルアミノメチル)フェノール(DMP−10)、2,4,6−トリス(ジメチルアミノメチル)フェノール(DMP−30)等の第三アミン;フェノールノボラック、o−クレゾールノボラック、p−クレゾールノボラック、tert−ブチルフェノールノボラック、ジシクロペンタジエンクレゾール、ビスフェノールA、ビスフェノールF、フェノール、炭素数16以下のアルキル鎖を有するアルキルフェノール等のフェノール系化合物;p−トルエンスルホン酸、チオシアン酸の1−アミノピロリジン塩;トリフェニルホスファイト、ジフェニルハイドロゲンホスファイト、ジフェニルモノデシルホスファイト等の亜リン酸フェニルエステル;トリメチロールプロパン、グリセリン等の多価アルコール;2,4,6−トリス(ジメチルアミノメチル)フェノール(DMP−30);酪酸;酢酸セルロース等が挙げられる。 Examples of the curing accelerator include trimethylamine, ethyldimethylamine, propyldimethylamine, N, N′-dimethylpiperazine, pyridine, picoline, 1,8-diazabiscyclo (5,4,0) undecene-1 (DBU), benzyl Tertiary amines such as dimethylamine, 2- (dimethylaminomethyl) phenol (DMP-10), 2,4,6-tris (dimethylaminomethyl) phenol (DMP-30); phenol novolak, o-cresol novolak, p Phenol compounds such as cresol novolak, tert-butylphenol novolak, dicyclopentadiene cresol, bisphenol A, bisphenol F, phenol, alkylphenol having an alkyl chain having 16 or less carbon atoms; p-toluenesulfonic acid, thio 1-aminopyrrolidine salt of an acid; phosphorous acid phenyl ester such as triphenyl phosphite, diphenyl hydrogen phosphite, diphenyl monodecyl phosphite; polyhydric alcohol such as trimethylolpropane, glycerin; 2,4,6-tris (Dimethylaminomethyl) phenol (DMP-30); butyric acid; cellulose acetate and the like.
可塑剤としては、例えば、フタル酸ジオクチル、フタル酸ジブチル、アジピン酸ジオクチル等の多塩基酸エステル;ジエチレングリコールジベンゾエート、ジエチレングリコールジオクトエート、グリセロールトリブチレート等の多価アルコールエステル;9,10−エポキシステアリン酸オクチル、エポキシ化植物油、4,5−エポキシヘキサヒドロフタル酸ジオクチル等のエポキシ化エステル;トリフェニルホスフェート、トリオクチルホスフェート、ジフェニルモノイソプロピルホスフェートのリン酸エステル等が挙げられる。 Examples of the plasticizer include polybasic acid esters such as dioctyl phthalate, dibutyl phthalate and dioctyl adipate; polyhydric alcohol esters such as diethylene glycol dibenzoate, diethylene glycol dioctate and glycerol tributyrate; 9,10-epoxy Examples include epoxidized esters such as octyl stearate, epoxidized vegetable oil, and dioctyl 4,5-epoxyhexahydrophthalate; and phosphoric esters of triphenyl phosphate, trioctyl phosphate, diphenyl monoisopropyl phosphate, and the like.
染料及び顔料としては、例えば、酸化チタン、カーボンブラック、酸化鉄、黄鉛、ジスアゾ系イエロー、キノフタロン系イエロー、モノアゾ系レッド、ベンズイミダゾロン系レッド、フタロシアニンブルー等が挙げられる。 Examples of the dyes and pigments include titanium oxide, carbon black, iron oxide, yellow lead, disazo yellow, quinophthalone yellow, monoazo red, benzimidazolone red, and phthalocyanine blue.
酸化防止剤としては、例えば、ジブチルヒドロキシトルエン等のヒンダードフェノール系酸化防止剤;ジラウリルチオジプロピオネート、2−メルカプトベンゾイミダゾール等の硫黄系酸化防止剤;トリデシルホスファイト、トリウリルトリチオホスファイト等の亜リン酸エステル等が挙げられる。 Examples of the antioxidant include hindered phenol-based antioxidants such as dibutylhydroxytoluene; sulfur-based antioxidants such as dilauryl thiodipropionate and 2-mercaptobenzimidazole; tridecyl phosphite, triuryl trithiophos. Examples thereof include phosphites such as fights.
紫外線吸収剤としては、例えば、2(2,−ヒドロキシ−5’−メチルフェニル)ベンゾトリアゾール等のベンゾトリアゾール系化合物;2,4−ジヒドロキシベンゾフェノン等のベンゾフェノン系化合物;サリチル酸フェニル等のサリチル酸エステル系化合物等が挙げられる。 Examples of the ultraviolet absorber include benzotriazole compounds such as 2 (2, -hydroxy-5′-methylphenyl) benzotriazole; benzophenone compounds such as 2,4-dihydroxybenzophenone; salicylic acid ester compounds such as phenyl salicylate. Etc.
光安定剤としては、例えば、ビス(2,2,6,6−テトラメチルー4−ピペリジル)セバケート等のヒンダードアミン系化合物等が挙げられる。 Examples of the light stabilizer include hindered amine compounds such as bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate.
難燃剤としては、例えば、三酸化アンチモン、塩素化パラフィン、塩素化ジフェニル、リン酸エステル等が挙げられる。 Examples of the flame retardant include antimony trioxide, chlorinated paraffin, chlorinated diphenyl, and phosphate ester.
たれ止剤としては、例えば、コロイダルシリ力、水添ヒマシ油系ワックス、ポリエチレンワックス、アマイドワックス、有機ベントナイト、ステアリン酸アルミニウム、ステアリン酸亜鉛等が挙げられる。 Examples of the anti-sagging agent include colloidal shear force, hydrogenated castor oil-based wax, polyethylene wax, amide wax, organic bentonite, aluminum stearate, and zinc stearate.
本発明の硬化剤組成物は、硬化性樹脂を硬化させるために用いられ、特に硬化性樹脂としてエポキシ樹脂の硬化剤として好適に用いられる。 The hardening | curing agent composition of this invention is used in order to harden curable resin, and is used suitably as a hardening | curing agent of an epoxy resin especially as curable resin.
1−4.硬化剤組成物の形態及びその用途
本発明の硬化剤組成物は、エポキシ樹脂を含むエポキシ樹脂組成物を別に設け、使用時に二液を混合するタイプの硬化剤組成物として用いることが貯蔵安定性に優れ、混合後は速やかに反応し想定する硬化物が得られる点で好ましい。
1-4. Form of Curing Agent Composition and Its Use The curing agent composition of the present invention is storage stable when used as a curing agent composition of a type in which an epoxy resin composition containing an epoxy resin is separately provided and two liquids are mixed at the time of use. It is preferable in that it can react quickly after mixing and an expected cured product can be obtained.
本発明の硬化剤組成物は、主剤であるエポキシ樹脂組成物と組み合わせて、例えば、コンクリート、セメントモルタル、各種金属、皮革、ガラス、ゴム、プラスチック、木、布、紙、床材等に対する塗料又は接着剤;包装用粘着テープ、粘着ラベル、冷凍食品ラベル、リムーバルラベル、POSラベル、粘着壁紙、粘着床材の粘着剤;アート紙、軽量コート紙、キャストコート紙、塗工板紙、カーボンレス複写機、含浸紙等の加工紙;天然繊維、合成繊維、ガラス繊維、炭素繊維、金属繊維等の収束剤、ほつれ防止剤、加工剤等の繊維処理剤;シーリング材(例えば、シールドセグメント及びボックスカルバートの接続部のシール材等)、ライニング材(例えば、上水用ピット等の水槽のライニング材)、土木用補修材(例えば、コンクリートのひび割れ補修用の注入材、欠損補修材、充填シーリング材等)、セメント混和剤、防水材等の建築材料等、広範な用途に使用することができる。 The curing agent composition of the present invention is combined with the epoxy resin composition as the main agent, for example, a paint for concrete, cement mortar, various metals, leather, glass, rubber, plastic, wood, cloth, paper, flooring, etc. Adhesive: Adhesive tape for packaging, adhesive label, frozen food label, removable label, POS label, adhesive wallpaper, adhesive for adhesive flooring; art paper, lightweight coated paper, cast coated paper, coated paperboard, carbonless copier Processed paper such as impregnated paper; fiber treatment agents such as converging agents such as natural fibers, synthetic fibers, glass fibers, carbon fibers and metal fibers, anti-fraying agents and processing agents; sealing materials (for example, shield segments and box culverts) Sealing materials for connecting parts), lining materials (for example, lining materials for water tanks such as water pits), civil engineering repair materials (for example, concrete) Grout for crack repair, defective repair materials, packing sealing material, etc.), cement admixture, etc. building materials such as waterproof material, can be used in a wide variety of applications.
本発明の硬化剤組成物は硬化剤特有の臭気を大幅に抑制することができるため、特に、飲食店の店舗等の内装で施工するために用いられる塗料又は接着剤等に使用することがより好ましい。 Since the curing agent composition of the present invention can greatly suppress the odor peculiar to the curing agent, it is particularly preferable to use it for paints or adhesives used for construction in interiors of restaurants and the like. preferable.
本発明の硬化剤組成物の粘度としては、上記の用途に応じて適宜設定されるものであり、溶剤、希釈剤等を用いて適宜調製することができる。 As a viscosity of the hardening | curing agent composition of this invention, it sets suitably according to said use, It can prepare suitably using a solvent, a diluent, etc.
本発明の硬化剤組成物は、従来のようにマンニッヒ反応によって硬化剤を変性させる方法において用いられるホルムアルデヒドのようなアルデヒドを用いず、硬化剤特有の臭気を低減することができる。 The curing agent composition of the present invention can reduce the odor peculiar to the curing agent without using an aldehyde such as formaldehyde used in the conventional method for modifying the curing agent by the Mannich reaction.
2.エポキシ樹脂の硬化物及びその製造方法
本発明のエポキシ樹脂の硬化物は、硬化剤組成物、及びエポキシ樹脂(C)を混合し、硬化することにより製造される。
2. Cured product of epoxy resin and production method thereof The cured product of the epoxy resin of the present invention is produced by mixing and curing the curing agent composition and the epoxy resin (C).
2−1.硬化剤組成物
硬化剤組成物としては、前記の「1.硬化剤組成物」で挙げられたものを用いることができる。
2-1. Curing Agent Composition As the curing agent composition, those listed in the above-mentioned “1. Curing agent composition” can be used.
2−2.エポキシ樹脂(成分C)
エポキシ樹脂(C)としては、特に限定されず、汎用的なエポキシ樹脂を用いることが可能であり、エポキシ基を分子中に2個以上含有するものであれば、制限なく使用することができる。例えば、クレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ビフェニル型エポキシ樹脂、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、脂環式エポキシ樹脂等が挙げられる。これらのエポキシ樹脂は、単独で使用してもよく、2種類以上を混合して使用することもできる。
2-2. Epoxy resin (component C)
It does not specifically limit as an epoxy resin (C), A general purpose epoxy resin can be used, If it contains two or more epoxy groups in a molecule | numerator, it can be used without a restriction | limiting. Examples thereof include a cresol novolac type epoxy resin, a phenol novolac type epoxy resin, a biphenyl type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and an alicyclic epoxy resin. These epoxy resins may be used alone or in combination of two or more.
また、上記のエポキシ樹脂は、液状であってもよく、固形のエポキシ樹脂である場合には、別の液状樹脂と加熱混合して液状としてもよい。液状樹脂としては、例えば、ビスフェノールA型液状エポキシ樹脂、ビスフェノールF型液状エポキシ樹脂等が挙げられるが、これらに限定されるものではない。 The epoxy resin may be in a liquid state, and when it is a solid epoxy resin, it may be mixed with another liquid resin by heating. Examples of the liquid resin include, but are not limited to, bisphenol A type liquid epoxy resin and bisphenol F type liquid epoxy resin.
本発明のエポキシ樹脂(C)の配合量としては、所定の効果が得られる限り特に限定されるものではないが、通常、硬化剤(A)中の活性水素1当量に対して、エポキシ樹脂中のエポキシ当量が0.5〜1.5当量、好ましくは、0.7〜1.2当量の範囲である。上記の範囲にエポキシ樹脂の配合量を設定することにより、得られる硬化物は機械的強度に優れ、且つ硬化物の透明性に優れる。 The blending amount of the epoxy resin (C) of the present invention is not particularly limited as long as a predetermined effect is obtained, but usually in the epoxy resin with respect to 1 equivalent of active hydrogen in the curing agent (A). In the range of 0.5 to 1.5 equivalents, preferably 0.7 to 1.2 equivalents. By setting the compounding amount of the epoxy resin within the above range, the obtained cured product is excellent in mechanical strength and excellent in transparency of the cured product.
エポキシ樹脂(C)及び硬化剤組成物を混合後に行われる、硬化する方法としては、エポキシ樹脂(C)と硬化剤組成物を混合する工程のみで、エポキシ樹脂(C)と硬化剤(A)の反応(架橋反応)の反応速度が早い場合には、特に必要はないが、例えば、加熱による硬化、UV照射による硬化等を行うことにより、より硬化を促進することができる。これらの硬化の方法において、作業性が容易であるという点から、熱による硬化が好ましい。 As a curing method performed after mixing the epoxy resin (C) and the curing agent composition, only the step of mixing the epoxy resin (C) and the curing agent composition, the epoxy resin (C) and the curing agent (A). When the reaction rate of this reaction (crosslinking reaction) is high, there is no particular need. However, for example, curing can be promoted by curing by heating, curing by UV irradiation, or the like. In these curing methods, curing by heat is preferable from the viewpoint of easy workability.
加熱により硬化する場合における加熱温度としては、所望の硬化物が得られる範囲において特に限定されるものではないが、例えば、50〜150℃程度が好ましく、70〜150℃程度がより好ましく、100〜150℃程度がさらに好ましい。 Although it does not specifically limit in the range in which desired hardened | cured material is obtained when it hardens | cures by heating, For example, about 50-150 degreeC is preferable, about 70-150 degreeC is more preferable, 100- About 150 ° C. is more preferable.
以下、実施例及び比較例を挙げ、本発明を詳しく説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not limited to these Examples.
実施例1〜17、及び比較例1
スチレン化フェノール(粘度(下記の粘度測定条件で測定):505mPa・s)、及び脂肪族ポリアミン(株式会社アデカ製のアデカハードナーEH−234)を表1に示す含有量で混合し、各硬化剤組成物を得た。得られた各硬化剤組成物について、以下の測定方法により、粘度及び臭気を測定評価した。表1にスチレン化フェノール、及び脂肪族ポリアミンの含有量、並びに物性評価を示す。
Examples 1 to 17 and Comparative Example 1
Styrenated phenol (viscosity (measured under the following viscosity measurement conditions): 505 mPa · s) and aliphatic polyamine (Adeka Hardener EH-234 manufactured by Adeka Co., Ltd.) were mixed at the contents shown in Table 1, and each curing agent was mixed. A composition was obtained. About each obtained hardening | curing agent composition, the viscosity and odor were measured and evaluated by the following measuring methods. Table 1 shows the content of styrenated phenol and aliphatic polyamine, and evaluation of physical properties.
<粘度>
BM型粘度計(東機産業(株)製のBM型粘度計)により、23℃において、適宜ローターと回転数を変更し、測定した。
<Viscosity>
Using a BM type viscometer (BM type viscometer manufactured by Toki Sangyo Co., Ltd.), at 23 ° C., the rotor and the number of revolutions were appropriately changed and measured.
<臭気評価>
検知管による測定と、人による官能検査を行った。
<Odor evaluation>
Measurements using detector tubes and human sensory tests were performed.
人による官能検査では、スチレン化フェノールと脂肪族ポリアミンの混合物を含む容器から硬化剤(脂肪族ポリアミン)が同量となるように、それぞれカップに採取し、直接臭いを嗅ぐことにより、以下の基準により臭気を評価した。なお、下記の基準は、比較例1の評価「1」を基準として、相対的に評価を行っている。 In the human sensory test, the following standards are obtained by collecting each curing agent (aliphatic polyamine) from a container containing a mixture of styrenated phenol and aliphatic polyamine in a cup and sniffing it directly. Was used to evaluate the odor. The following criteria are relatively evaluated based on the evaluation “1” of Comparative Example 1.
5:アミンの臭気が全く確認されない
4:アミンの臭気がほとんど確認されない
3:アミンの臭気が若干確認されるが、施工作業等に影響が全くでない程度である
2:アミンの臭気は確認されるが、施工作業等に影響がでない程度である
1:アミンの臭気が著しい
5: The odor of amine is not confirmed at all. 4: The odor of amine is scarcely confirmed. 3: The odor of amine is slightly confirmed, but there is no effect on construction work. 2: The odor of amine is confirmed. However, there is no effect on construction work, etc. 1: The amine odor is remarkable
<結果及び考察>
実施例1〜17の結果より、スチレン化フェノールの含有量の増加に伴い、粘度は上昇した。臭気評価においては、スチレン化フェノールの含有量が5重量部以上で臭気低減効果がみられ、特にスチレン化フェノールの含有量が30重量部以上で臭気の低減効果がより顕著に現れた。
<Results and discussion>
From the results of Examples 1 to 17, the viscosity increased with an increase in the content of styrenated phenol. In the odor evaluation, the effect of reducing odor was observed when the content of styrenated phenol was 5 parts by weight or more, and the effect of reducing odor was particularly prominent when the content of styrenated phenol was 30 parts by weight or more.
実施例18〜19、及び比較例2〜10
硬化剤として、脂肪族ポリアミン(株式会社アデカ製のアデカハードナーEH−479A)を70重量部、及びn−アミノエチルピペラジンを30重量部用い、当該硬化剤(合計量:100重量部)と、表2に示す各種添加剤(30重量部)をそれぞれ混合し、各硬化剤組成物を得た。得られた各硬化剤組成物について粘度を測定し、さらに臭気を以下の方法、及び基準により、測定評価した。なお、粘度は実施例1と同様の方法により測定を行った。表2に各硬化剤組成物における添加剤の成分、及び物性評価を示す。
Examples 18 to 19 and Comparative Examples 2 to 10
As a curing agent, 70 parts by weight of an aliphatic polyamine (ADEKA HARDNER EH-479A manufactured by ADEKA CORPORATION) and 30 parts by weight of n- aminoethylpiperazine , the curing agent (total amount: 100 parts by weight), Various additives (30 parts by weight) shown in 2 were mixed to obtain each curing agent composition. The viscosity of each of the obtained curing agent compositions was measured, and the odor was measured and evaluated by the following methods and standards. The viscosity was measured by the same method as in Example 1. Table 2 shows the components of the additives in each curing agent composition and the evaluation of physical properties.
また、表2に示す添加剤として示す、高沸点芳香族炭化水素化合物は、JX日鉱日石エネルギー株式会社製のハイゾールSAS−296;キシレン樹脂は、フドー株式会社製のニカノールY−50を用いた。 Moreover, the high boiling point aromatic hydrocarbon compound shown as an additive shown in Table 2 used Hysol SAS-296 made by JX Nippon Mining & Energy Corporation; Nixanol Y-50 made by Fudou Co., Ltd. was used as the xylene resin. .
<臭気評価>
検知管による測定と、人による官能検査を行った。検知管による臭気測定は、前記実施例1で行った方法と同様の方法により、臭気を測定した。
<Odor evaluation>
Measurements using detector tubes and human sensory tests were performed. For the odor measurement by the detector tube, the odor was measured by the same method as that used in Example 1.
人による官能検査は、各硬化剤組成物中の硬化剤が同量となるように、それぞれ採取し、500ml角缶の容器に入れ密封した。その後、24時間放置後開封し、再度密封した。さらに、30分後、1.5時間後に、それぞれ開封し、各開封時の臭気を直接臭いを嗅ぐことによって、以下の基準より評価した。なお、下記の基準は、比較例2の評価「1」を基準として、相対的に評価を行っている。 In the sensory test by humans, each of the curing agents was collected so that the amount of the curing agent was the same amount, and sealed in a 500 ml square can container. Then, after leaving for 24 hours, it was opened and sealed again. Furthermore, 30 minutes and 1.5 hours later, each was opened, and the odor at the time of each opening was directly smelled, and evaluated according to the following criteria. The following criteria are relatively evaluated based on the evaluation “1” of Comparative Example 2.
5:アミンの臭気が全く確認されない
4:アミンの臭気がほとんど確認されない
3:アミンの臭気が若干確認されるが、施工作業等に影響が全くでない程度である
2:アミンの臭気は確認されるが、施工作業等に影響がでない程度である
1:アミンの臭気が著しい
5: The odor of amine is not confirmed at all. 4: The odor of amine is scarcely confirmed. 3: The odor of amine is slightly confirmed, but there is no effect on construction work. 2: The odor of amine is confirmed. However, there is no effect on construction work, etc. 1: The amine odor is remarkable
<結果と考察>
実施例18及び19より、添加剤としてトリベンジルフェノール、及びスチレン化フェノールを用いた場合には、アミンの臭気の低減効果が確認できた。
<Results and discussion>
From Examples 18 and 19, when tribenzylphenol and styrenated phenol were used as additives, the effect of reducing the odor of amine could be confirmed.
一方、比較例2〜10で用いた添加剤では、アミンの臭気抑制効果が充分得られなかった。なお、比較例3、5、6、及び8〜10においては、アミンの臭気が多少低減されるものもあったが、添加剤自体の臭気が確認され、充分な効果が発揮されないものとなった。 On the other hand, the additives used in Comparative Examples 2 to 10 did not provide a sufficient amine odor suppression effect. In Comparative Examples 3, 5, 6, and 8 to 10, some amine odors were somewhat reduced, but the odor of the additive itself was confirmed, and sufficient effects were not exhibited. .
実施例20〜32
硬化剤として、脂肪族ポリアミン(株式会社アデカ製のアデカハードナーEH−479A)を70重量部、及びn−アミノエチルピペラジンを30重量部用い、当該硬化剤(合計量:100重量部)と、表3に示す添加剤(30重量部)を、90℃で30分間加熱しながらそれぞれ混合し、各硬化剤組成物を得た。得られた各硬化剤組成物について、実施例18と同様の方法、及び基準により、粘度及び臭気を測定評価した。表3に各硬化剤組成物における添加剤の成分、及び物性評価を示す。
Examples 20-32
As a curing agent, 70 parts by weight of an aliphatic polyamine (ADEKA HARDNER EH-479A manufactured by ADEKA CORPORATION) and 30 parts by weight of n- aminoethylpiperazine , the curing agent (total amount: 100 parts by weight), The additives shown in No. 3 (30 parts by weight) were mixed while being heated at 90 ° C. for 30 minutes to obtain respective curing agent compositions. About each obtained hardening | curing agent composition, the viscosity and odor were measured and evaluated by the method similar to Example 18, and a reference | standard. Table 3 shows the components of the additives in each curing agent composition and the evaluation of physical properties.
なお、表3に示す添加剤において、実施例20〜24の添加剤は、ベンジルアルコールで濃度50%に希釈した添加剤を用いた。 In addition, in the additive shown in Table 3, the additive diluted with 50% of the concentration with benzyl alcohol was used for the additive of Examples 20-24.
<結果と考察>
実施例25〜32のように、添加物が固体である場合においても、アミン硬化剤と充分に均一混合することによって、アミンの臭気抑制効果が得られることが分かった。
<Results and discussion>
As in Examples 25 to 32, even when the additive was solid, it was found that an amine odor suppressing effect can be obtained by sufficiently uniformly mixing with the amine curing agent.
また、実施例20〜24のように、ベンジルアルコールで濃度50%に希釈した場合においても、相対的に臭気抑制効果が発揮できる添加剤中の化合物の量が減ったが、その場合においても、アミンの臭気抑制が充分に得られることが分かった。 Further, as in Examples 20 to 24, even when diluted with benzyl alcohol to a concentration of 50%, the amount of the compound in the additive capable of relatively exerting the odor suppressing effect decreased, but even in that case, It was found that the odor suppression of amine can be sufficiently obtained.
なお、実施例32においては、ナフトール臭が確認されたが、アミンの臭気評価が「4」と高く、臭気抑制が充分に得られていることが確認できた。 In Example 32, a naphthol odor was confirmed, but the amine odor evaluation was as high as “4”, and it was confirmed that odor suppression was sufficiently obtained.
実施例33〜40
表4に示す硬化剤、及びスチレン化フェノールを表4に示す含有量となるようにそれぞれ混合し、各硬化剤組成物を得た。得られた各硬化剤組成物について、実施例18と同様の方法、及び基準により、粘度及び臭気を測定評価した。表4に硬化剤組成物の含有量、及び各硬化剤組成物における添加剤の成分、並びに物性評価を示す。
Examples 33-40
The curing agent shown in Table 4 and the styrenated phenol were mixed so as to have the contents shown in Table 4 to obtain each curing agent composition. About each obtained hardening | curing agent composition, the viscosity and odor were measured and evaluated by the method similar to Example 18, and a reference | standard. Table 4 shows the content of the curing agent composition, the components of the additives in each curing agent composition, and the evaluation of physical properties.
なお、表4に示す硬化剤において、実施例37のアミドアミンは、コグニスジャパン株式会社製のゼナミド747;実施例38のポリメルカプタンは、三菱化学株式会社製のQX−11;実施例39のDDM変性ポリアミン(ジアミノジフェニルメタン変性ポリアミン)は、大都産業株式会社製のダイトクラールM−1086;実施例40の3級アミンは、株式会社アデカ製のアデカハードナーEHC−30を用いた。
Note that in the curing agents shown in Table 4, amidoamine of Example 37, Cognis Zenamido 747 K.K.; polymercaptan of Example 38, QX-11 manufactured by Mitsubishi Chemical Corporation; DDM modified embodiment 39 The polyamine (diaminodiphenylmethane-modified polyamine) was Daitokural M-1086 manufactured by Daito Sangyo Co., Ltd .; the tertiary amine of Example 40 was Adeka Hardener EHC-30 manufactured by Adeka Corporation.
<結果と考察>
実施例33〜40において示すように、硬化剤の種類に関わらず、本願発明の添加剤を使用することにより、硬化剤由来の臭気抑制効果が得られることが確認できた。
<Results and discussion>
As shown in Examples 33 to 40, it was confirmed that the effect of suppressing odor derived from the curing agent was obtained by using the additive of the present invention regardless of the type of the curing agent.
実施例41〜61
前記実施例7、8、及び18〜36で得られた硬化剤組成物と、エポキシ樹脂(株式会社服部商店製のコーレジンEC(冬用)(エポキシ当量:300当量)を、硬化剤組成物中の硬化剤の活性水素当量1当量に対して、コーレジンEC(冬用)中のエポキシ当量が1当量となるように混合した。
Examples 41-61
In the curing agent composition, the curing agent composition obtained in Examples 7, 8, and 18 to 36 and an epoxy resin (Corresin EC (for winter) manufactured by Hattori Shoten Co., Ltd. (epoxy equivalent: 300 equivalents)) It mixed so that the epoxy equivalent in Core Resin EC (for winter) might become 1 equivalent with respect to 1 equivalent of active hydrogen equivalents of the hardening | curing agent.
また、得られた各混合物を、23℃、湿度50%の条件でスレート板に塗布して塗膜を形成し、23℃、湿度50%の条件にて塗膜を硬化させた。 Moreover, each obtained mixture was apply | coated to the slate board on the conditions of 23 degreeC and the humidity 50%, the coating film was formed, and the coating film was hardened on the conditions of 23 degreeC and the humidity 50%.
得られた硬化物について、光沢・表面状態、耐水白化、鉛筆硬度、及びD硬度(タイプD硬度)を以下の方法により、測定した。なお、上記の物性値は、硬化後24時間放置した後の物性である。測定結果を表5及び表6に示す。 About the obtained hardened | cured material, gloss / surface state, water-whitening, pencil hardness, and D hardness (type D hardness) were measured with the following method. In addition, said physical property value is a physical property after leaving to stand for 24 hours after hardening. The measurement results are shown in Tables 5 and 6.
<光沢・表面状態>
得られた硬化物の表面の外観を以下の基準により評価した。
<Gloss / Surface condition>
The appearance of the surface of the obtained cured product was evaluated according to the following criteria.
5:光沢を有し、表面が非常に滑らかである
4:光沢を有し、表面が滑らかである
3:極小さなゆず肌が見られる
2:細かなゆず肌が見られ、光沢が充分に得られない
1:光沢が全く得られない
<耐水白化>
得られた硬化物の表面の外観を以下の基準により評価した。
5: Glossy, surface is very smooth 4: Glossy, surface is smooth 3: Extremely small Yuzu skin is seen 2: Fine Yuzu skin is seen, sufficient gloss is obtained 1: No gloss at all <Water whitening>
The appearance of the surface of the obtained cured product was evaluated according to the following criteria.
5:白化が全く確認できない
4:白化が若干生じているものの、他の塗膜物性に影響のない程度である
3:白化が生じており、他の塗膜物性に影響が生じる程度である
2:白化が著しく生じている
1:硬化物の表面にクレーターが大きく生じる
<鉛筆硬度>
JIS K−5600に準拠して、鉛筆硬度を測定した。
5: No whitening can be confirmed 4: Although whitening has occurred slightly, there is no influence on the physical properties of other coatings 3: Whitening has occurred, and other physical properties of the coatings are affected 2 : Whitening is remarkable 1: Large craters are generated on the surface of the cured product <Pencil hardness>
The pencil hardness was measured according to JIS K-5600.
<D硬度(タイプD硬度)>
硬度計(株式会社テクロック製のGS−702N)を用いて、JIS K7215Dに準拠して、D硬度を測定した。
<D hardness (type D hardness)>
The D hardness was measured in accordance with JIS K7215D using a hardness meter (GS-702N manufactured by Teclock Co., Ltd.).
比較例11〜15
前記比較例3〜7で得られた硬化剤組成物と、エポキシ樹脂(株式会社服部商店製のコーレジンEC(冬用))を、硬化剤組成物中のアミンの活性水素当量1当量に対して、コーレジンEC(冬用)中のエポキシ当量が1当量となるように混合した。得られた混合物を、実施例41と同様の条件で塗布して塗膜を形成し、塗膜を硬化させた。
Comparative Examples 11-15
The curing agent composition obtained in Comparative Examples 3 to 7 and an epoxy resin (Corresin EC (for winter) manufactured by Hattori Shoten Co., Ltd.) are used with respect to 1 equivalent of active hydrogen equivalent of amine in the curing agent composition. The mixture was mixed so that the epoxy equivalent in Core Resin EC (for winter) was 1 equivalent. The obtained mixture was applied under the same conditions as in Example 41 to form a coating film, and the coating film was cured.
得られた硬化物について、光沢・表面状態、鉛筆硬度、及びD硬度を実施例41と同様の方法により測定した。測定結果を表7に示す。 About the obtained hardened | cured material, gloss / surface state, pencil hardness, and D hardness were measured by the method similar to Example 41. FIG. Table 7 shows the measurement results.
<結果と考察>
表5〜表7の結果より、実施例41〜61のように、樹脂硬化物の形成において、添加剤の配合は塗膜の物性、性状に影響を及ぼすものではなく、また、良好な硬度を有する塗膜硬化物を得ることができることが確認できた。
<Results and discussion>
From the results of Table 5 to Table 7, as in Examples 41 to 61, in the formation of the cured resin, the blending of the additive does not affect the physical properties and properties of the coating film, and has good hardness. It was confirmed that the cured coating film can be obtained.
なお、硬化剤組成物として実施例9〜15を用いて、実施例41と同様の方法により、塗膜を形成し、塗膜を硬化させたところ、スチレン化フェノールの含有量の増加に伴い、硬化物が軟化する傾向にあったが、硬化状態が良好であることが確認できた。 In addition, when Example 9-15 was used as a hardening | curing agent composition and the coating film was formed by the method similar to Example 41 and the coating film was hardened, with the increase in content of styrenated phenol, Although the cured product tended to soften, it was confirmed that the cured state was good.
Claims (5)
前記硬化剤由来臭気低減用硬化剤組成物は、
(A)
ポリアミン、及びポリメルカプタンよりなる群から選ばれる少なくとも1種の硬化剤、
並びに
(B)
一般式(1):
R1は、
炭素数1〜10のアルキル基、カルボキシル基、フェニル基、ヒドロキシル基、及び炭素数1〜6のアルキル基を置換していてもよいアミノ基よりなる群から選ばれる少なくとも1種の置換基を有していてもよいフェニルアルキル基;
炭素数1〜6のアルキル基;
カルボキシル基;
ヒドロキシル基;
炭素数1〜6のアルキル基を有していてもよいフェニル基;又は
炭素数1〜6のアルキル基を置換していてもよいアミノ基
であり、
R1の位置は、オルト位、メタ位、パラ位のいずれの位置に置換されていてもよく、
nが2以上の場合、R1は同一であっても異なっていてもよい)、
又は
一般式(2):
R2は、
水素原子;
炭素数1〜10のアルキル基、カルボキシル基、フェニル基、ヒドロキシル基、及び炭素数1〜6のアルキル基を置換していてもよいアミノ基よりなる群から選ばれる少なくとも1種の置換基を有していてもよいフェニルアルキル基;
炭素数1〜6のアルキル基;
カルボキシル基;
ヒドロキシル基;
炭素数1〜6のアルキル基を有していてもよいフェニル基;又は
炭素数1〜6のアルキル基を置換していてもよいアミノ基であり、
nが2以上の場合、R2は同一であっても異なっていてもよい)
で表される水酸基含有芳香族化合物
(但し、当該水酸基含有芳香族化合物はm-クレゾールを除く)
を含み、
前記硬化剤(A)100重量部に対して、
前記水酸基含有芳香族化合物(B)を5〜2000重量部含む、
硬化剤由来臭気低減用硬化剤組成物であり、
前記(A)硬化剤に対して、前記(B)水酸基含有芳香族化合物を更に含有することを特徴とする方法。 Used hardening agents derived odor reducing curing agent composition, a method for reducing the odor from the curing agent,
The curing agent composition for reducing odor derived from the curing agent is:
(A)
At least one curing agent selected from the group consisting of polyamines and polymercaptans,
And (B)
General formula (1):
R 1 is
It has at least one substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group, a hydroxyl group, and an amino group that may be substituted with an alkyl group having 1 to 6 carbon atoms. An optionally substituted phenylalkyl group;
An alkyl group having 1 to 6 carbon atoms;
Carboxyl group;
A hydroxyl group;
A phenyl group optionally having an alkyl group having 1 to 6 carbon atoms; or an amino group which may be substituted with an alkyl group having 1 to 6 carbon atoms;
The position of R 1 may be substituted at any of the ortho, meta, and para positions,
when n is 2 or more, R 1 may be the same or different).
Or general formula (2):
R 2 is
Hydrogen atom;
It has at least one substituent selected from the group consisting of an alkyl group having 1 to 10 carbon atoms, a carboxyl group, a phenyl group, a hydroxyl group, and an amino group that may be substituted with an alkyl group having 1 to 6 carbon atoms. An optionally substituted phenylalkyl group;
An alkyl group having 1 to 6 carbon atoms;
Carboxyl group;
A hydroxyl group;
A phenyl group optionally having an alkyl group having 1 to 6 carbon atoms; or an amino group which may be substituted with an alkyl group having 1 to 6 carbon atoms;
When n is 2 or more, R 2 may be the same or different)
Hydroxyl group-containing aromatic compound represented by the formula (However, the hydroxyl group-containing aromatic compound excludes m-cresol)
Including
For 100 parts by weight of the curing agent (A),
Containing 5 to 2000 parts by weight of the hydroxyl group-containing aromatic compound (B),
It is a curing agent composition for reducing odor from a curing agent ,
The method (A) further comprising (B) a hydroxyl group-containing aromatic compound with respect to the curing agent.
請求項1に記載の方法。 The polyamine is at least one polyamine selected from the group consisting of chain aliphatic polyamines, cycloaliphatic polyamines, aromatic polyamines, and polyamides.
The method of claim 1.
請求項1又は2に記載の方法。 When R 1 of the hydroxyl group-containing aromatic compound represented by the general formula (1) is a phenylalkyl group which may have the substituent, the alkyl group substituted by the phenyl group has 1 carbon atom. ~ 6,
The method according to claim 1 or 2.
式(1’):
Ra及びRbは、同一又は異なり、
水素原子;又は
炭素数1〜6のアルキル基であり、
Rcは、
水素原子;
炭素数1〜6のアルキル基;
ヒドロキシル基;又は
炭素数1〜6のアルキル基を置換していてもよいアミノ基である)
で表される水酸基含有芳香族化合物である、
請求項1又は2に記載の方法。 The (B) hydroxyl group-containing aromatic compound is
Formula (1 ′):
Ra and Rb are the same or different,
A hydrogen atom; or an alkyl group having 1 to 6 carbon atoms,
Rc is
Hydrogen atom;
An alkyl group having 1 to 6 carbon atoms;
A hydroxyl group; or an amino group which may be substituted with an alkyl group having 1 to 6 carbon atoms)
Is a hydroxyl group-containing aromatic compound represented by:
The method according to claim 1 or 2.
一般式(1”):
で表されるスチレン化フェノール;
ベンジルフェノール;
ジベンジルフェノール;
トリベンジルフェノール;
ビスフェノールF;
フェニルフェノール;
サリチル酸;
ヒドロキノン;
ビスフェノールA、
フェニルフェノール、
tert−ブチルフェノール;
アミノベンジルフェノール;
アミノフェノール;又は
ナフトールである、
請求項1又は2に記載の方法。 The (B) hydroxyl group-containing aromatic compound is
General formula (1 "):
A styrenated phenol represented by:
Benzylphenol;
Dibenzylphenol;
Tribenzylphenol;
Bisphenol F;
Phenylphenol;
Salicylic acid;
Hydroquinone;
Bisphenol A,
Phenylphenol,
tert-butylphenol;
Aminobenzylphenol;
Aminophenol; or naphthol,
The method according to claim 1 or 2.
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