JP5758923B2 - Epoxy acrylate, acrylic curable composition, cured product and method for producing the same - Google Patents
Epoxy acrylate, acrylic curable composition, cured product and method for producing the same Download PDFInfo
- Publication number
- JP5758923B2 JP5758923B2 JP2012556834A JP2012556834A JP5758923B2 JP 5758923 B2 JP5758923 B2 JP 5758923B2 JP 2012556834 A JP2012556834 A JP 2012556834A JP 2012556834 A JP2012556834 A JP 2012556834A JP 5758923 B2 JP5758923 B2 JP 5758923B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy acrylate
- acrylate
- meth
- acrylic
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 title claims description 67
- 239000000203 mixture Substances 0.000 title claims description 44
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims description 28
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- -1 epoxycyclohexane compound Chemical class 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 21
- 239000004925 Acrylic resin Substances 0.000 claims description 14
- 229920000178 Acrylic resin Polymers 0.000 claims description 13
- 239000003505 polymerization initiator Substances 0.000 claims description 13
- 230000003287 optical effect Effects 0.000 claims description 9
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 45
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 239000011347 resin Substances 0.000 description 17
- 229920005989 resin Polymers 0.000 description 17
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 239000011521 glass Substances 0.000 description 11
- 239000000178 monomer Substances 0.000 description 11
- 239000004593 Epoxy Substances 0.000 description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 8
- 239000003112 inhibitor Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- 238000007772 electroless plating Methods 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 239000004973 liquid crystal related substance Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910000679 solder Inorganic materials 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 238000001723 curing Methods 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- FNXVRKAAKSJEIQ-UHFFFAOYSA-N cyclohexane;prop-2-enoic acid Chemical compound OC(=O)C=C.C1CCCCC1 FNXVRKAAKSJEIQ-UHFFFAOYSA-N 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 239000003504 photosensitizing agent Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- NSIHCJDYMGWYKW-UHFFFAOYSA-N (2-hydroxy-2-phenylethyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)C1=CC=CC=C1 NSIHCJDYMGWYKW-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- 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
- FJJYHTVHBVXEEQ-UHFFFAOYSA-N 2,2-dimethylpropanal Chemical compound CC(C)(C)C=O FJJYHTVHBVXEEQ-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 244000028419 Styrax benzoin Species 0.000 description 2
- 235000000126 Styrax benzoin Nutrition 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000005827 chlorofluoro hydrocarbons Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 235000019382 gum benzoic Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 1
- ROGKOUKGHMDPLN-UHFFFAOYSA-N 1-methoxy-10h-phenothiazine Chemical compound S1C2=CC=CC=C2NC2=C1C=CC=C2OC ROGKOUKGHMDPLN-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- FPKCTSIVDAWGFA-UHFFFAOYSA-N 2-chloroanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3C(=O)C2=C1 FPKCTSIVDAWGFA-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- DIVXVZXROTWKIH-UHFFFAOYSA-N 2-hydroxy-1,2-diphenylpropan-1-one Chemical compound C=1C=CC=CC=1C(O)(C)C(=O)C1=CC=CC=C1 DIVXVZXROTWKIH-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- 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
- UOYIYWCAYFTQLH-UHFFFAOYSA-N 3,7-dinitro-1,3,5,7-tetrazabicyclo[3.3.1]nonane Chemical compound C1N2CN([N+](=O)[O-])CN1CN([N+]([O-])=O)C2 UOYIYWCAYFTQLH-UHFFFAOYSA-N 0.000 description 1
- BJEMXPVDXFSROA-UHFFFAOYSA-N 3-butylbenzene-1,2-diol Chemical compound CCCCC1=CC=CC(O)=C1O BJEMXPVDXFSROA-UHFFFAOYSA-N 0.000 description 1
- RDFQSFOGKVZWKF-UHFFFAOYSA-N 3-hydroxy-2,2-dimethylpropanoic acid Chemical compound OCC(C)(C)C(O)=O RDFQSFOGKVZWKF-UHFFFAOYSA-N 0.000 description 1
- UGVRJVHOJNYEHR-UHFFFAOYSA-N 4-chlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 UGVRJVHOJNYEHR-UHFFFAOYSA-N 0.000 description 1
- ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 description 1
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 description 1
- RZVHIXYEVGDQDX-UHFFFAOYSA-N 9,10-anthraquinone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1 RZVHIXYEVGDQDX-UHFFFAOYSA-N 0.000 description 1
- 229940076442 9,10-anthraquinone Drugs 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-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
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- IDLJKTNBZKSHIY-UHFFFAOYSA-N [4-(diethylamino)phenyl]-phenylmethanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=CC=C1 IDLJKTNBZKSHIY-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- PTWJGGCOPUFTFL-UHFFFAOYSA-N cyclohexane;2-methylprop-2-enoic acid Chemical compound CC(=C)C(O)=O.C1CCCCC1 PTWJGGCOPUFTFL-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- DWYKRMTVNUXSIM-UHFFFAOYSA-N hexane-1,6-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OCCCCCCO DWYKRMTVNUXSIM-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- RGBXDEHYFWDBKD-UHFFFAOYSA-N propan-2-yl propan-2-yloxy carbonate Chemical compound CC(C)OOC(=O)OC(C)C RGBXDEHYFWDBKD-UHFFFAOYSA-N 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical class [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 description 1
- 229950006389 thiodiglycol Drugs 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000001993 wax Substances 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
- 239000004711 α-olefin Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
- C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
- C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
- C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
- C08G59/1461—Unsaturated monoacids
- C08G59/1466—Acrylic or methacrylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Emergency Medicine (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Epoxy Resins (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、耐熱性、流動性、靭性、感光性、耐薬品性、硬度、透明性、耐候性に優れた新規なエポキシアクリレート、アクリル系硬化性組成物、硬化物及びその製造法に関するものである。このエポキシアクリレートは、それ自体を重合させるか、又は、各種の不飽和結合を有する化合物と共重合させることにより、耐熱性、靭性、耐薬品性、硬度、透明性、耐候性等に優れた高分子材料を与えることができ、塗料、積層板、接着剤等各種用途に使用できる。また、光硬化性樹脂組成物又は熱硬化性樹脂組成物とすることにより、ソルダーレジスト用樹脂又は、無電解メッキレジスト用樹脂、ハードコート材料、UV硬化塗料、ガラス代替材料、さらには液晶のカラーフィルター等の保護膜としても好適に使用される。 The present invention relates to a novel epoxy acrylate, an acrylic curable composition, a cured product, and a production method thereof excellent in heat resistance, fluidity, toughness, photosensitivity, chemical resistance, hardness, transparency, and weather resistance. is there. This epoxy acrylate has high heat resistance, toughness, chemical resistance, hardness, transparency, weather resistance, etc. by polymerizing itself or copolymerizing with compounds having various unsaturated bonds. A molecular material can be given, and it can be used for various applications such as paints, laminates and adhesives. In addition, by using a photo-curable resin composition or a thermosetting resin composition, a solder resist resin, an electroless plating resist resin, a hard coat material, a UV curable paint, a glass substitute material, or even a liquid crystal color It is also suitably used as a protective film for filters and the like.
主にエポキシ化合物とアクリル酸との反応により得られるエポキシアクリレート樹脂は、感光材料、架橋剤等、各種機能性高分子材料として幅広く使用されている。この樹脂は分子中に水酸基を有するため、溶剤溶解性、耐熱性等に優れる(非特許文献1)。特に、ベンゼンにエポキシ基が直接結合したエポキシフェニル化合物であるエポキシエチルベンゼン由来のエポキシアクリレートである2−ヒドロキシ−2−フェニルエチルアクリレートを硬化した樹脂では、一般的なグリジジルエーテル基を有するエポキシアクリレート樹脂と比較して、柔軟なオキシメチレン部位を持たないため、硬化物の分子運動が抑制されることにより優れた耐熱性、低熱膨張性が期待される。さらに、各種の不飽和結合を有する化合物との共重合(特許文献1)や、イソシアネート等水酸基と反応可能な化合物との架橋(特許文献2)により耐熱性、耐湿性、耐薬品性等に優れた高分子材料を与える。 Epoxy acrylate resins obtained mainly by reaction of epoxy compounds with acrylic acid are widely used as various functional polymer materials such as photosensitive materials and crosslinking agents. Since this resin has a hydroxyl group in the molecule, it is excellent in solvent solubility, heat resistance and the like (Non-Patent Document 1). In particular, an epoxy acrylate resin having a general glycidyl ether group in a resin obtained by curing 2-hydroxy-2-phenylethyl acrylate, which is an epoxy acrylate derived from epoxyethylbenzene, which is an epoxyphenyl compound in which an epoxy group is directly bonded to benzene Compared with the above, since it does not have a flexible oxymethylene moiety, excellent heat resistance and low thermal expansion are expected by suppressing the molecular motion of the cured product. Furthermore, it is excellent in heat resistance, moisture resistance, chemical resistance, etc. by copolymerization with compounds having various unsaturated bonds (Patent Document 1) and crosslinking with a compound capable of reacting with a hydroxyl group such as isocyanate (Patent Document 2). Give a high polymer material.
しかしながら、エポキシエチルベンゼン由来のエポキシアクリレートに関する唯一の開示例である2−ヒドロキシ−2−フェニルエチルアクリレートの役割は、専ら反応希釈剤や架橋剤であり、樹脂の物性向上を目的としたエポキシアクリレート自体の改良については着目されていなかった。 However, the role of 2-hydroxy-2-phenylethyl acrylate, which is the only disclosed example regarding epoxy acrylate derived from epoxyethylbenzene, is exclusively a reaction diluent and a cross-linking agent, and the role of epoxy acrylate itself for the purpose of improving the physical properties of the resin. There was no focus on improvement.
さらに、エポキシエチルベンゼン由来のエポキシアクリレートについては、芳香族化合物であるため、光学部品分野へ適用するためには、透明性、耐候性が不十分であると考えられる。 Furthermore, since the epoxy acrylate derived from epoxyethylbenzene is an aromatic compound, it is considered that transparency and weather resistance are insufficient for application to the field of optical components.
従って、本発明の目的は、耐熱性、低熱膨張性、透明性、耐候性に優れ、ソルダーレジスト用樹脂又は、無電解メッキレジスト用樹脂、ハードコート材料、UV硬化塗料、ガラス代替材料、液晶のカラーフィルター等に有用なエポキシアクリレート、アクリル系組成物及び硬化物を提供することである。特に、光学材料として有用なアクリル樹脂組成物及び硬化物を提供することである。 Therefore, the object of the present invention is excellent in heat resistance, low thermal expansion, transparency, and weather resistance, and is a resin for solder resist or resin for electroless plating resist, hard coat material, UV curable paint, glass substitute material, liquid crystal It is to provide an epoxy acrylate, an acrylic composition and a cured product useful for a color filter and the like. In particular, it is to provide an acrylic resin composition and a cured product useful as an optical material.
本発明者等は、上述した従来技術における実状に鑑みて、耐熱性、低熱膨張性、高屈折率、透明性、耐候性に優れ、ソルダーレジスト用樹脂又は、無電解メッキレジスト用樹脂、ハードコート材料、UV硬化塗料、ガラス代替材料、液晶のカラーフィルター等に有用なアクリル樹脂を得るべく鋭意研究した結果、エポキシアクリレートとして、エポキシシクロヘキサン化合物と不飽和カルボン酸とを反応させて得られるエポキシアクリレートを用いることにより、上記の課題が解決することを見出し、本発明を完成するに至った。 In light of the actual situation in the prior art described above, the present inventors have excellent heat resistance, low thermal expansion, high refractive index, transparency, weather resistance, solder resist resin or electroless plating resist resin, hard coat As a result of earnest research to obtain acrylic resins useful for materials, UV curable paints, glass substitute materials, liquid crystal color filters, etc., epoxy acrylate obtained by reacting an epoxy cyclohexane compound with an unsaturated carboxylic acid is used as an epoxy acrylate. By using it, it has been found that the above problems can be solved, and the present invention has been completed.
すなわち、本発明は、下記一般式(1)で表されるエポキシアクリレートに関する。
(但し、Xは水素原子又はメチル基を表す。ZはC1〜C6のアルキル基を表し、全てが同一でも異なっていてもよい。nは2〜3の数を示す。aは0〜4の数を示す。)That is, the present invention relates to an epoxy acrylate represented by the following general formula (1).
(However, X represents a hydrogen atom or a methyl group. Z represents a C1-C6 alkyl group, all may be the same or different. N represents a number of 2 to 3. a represents 0-4. Indicates the number.)
また、本発明は、上記一般式(1)で表されるエポキシアクリレートを主成分として含み、下記一般式(2)で表わされるエポキシアクリレートを副成分として含むエポキシアクリレートに関する。
Moreover, this invention relates to the epoxy acrylate which contains the epoxy acrylate represented by the said General formula (1) as a main component, and contains the epoxy acrylate represented by the following General formula (2) as a subcomponent.
但し、Aは式(3)で表されるエステル結合含有基であり、Bは式(3)又は式(4)で表されるエステル結合含有基である。bは1〜2の整数を示す。Z、X、aは一般式(1)と同じ意味である。 However, A is an ester bond-containing group represented by Formula (3), and B is an ester bond-containing group represented by Formula (3) or Formula (4). b shows the integer of 1-2. Z, X, and a have the same meaning as in general formula (1).
また、本発明は、上記エポキシアクリレートと、重合開始剤を含有することを特徴とするアクリル系硬化性組成物に関する。また、本発明は、このアクリル系硬化性組成物を成形硬化させてなることを特徴とするアクリル樹脂硬化物に関する。 The present invention also relates to an acrylic curable composition comprising the above epoxy acrylate and a polymerization initiator. Moreover, this invention relates to the acrylic resin hardened | cured material characterized by shape-hardening this acrylic curable composition.
また、本発明は、一般式(5)で表されるエポキシシクロヘキサン化合物とアクリル酸又はメタクリル酸とを反応させることを特徴とする上記エポキシアクリレートの製造方法に関する。 Moreover, this invention relates to the manufacturing method of the said epoxy acrylate characterized by making the epoxy cyclohexane compound and acrylic acid or methacrylic acid represented by General formula (5) react.
(但し、Z、a及びnは、一般式(1)と同じ意味を有する。)
(However, Z, a and n have the same meaning as in general formula (1).)
また、本発明は上記アクリル系硬化性組成物又はアクリル樹脂硬化物が、光学材料用であることを特徴とするアクリル系硬化性組成物又はアクリル樹脂硬化物である。 Moreover, this invention is an acrylic curable composition or acrylic resin hardened | cured material characterized by using the said acrylic curable composition or acrylic resin hardened | cured material for optical materials.
まず、本発明のエポキシアクリレートについて説明する。 First, the epoxy acrylate of the present invention will be described.
本発明のエポキシアクリレートは、上記一般式(1)で表される。ここで、Xは水素原子又はメチル基を表す。ZはC1〜C6のアルキル基を表し、全てが同一でも異なっていてもよい。nは2〜3の整数を示す。aは0〜4の整数を示す。但し、n+aは6を超えることはない。 The epoxy acrylate of the present invention is represented by the general formula (1). Here, X represents a hydrogen atom or a methyl group. Z represents a C1-C6 alkyl group, and all may be the same or different. n shows the integer of 2-3. a represents an integer of 0 to 4. However, n + a does not exceed 6.
上記一般式(1)で表されるエポキシアクリレートは上記一般式(5)で表されるエポキシシクロヘキサン化合物と不飽和カルボン酸(アクリル酸、メタアクリル酸、又は両者を含む意味である)を反応させアクリレート化を行うことで製造することができる。従って、Zの種類は、原料として使用されるエポキシシクロヘキサン化合物の構造に由来することになる。エポキシシクロヘキサン化合物の入手の容易さや得られるエポキシアクリレートの特性の点から、ZはC1〜C6のアルキル基であり、aは0〜4、好ましくは0〜1の整数である。 The epoxy acrylate represented by the general formula (1) is obtained by reacting the epoxycyclohexane compound represented by the general formula (5) with an unsaturated carboxylic acid (meaning including acrylic acid, methacrylic acid, or both). It can be produced by acrylated. Therefore, the kind of Z comes from the structure of the epoxycyclohexane compound used as a raw material. Z is a C1-C6 alkyl group, and a is an integer of 0-4, preferably 0-1, in view of the availability of the epoxycyclohexane compound and the properties of the resulting epoxy acrylate.
上記一般式(5)で表されるエポキシシクロヘキサン化合物は、シクロヘキサン骨格にエポキシエチル基が2個置換された構造(ジ置換体)又は3個置換された構造(トリ置換体)を取り得る。ジ置換体の異性体としては、1,2−ジ置換体(o−体)、1,3−ジ置換体(m−体)及び1,4−ジ置換体(p−体)があり、トリ置換体の異性体としては、1,2,3−トリ置換体、1,2,4−トリ置換体、1,3,5−トリ置換体がある。本発明の製造方法で使用するエポキシシクロヘキサン化合物としては、これら異性体の混合物(ジ置換体同士、トリ置換体同士又はジ置換体とトリ置換体の混合物であっても良い。)が、ジ置換体同士の混合物の場合は、m−体及びp−体の含有率が高いものが耐熱性及び低粘度性両立の観点で好ましく、90重量%以上、好ましくは95重量%以上m−体及びp−体を含有するものが好適に使用される。また、アクリル樹脂硬化物の耐熱性の点から、トリ置換体が好ましく、1,2,4−トリ置換体が特に好ましい。 The epoxycyclohexane compound represented by the general formula (5) can take a structure in which two epoxyethyl groups are substituted on the cyclohexane skeleton (disubstituted product) or a structure in which three epoxyethyl groups are substituted (trisubstituted product). As isomers of the di-substituted product, there are 1,2-di-substituted product (o-isomer), 1,3-di-substituted product (m-isomer) and 1,4-di-substituted product (p-isomer). Tri-substituted isomers include 1,2,3-tri-substituted, 1,2,4-tri-substituted, and 1,3,5-tri-substituted. As an epoxycyclohexane compound used in the production method of the present invention, a mixture of these isomers (may be a di-substituted product, a tri-substituted product or a mixture of a di-substituted product and a tri-substituted product). In the case of a mixture of bodies, one having a high content of m-form and p-form is preferred from the viewpoint of both heat resistance and low viscosity, and is 90% by weight or more, preferably 95% by weight or more. -The thing containing a body is used suitably. Further, from the viewpoint of heat resistance of the cured acrylic resin, a tri-substituted product is preferable, and a 1,2,4-tri-substituted product is particularly preferable.
本発明のエポキシアクリレートは、エポキシシクロヘキサン化合物と不飽和カルボン酸を反応させることで製造することができる。この反応では、エポキシシクロヘキサン化合物のエポキシ基が開環して不飽和カルボン酸とエステル結合を生じて結合する。この開環はα位とβ位のいずれからでも起こるが、α位で開環した上記一般式(1)のエポキシアクリレート(α付加体)が主成分となり、β位で開環した上記一般式(2)のエポキシアクリレート(β付加体)が副成分となる。一般式(2)のエポキシアクリレートには2種類がある。すなわち、一般式(2)中のA及びBの両方が式(3)で表されるエステル結合含有基(β付加体)である場合と、一般式(2)中のAが式(3)で表されるエステル結合含有基(β付加体)で、Bの一部又は全てが式(4)で表されるエステル結合含有基(α付加体)である場合がある。前者を全β付加体といい、後者を半β付加体といい、両者をまとめてβ付加体という。全β付加体の生成割合は、半β付加体のそれより十分に低い。なお、一般式(2)中のA及びBの両方が式(3)で表されるエステル結合含有基(α付加体)である場合は、一般式(1)と同じとなる。 The epoxy acrylate of the present invention can be produced by reacting an epoxycyclohexane compound with an unsaturated carboxylic acid. In this reaction, the epoxy group of the epoxycyclohexane compound is ring-opened to form an ester bond with the unsaturated carboxylic acid. This ring-opening occurs from both α-position and β-position, but the epoxy acrylate (α-adduct) of the above general formula (1) opened at the α-position is a main component, and the above-described general formula opened at the β-position. The epoxy acrylate (β adduct) of (2) is a subcomponent. There are two types of epoxy acrylates of general formula (2). That is, both A and B in the general formula (2) are ester bond-containing groups (β adducts) represented by the formula (3), and A in the general formula (2) is the formula (3). In some cases, a part or all of B is an ester bond-containing group (α adduct) represented by the formula (4). The former is called a full β adduct, the latter is called a half β adduct, and both are collectively called a β adduct. The production rate of the total β-adduct is sufficiently lower than that of the half-β-adduct. In addition, when both A and B in General formula (2) are ester bond containing groups ((alpha) adduct) represented by Formula (3), it becomes the same as General formula (1).
上記の製造方法では、通常α付加体とβ付加体の生成割合は、モル比で100/0.01〜100/70であり、好ましくは100/0.1〜100/50である。したがって、上記の製造方法では、通常本発明のα付加体とβ付加体の両者を含むエポキシアクリレートが得られる。α付加体とβ付加体の両者を含むエポキシアクリレートを、一般式(1)のエポキシアクリレートのみからなるエポキシアクリレートと区別する場合は、前者をエポキシアクリレート組成物といい、後者を一般式(1)のエポキシアクリレートという。特に、区別する必要がない場合は、両者をエポキシアクリレートという。
エポキシアクリレート組成物から一般式(1)のエポキシアクリレートの分離は公知の方法に分離することができる。なお、主成分として含みとは、60%以上、好ましくは70%以上含むことをいい、副成分は、40%以下、好ましくは30%以下含むことがよい。In said manufacturing method, the production | generation ratio of (alpha) adduct and (beta) adduct is 100 / 0.01-100 / 70 by molar ratio normally, Preferably it is 100 / 0.1-100 / 50. Therefore, in the above production method, an epoxy acrylate containing both the α adduct and β adduct of the present invention is usually obtained. When distinguishing an epoxy acrylate containing both an α-adduct and a β-adduct from an epoxy acrylate comprising only the epoxy acrylate of the general formula (1), the former is called an epoxy acrylate composition, and the latter is a general formula (1). This is called epoxy acrylate. Especially when it is not necessary to distinguish, both are called epoxy acrylate.
The epoxy acrylate of the general formula (1) can be separated from the epoxy acrylate composition by a known method. In addition, including as a main component means containing 60% or more, preferably 70% or more, and a subcomponent may contain 40% or less, preferably 30% or less.
上記の製造方法では、一般式(1)及び(2)で表されるエポキシアクリレートを含むエポキシアクリレートが得られる。これらのエポキシアクリレートは、いずれもがシクロヘキサン環化合物であることから、椅子型、船型の異性体があり、また、シス、トランス異性体、又は光学異性体があるので、主成分及び副成分は、これらの異性体を含む混合物であってもよい。上記の製造方法で得られる、一般式(1)及び(2)で表されるエポキシアクリレートは、いずれもエポキシアクリレートであるので、一般式(1)及び(2)で表されるエポキシアクリレートを含む組成物であっても、エポキシアクリレートともいう。 In said manufacturing method, the epoxy acrylate containing the epoxy acrylate represented by General formula (1) and (2) is obtained. Since these epoxy acrylates are all cyclohexane ring compounds, there are chair-type and ship-type isomers, and since there are cis, trans isomers, or optical isomers, the main component and subcomponents are: A mixture containing these isomers may also be used. Since the epoxy acrylates represented by the general formulas (1) and (2) obtained by the above production method are both epoxy acrylates, the epoxy acrylates represented by the general formulas (1) and (2) are included. Even if it is a composition, it is also called epoxy acrylate.
本発明のエポキシアクリレートは、エポキシシクロヘキサン化合物と不飽和カルボン酸とを必要に応じて触媒、重合禁止剤の存在下、50〜200℃で1〜50時間反応することで製造することができる。 The epoxy acrylate of the present invention can be produced by reacting an epoxycyclohexane compound and an unsaturated carboxylic acid at 50 to 200 ° C. for 1 to 50 hours in the presence of a catalyst and a polymerization inhibitor as necessary.
エポキシシクロヘキサン化合物と不飽和カルボン酸の原料仕込み割合は、エポキシシクロヘキサン化合物と不飽和カルボン酸のモル比で100/5〜5/100、好ましくは、100/10〜10/100となる反応割合が好ましい。 The raw material charge ratio of the epoxycyclohexane compound and the unsaturated carboxylic acid is 100/5 to 5/100, preferably 100/10 to 10/100, as the molar ratio of the epoxycyclohexane compound and the unsaturated carboxylic acid. .
この際に使用できる触媒としては、例えば水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物、トリエチルアミン、ベンジルジメチルアミン等の第三級アミン、テトラメチルアンモニウムクロライド等の第4級アンモニウム塩、イミダゾール化合物、トリフェニルホスフィン等のホスフィン類、テトラ−n−ブチルホスホニウムテトラフェニルボレート等のホスホニウム塩等が挙げられる。これらの触媒は単独でも2種以上の併用でもよい。触媒使用量としては、用いる触媒により異なるが、エポキシシクロヘキサン化合物の100モルに対して、0.01〜100モルであることが好ましく、さらに好ましくは0.1〜80モルである。 Examples of the catalyst that can be used in this case include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, tertiary amines such as triethylamine and benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride, imidazole, and the like. Compounds, phosphines such as triphenylphosphine, and phosphonium salts such as tetra-n-butylphosphonium tetraphenylborate. These catalysts may be used alone or in combination of two or more. The amount of the catalyst used varies depending on the catalyst used, but is preferably 0.01 to 100 mol, more preferably 0.1 to 80 mol, per 100 mol of the epoxycyclohexane compound.
反応を行うに際に使用できる重合禁止剤としては、ビニル化合物の重合禁止剤として公知の重合禁止剤で良く、例えばフェノチアジン、メトキシフェノチアジン、ヒンダードアミン等のアミン類、フェノール、メトキシフェノール、ヒドロキノン、t−ブチルカテコール、ブチルヒドロキシトルエン、クレゾール等のフェノール類等が挙げられるが、好ましくはフェノール類である。これらの重合禁止剤は単独でも2種以上の併用でもよい。重合禁止剤使用量としては、用いる触媒により異なるが、エポキシシクロヘキサン化合物の100モルに対して、0.001〜10モルであることが好ましく、さらに好ましくは0.01〜1モルである。 As the polymerization inhibitor that can be used in carrying out the reaction, known polymerization inhibitors may be used as polymerization inhibitors for vinyl compounds, for example, amines such as phenothiazine, methoxyphenothiazine, hindered amine, phenol, methoxyphenol, hydroquinone, t- Phenols such as butylcatechol, butylhydroxytoluene, cresol and the like can be mentioned, and phenols are preferable. These polymerization inhibitors may be used alone or in combination of two or more. The amount of polymerization inhibitor used varies depending on the catalyst used, but is preferably 0.001 to 10 mol, more preferably 0.01 to 1 mol, per 100 mol of the epoxycyclohexane compound.
反応を行うに際しては、必要に応じて有機溶媒を用いてもよい。有機溶媒としては、例えばトルエン、キシレン等の芳香族炭化水素系溶媒、MIBK、MEK等のケトン系溶媒等が挙げられる。溶媒の使用量としては、エポキシシクロヘキサン化合物及び不飽和カルボン酸の合計重量100重量部に対して通常50〜5000重量部、好ましくは100〜2000重量部である。 In carrying out the reaction, an organic solvent may be used as necessary. Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as MIBK and MEK, and the like. As a usage-amount of a solvent, it is 50-5000 weight part normally with respect to 100 weight part of total weights of an epoxy cyclohexane compound and unsaturated carboxylic acid, Preferably it is 100-2000 weight part.
反応を行うに際しては、必要に応じて空気又は酸素を導入してもよい。反応の制御の点から、好ましくは空気を導入するとよい。 In carrying out the reaction, air or oxygen may be introduced as necessary. From the viewpoint of controlling the reaction, air is preferably introduced.
反応で得られたエポキシアクリレートは、一般式(1)のエポキシアクリレートを主成分とし、一般式(2)のエポキシアクリレートのような異性体を副成分とする混合物、又はn数の異なる混合物が得られることになる。これらの混合物は、樹脂原料として使用する場合は、エポキシアクリレートとしてそのまま使用することができる。有機薬品等の原料とする場合は、再結晶等により精製又は分離することもできる。 The epoxy acrylate obtained by the reaction is a mixture containing the epoxy acrylate of the general formula (1) as a main component and an isomer such as the epoxy acrylate of the general formula (2) as a minor component, or a mixture having a different n number. Will be. When these mixtures are used as resin raw materials, they can be used as they are as epoxy acrylates. When used as a raw material for organic chemicals, it can be purified or separated by recrystallization or the like.
エポキシシクロヘキサン化合物は、ビニルシクロヘキシル化合物を過酸化物によりエポキシ化したものを使用できる。エピクロロヒドリンを用いないため、得られる化合物は、塩素含有量が少ない。過酸化物としては、通常の方法により得られる過酸、過酸化水素、又は有機過酸化物を使用することができる。 As the epoxycyclohexane compound, one obtained by epoxidizing a vinylcyclohexyl compound with a peroxide can be used. Since epichlorohydrin is not used, the resulting compound has a low chlorine content. As the peroxide, a peracid, hydrogen peroxide, or an organic peroxide obtained by a usual method can be used.
本発明のアクリル系硬化性組成物は、上記一般式(1)のエポキシアクリレート又はこれを主成分とする上記エポキシアクリレート組成物と、重合開始剤を含む。 The acrylic curable composition of the present invention includes the epoxy acrylate of the general formula (1) or the epoxy acrylate composition containing the epoxy acrylate as a main component and a polymerization initiator.
重合開始剤としては、ビニル化合物の重合開始剤として公知の重合開始剤で良く、紫外線、電子線等の活性エネルギー線の照射又はラジカル重合開始剤を適用することにより硬化する。 The polymerization initiator may be a known polymerization initiator as a polymerization initiator for a vinyl compound, and is cured by irradiation with an active energy ray such as an ultraviolet ray or an electron beam or by applying a radical polymerization initiator.
紫外線照射による硬化に際しては、光重合開始剤を添加する。光重合開始剤としては、特に限定されるものではないが、紫外線の照射により励起されてラジカルを発生するタイプの通常の光重合開始剤が挙げられ、具体的には、適当な開始剤として、ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾイン−iso−プロピルエーテル、α−メチルベンゾイン等のベンゾイン類、α−ヒドロキシイソブチルフェノン、ベンゾフェノン、p−メチルベンゾフェノン、p−クロロベンゾフェノン、p−ジエチルアミノベンゾフェノン等のベンゾフェノン類、アセトフェノン、9,10−アントラキノン、1−クロロアントラキノン、2−クロロアントラキノン等のアントラキノン類、ジフェニルジスルフィド、テトラメチルチウラムジスルフィド等の含イオウ化合物類等が例示される。 When curing by ultraviolet irradiation, a photopolymerization initiator is added. Although it does not specifically limit as a photoinitiator, The normal photoinitiator of the type which generate | occur | produces a radical by being excited by ultraviolet irradiation is mentioned, Specifically, as a suitable initiator, Benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin-iso-propyl ether, α-methylbenzoin, α-hydroxyisobutylphenone, benzophenone, p-methylbenzophenone, p-chlorobenzophenone, p-diethylaminobenzophenone, etc. Examples include benzophenones, acetophenone, 9,10-anthraquinone, 1-chloroanthraquinone, anthraquinones such as 2-chloroanthraquinone, and sulfur-containing compounds such as diphenyl disulfide and tetramethylthiuram disulfide.
これらの光重合開始剤は、単独で又は2種以上混合して使用され、その配合量としては、重合性化合物の合計量に対して0.1〜10重量%程度が推奨される。 These photopolymerization initiators are used alone or in admixture of two or more, and the blending amount is recommended to be about 0.1 to 10% by weight with respect to the total amount of the polymerizable compound.
また、光重合開始剤による光重合反応を促進するために、光増感剤を添加してもよい。 Moreover, in order to accelerate the photopolymerization reaction by the photopolymerization initiator, a photosensitizer may be added.
この光増感剤は、特に限定されるものではなく、具体的には、トリエチルアミン、トリエタノールアミン等の3級アミン類、トリフェニルホスフィン等のアルキルホスフィン類、チオジクリコール等のチオエーテル類等が例示され、その配合量としては、重合性化合物(上記エポキシアクリレート又はエポキシアクリレート組成物と、必要により加えられる他の重合性モノマーをいう)の合計量に対して0.01〜5重量%程度が推奨される。 The photosensitizer is not particularly limited. Specifically, tertiary amines such as triethylamine and triethanolamine, alkylphosphines such as triphenylphosphine, thioethers such as thiodiglycol, and the like. The blending amount thereof is about 0.01 to 5% by weight with respect to the total amount of the polymerizable compound (referring to the above-mentioned epoxy acrylate or epoxy acrylate composition and other polymerizable monomer added if necessary). Recommended.
紫外線の光源としては、ケミカルランプ、低圧水銀灯、高圧水銀灯、キセノンランプ、メタルハライドランプ等が用いられる。 As the ultraviolet light source, a chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a xenon lamp, a metal halide lamp, or the like is used.
電子線により硬化する場合には、光重合開始剤や光増感剤を用いる必要はなく、汎用の電子線発生装置により、通常、1〜20メガラッド程度の線量の電子線を照射すればよい。 In the case of curing with an electron beam, it is not necessary to use a photopolymerization initiator or a photosensitizer, and an electron beam with a dose of about 1 to 20 megarads is usually irradiated with a general-purpose electron beam generator.
本発明に係るアクリル系硬化性組成物をラジカル重合するに際して用いられるラジカル重合開始剤は、特に限定されるものではなく、具体的には、過酸化ベンゾイル、ジイソプロピルパーオキシカーボネート、過酸化ラウロイル等の過酸化物、アゾビスイソブチロニトリル等のアゾ化合物が例示され、これらの重合開始剤は単独でも2種以上の併用でもよい。重合開始剤は、熱硬化用のものと光硬化用のものを用途に応じて使い分けることが好ましい。 The radical polymerization initiator used for radical polymerization of the acrylic curable composition according to the present invention is not particularly limited, and specific examples thereof include benzoyl peroxide, diisopropyl peroxycarbonate, lauroyl peroxide, and the like. Azo compounds such as peroxide and azobisisobutyronitrile are exemplified, and these polymerization initiators may be used alone or in combination of two or more. As the polymerization initiator, it is preferable to use one for thermosetting and one for photocuring depending on the application.
これら重合開始剤の使用量は、用いる重合禁止剤により異なるが、重合性化合物の合計量に対して0.001〜5重量部であることが好ましく、さらに好ましくは0.01〜1重量部である。但し、この混合比は使用する硬化剤の種類により大きく変化するので最適条件を適宜決定することが必要である。 The amount of these polymerization initiators used varies depending on the polymerization inhibitor used, but is preferably 0.001 to 5 parts by weight, more preferably 0.01 to 1 part by weight, based on the total amount of polymerizable compounds. is there. However, since this mixing ratio varies greatly depending on the type of curing agent used, it is necessary to appropriately determine the optimum conditions.
本発明のアクリル系硬化性組成物には、必要に応じて一般式(1)のエポキシアクリレート又はこれを主成分とする上記エポキシアクリレート組成物の他に、熱又は光による他の重合性モノマーを添加することができる。しかし、重合性成分中には、上記一般式(1)のエポキシアクリレート又はこれを主成分とする上記エポキシアクリレート組成物を合計で50wt%以上含むことがよい。他の重合性モノマーとしては、公知の熱又は光による重合性モノマーで良く、以下に例示する各種のアクリレート系化合物を単独で又は2種以上混合し、硬化性成分として併用することができる。 In addition to the epoxy acrylate of the general formula (1) or the above-mentioned epoxy acrylate composition containing this as a main component, the acrylic curable composition of the present invention may contain other polymerizable monomers by heat or light as necessary. Can be added. However, the polymerizable component preferably contains 50 wt% or more of the epoxy acrylate of the general formula (1) or the epoxy acrylate composition containing the same as the main component. The other polymerizable monomer may be a known heat or light polymerizable monomer, and various acrylate compounds exemplified below may be used alone or in combination of two or more, and used together as a curable component.
単官能性(メタ)アクリレートとしては、メチル(メタ)アクリレート、エチル(メタ)アクリレート、n−プロピル(メタ)アクリレート、ブチル(メタ)アクリレート、iso−ブチル(メタ)アクリレート、n−ヘキシル(メタ)アクリレート、2−エチルヘキシル(メタ)アクリレート、デシル(メタ)アクリレート、ラウリル(メタ)アクリレート、ステアリル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート、2−ヒドロキシエチル(メタ)アクリレート、2−ヒドロキシプロピル(メタ)アクリレート、ジメチルアミノエチル(メタ)アクリレート、ジエチルアミノエチル(メタ)アクリレート、3−クロロ−2−ヒドロキシプロピル(メタ)アクリレート、2,3−ジブロムプロピル(メタ)アクリレート等が例示される。 Monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, butyl (meth) acrylate, iso-butyl (meth) acrylate, and n-hexyl (meth). Acrylate, 2-ethylhexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) Examples include acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, and 2,3-dibromopropyl (meth) acrylate. It is.
二官能性(メタ)アクリレートとしては、エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、テトラエチレングリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、ジプロピレングリコールジ(メタ)アクリレート、トリプロピレングリコールジ(メタ)アクリレート、ポリプロピレングリコールジ(メタ)アクリレート、プロパンジオールジ(メタ)アクリレート、グリセリンジ(メタ)アクリレート、1,3−ブチレングリコールジ(メタ)アクリレート、1,4−ブタンジオールジ(メタ)アクリレート、1,5−ペンタンジオールジ(メタ)アクリレート、1,6−ヘキサンジオールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、ビス(オキシメチル)トリシクロ[5.2.2.02,5 ]デカンジ(メタ)アクリレート、シクロヘキサンジオールジ(メタ)アクリレート、ビス[(メタ)アクリロキシメチル]シクロヘキサン、トリメチロールプロパンとピバルアルデヒドとのアセタールのジアクリレート、ヒドロキシピバリン酸ネオペンチルグリコールエステルジアクリレート、ビスフェノールA−ジ(メタ)アクリレート、ビスフェノールAのアルキレンオキシド付加物のジ(メタ)アクリレート等が例示される。 Bifunctional (meth) acrylates include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and polyethylene glycol di (meth) acrylate. , Propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, propanediol di (meth) acrylate, glycerin di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, bis (oxymethyl) tricyclo [5.2.2.02,5] decanedi (meth) acrylate, cyclohexanediol di (meth) Acrylate, bis [(meth) acryloxymethyl] cyclohexane, acetal diacrylate of trimethylolpropane and pivalaldehyde, neopentyl glycol ester diacrylate of hydroxypivalate, bisphenol A-di (meth) acrylate, alkylene of bisphenol A Examples thereof include di (meth) acrylates of oxide adducts.
三乃至四官能性(メタ)アクリレートとしては、トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート等が例示される。 Examples of tri- to tetrafunctional (meth) acrylates include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like. The
アクリル系重合性オリゴマーとしては、エポキシ(メタ)アクリレート、ウレタン(メタ)アクリレート、ポリエステル(メタ)アクリレート、ポリブタジエンオリゴマーの(メタ)アクリレート、ポリアミド型(メタ)アクリルオリゴマー、メラミン(メタ)アクリレート、シクロペンタジエンオリゴマーの(メタ)アクリレート、シリコーンオリゴマーの(メタ)アクリレート等が例示される。 Acrylic polymerizable oligomers include epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polybutadiene oligomer (meth) acrylate, polyamide-type (meth) acryl oligomer, melamine (meth) acrylate, cyclopentadiene Examples include oligomeric (meth) acrylates and silicone oligomer (meth) acrylates.
また、上記のアクリレート系モノマーに加えて、他の重合性モノマー、例えば、スチレン、酢酸ビニル、塩化ビニル、塩化ビニリデン、アクリロニトリル、ビニルエーテル、アクロレイン等のビニル系化合物、エチレン、ブタジエン等のα−オレフィン等を適宜併用することができる。これらの熱又は光による重合性モノマーは単独でも2種以上の併用でもよい。熱又は光による重合性モノマーは、熱重合性モノマーと光重合性モノマーを用途に応じて使い分けることが好ましい。 In addition to the above acrylate monomers, other polymerizable monomers such as styrene, vinyl acetate, vinyl chloride, vinylidene chloride, acrylonitrile, vinyl ether, vinyl compounds such as acrolein, α-olefins such as ethylene and butadiene, etc. Can be used in combination as appropriate. These heat or light polymerizable monomers may be used alone or in combination of two or more. As the polymerizable monomer by heat or light, it is preferable to use either a thermally polymerizable monomer or a photopolymerizable monomer depending on the application.
本発明のアクリル系硬化性組成物には、必要に応じて充填剤、繊維、カップリング剤、難燃剤、離型剤、発泡剤等のその他の成分を添加することができる。この際の充填剤としては、例えばポリエチレン粉末、ポリプロピレン粉末、石英、シリカ、珪酸塩、炭酸カルシウム、炭酸マグネシウム、石膏、ベントナイト、蛍石、二酸化チタン、カーボンブラック、黒鉛、酸化鉄、アルミニウム粉末、鉄粉、タルク、マイカ、カオリンクレー等が、繊維としては、例えばセルロース繊維、ガラス繊維、炭素繊維、アラミド繊維等が挙げられる。カップリング剤としては、例えばシランカップリング剤、チタンカップリング剤等が挙げられる。難燃剤としては、例えば臭素化ビスフェノールA、三酸化アンチモン、燐系化合物等が挙げられる。離型剤としては、例えばステアリン酸塩、シリコーン、ワックス等が挙げられる。発泡剤としては、例えばフロン、ジクロロエタン、ブタン、ペンタン、ジニトロペンタメチレンテトラミン、パラトルエンスルホニルヒドラジッド、あるいは、フロン、ジクロロエタン、ブタン、ペンタン等が塩化ビニル−塩化ビニリデン共重合体やスチレン−(メタ)アクリル酸エステル共重合体の殻内に充填されている膨張性熱可塑性樹脂粒子等が挙げられる。 Other components such as a filler, a fiber, a coupling agent, a flame retardant, a release agent, and a foaming agent can be added to the acrylic curable composition of the present invention as necessary. Examples of the filler include polyethylene powder, polypropylene powder, quartz, silica, silicate, calcium carbonate, magnesium carbonate, gypsum, bentonite, fluorite, titanium dioxide, carbon black, graphite, iron oxide, aluminum powder, iron Examples of fibers such as powder, talc, mica, kaolin clay, and the like include cellulose fibers, glass fibers, carbon fibers, and aramid fibers. Examples of the coupling agent include a silane coupling agent and a titanium coupling agent. Examples of the flame retardant include brominated bisphenol A, antimony trioxide, and phosphorus compounds. Examples of the mold release agent include stearates, silicones, waxes and the like. Examples of the blowing agent include CFC, dichloroethane, butane, pentane, dinitropentamethylenetetramine, p-toluenesulfonyl hydrazide, or CFC, dichloroethane, butane, pentane and the like, such as vinyl chloride-vinylidene chloride copolymer and styrene- (meth). Examples thereof include expandable thermoplastic resin particles filled in an acrylic ester copolymer shell.
本発明のアクリル系硬化性組成物は従来知られている方法と同様の方法で容易にアクリル樹脂硬化物とすることができる。例えば本発明のエポキシアクリレート又はエポキシアクリレート組成物、重合開始剤、必要により熱又は光による重合性モノマー及びその他の添加剤とを、必要に応じて押出機,ニーダ,ロール等を用いて均一になるまで充分に混合してアクリル樹脂組成物を得て、そのアクリル樹脂組成物を溶融後注型あるいはトランスファー成形機などを用いて成形し、さらに80〜200℃に加熱することにより硬化物を得ることができる。 The acrylic curable composition of the present invention can be easily made into a cured acrylic resin by a method similar to a conventionally known method. For example, the epoxy acrylate or epoxy acrylate composition of the present invention, a polymerization initiator, if necessary, a polymerizable monomer by heat or light and other additives are made uniform by using an extruder, a kneader, a roll or the like, if necessary. To obtain an acrylic resin composition, melt the acrylic resin composition after molding using a casting or transfer molding machine, and further heat to 80 to 200 ° C. to obtain a cured product Can do.
また、本発明のアクリル系硬化性組成物を溶剤に溶解させ、ガラス繊維,カーボン繊維,ポリエステル繊維,ポリアミド繊維,アルミナ繊維,紙などの基材に含浸させ加熱乾燥して得たプリプレグを熱プレス成形して硬化物を得ることなどもできる。例えば本発明のエポキシアクリレート又はエポキシアクリレート組成物、重合開始剤及びその他の添加剤などを均一になるまで加熱、撹拌し、これをガラスクロスに含浸させ加熱半乾燥して溶剤分を飛ばしたプリプレグを、必要枚数重ねて80〜200℃で1時間以上加熱プレスすることによりガラスクロス積層板を作製することができる。 In addition, a prepreg obtained by dissolving the acrylic curable composition of the present invention in a solvent, impregnating a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc., and drying by heating is hot-pressed. It can be molded to obtain a cured product. For example, the epoxy acrylate or epoxy acrylate composition of the present invention, a polymerization initiator and other additives are heated and stirred until uniform, impregnated into a glass cloth, heated and semi-dried, and the solvent is removed. The glass cloth laminate can be produced by stacking the required number and heating and pressing at 80 to 200 ° C. for 1 hour or more.
この際用いうる希釈用溶剤の具体例としては、トルエン、キシレン、メチルエチルケトン、メチルイソブチルケトン、メチルセロソルブ等が好ましく、その使用量は、アクリル系硬化性組成物と該希釈用溶剤の合計重量に対し、10〜70重量%、好ましくは、15〜65重量%である。 Specific examples of the dilution solvent that can be used in this case include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, and the like, and the amount used is based on the total weight of the acrylic curable composition and the dilution solvent. 10 to 70% by weight, preferably 15 to 65% by weight.
こうして得られる硬化物は高い耐熱性、靭性、耐薬品性及び硬度を有しているため、本発明のアクリル樹脂硬化物は、光学樹脂等広範な分野で用いることができる。具体的にはソルダーレジスト用樹脂又は、無電解メッキレジスト用樹脂、ハードコート材料、UV硬化塗料、ガラス代替材料、さらには液晶のカラーフィルター等の保護膜としても好適に使用される。特に、レンズ、プリズム、カラーフィルター、又はこれらの保護膜等の光学材料として優れる。 Since the cured product thus obtained has high heat resistance, toughness, chemical resistance and hardness, the cured acrylic resin of the present invention can be used in a wide range of fields such as optical resins. Specifically, it is also suitably used as a protective film for solder resist resins or electroless plating resist resins, hard coat materials, UV curable paints, glass substitute materials, and liquid crystal color filters. In particular, it is excellent as an optical material such as a lens, a prism, a color filter, or a protective film thereof.
次に本発明の特徴を更に明確にするため実施例を挙げて具体的に説明する。なお、文中の「部」、「%」は全て重量基準を示すものである。 Next, in order to further clarify the characteristics of the present invention, examples will be described in detail. In the text, “part” and “%” all indicate weight standards.
実施例1
冷却管、温度計、空気吹き込み管を取り付けた300mlのガラス製三口フラスコに、1,2,4−トリエポキシエチルシクロヘキサン10.51g(50mmol)、アクリル酸 18.01g(250mmol)、ベンジルトリエチルアンモニウムクロリド0.23g(1mmol)、ジブチルヒドロキシトルエン0.055g(0.25mmol)、トルエン100mlを入れ、空気を装入しながら、80℃で加熱攪拌し、24時間反応させた。反応後、室温まで冷却し、蒸留水100mlで3回洗浄した。トルエン層を分離し、トルエン留去後、酢酸エチル+ヘキサン(4:6)を展開液としたシリカゲルカラムにより精製した。無色透明で粘稠液体のトリエポキシアクリレートシクロヘキサン13.00g(収率61%)を得た。このトリエポキシアクリレートシクロヘキサンは一般式(1)において、aが0であり、XがHであり、nが3であるエポキシアクリレートを主成分とすることがGC分析で確認された。このトリエポキシアクリレートシクロヘキサンの1H-NMRスペクトルを図1に示す。Example 1
A 300 ml glass three-necked flask equipped with a cooling tube, a thermometer, and an air blowing tube was charged with 10.51 g (50 mmol) of 1,2,4-triepoxyethylcyclohexane, 18.01 g (250 mmol) of acrylic acid, and benzyltriethylammonium chloride. 0.23 g (1 mmol), 0.055 g (0.25 mmol) of dibutylhydroxytoluene and 100 ml of toluene were added, and the mixture was heated and stirred at 80 ° C. while introducing air, and reacted for 24 hours. After the reaction, the mixture was cooled to room temperature and washed with 100 ml of distilled water three times. The toluene layer was separated and the toluene was distilled off, followed by purification with a silica gel column using ethyl acetate + hexane (4: 6) as a developing solution. A colorless transparent viscous liquid triepoxy acrylate cyclohexane (13.00 g, yield 61%) was obtained. It was confirmed by GC analysis that this triepoxy acrylate cyclohexane was mainly composed of an epoxy acrylate having a of 0, X of H, and n of 3 in the general formula (1). The 1 H-NMR spectrum of this triepoxyacrylate cyclohexane is shown in FIG.
比較例1
冷却管、温度計、空気吹き込み管を取り付けた500mlのガラス製三口フラスコに、スチレンオキサイド50.00g(416mmol)、アクリル酸29.98g(416mmol)、トリフェニルホスフィン1.09g(4.16mmol)、4−ターシャリー・ブチルカテコール0.346g(2.08mmol)、トルエン100mlを入れ、空気を装入しながら、60℃で加熱攪拌し、24時間反応させた。反応後、室温まで冷却し、蒸留水100mlで3回洗浄した。トルエン層を分離し、トルエン留去後、酢酸エチル+クロロホルム(2:8)を展開液としたシリカゲルカラムにより精製した。無色透明な液体のエポキシアクリレートベンゼン54.37g(収率68%)を得た。Comparative Example 1
In a 500 ml glass three-necked flask equipped with a cooling tube, a thermometer, and an air blowing tube, 50.00 g (416 mmol) of styrene oxide, 29.98 g (416 mmol) of acrylic acid, 1.09 g (4.16 mmol) of triphenylphosphine, 4-Tertiary butylcatechol (0.346 g, 2.08 mmol) and toluene (100 ml) were added, and the mixture was heated and stirred at 60 ° C. while introducing air, and reacted for 24 hours. After the reaction, the mixture was cooled to room temperature and washed with 100 ml of distilled water three times. The toluene layer was separated and the toluene was distilled off, followed by purification with a silica gel column using ethyl acetate + chloroform (2: 8) as a developing solution. A colorless and transparent liquid epoxy acrylate benzene (54.37 g, yield 68%) was obtained.
実施例2
実施例1で得たトリエポキシアクリレートシクロヘキサンの100重量部と、重合開始剤であるイルガキュア184[チバスペシャリティーケミカルズ株式会社製;商品名]5重量部とを、混練して、組成物を調製した。それをガラス板またはアルミ皿上に塗布し、離型PETフィルムを被せ、高圧水銀灯を用いエネルギー線量が600mJ/cm2となるように紫外線照射することにより、硬化させ、膜状の硬化物を得た。
次に、得られた硬化物を試料とし、その鉛筆硬度、ガラス転移点、および熱膨張係数(α1)の分析を、下記の方法により行った。その結果を表1に示した。Example 2
100 parts by weight of the triepoxy acrylate cyclohexane obtained in Example 1 and 5 parts by weight of Irgacure 184 [manufactured by Ciba Specialty Chemicals Co., Ltd .; trade name] as a polymerization initiator were kneaded to prepare a composition. . It is coated on a glass plate or an aluminum pan, covered with a release PET film, and cured by irradiating it with ultraviolet rays so that the energy dose becomes 600 mJ / cm 2 using a high-pressure mercury lamp, and a film-like cured product is obtained. It was.
Next, the obtained cured product was used as a sample, and the pencil hardness, glass transition point, and thermal expansion coefficient (α1) were analyzed by the following method. The results are shown in Table 1.
(鉛筆硬度)
ガラス板上に10〜20μmになるように硬化させた塗膜について、JISK5600に基づき加重1kgで測定を行い、傷の入らない最も硬い鉛筆の硬度で示した。(Pencil hardness)
About the coating film hardened so that it might become 10-20 micrometers on a glass plate, it measured by 1 kg of load based on JISK5600, and showed it with the hardness of the hardest pencil which does not enter a damage | wound.
(ガラス転移点;Tg、熱膨張係数;α1)
試料を長さ20mm、幅5mm、厚さ0.1mmに調整したものについて、エスアイアイ・ナノテクノロジー株式会社製 熱機械的分析装置(TMA/SS)により、窒素雰囲気下、昇温速度7℃/分の条件で求めた。(Glass transition point; Tg, thermal expansion coefficient; α1)
A sample adjusted to a length of 20 mm, a width of 5 mm, and a thickness of 0.1 mm was measured with a thermomechanical analyzer (TMA / SS) manufactured by SII NanoTechnology Co., Ltd. under a nitrogen atmosphere in a temperature rising rate of 7 ° C Calculated under the condition of minutes.
(YI値)
厚み50μmのフィルムを試料とし、JIS K7373に準拠して評価した。(YI value)
A film having a thickness of 50 μm was used as a sample and evaluated according to JIS K7373.
(全光線透過率;Tt)
厚み50μmのフィルムを試料とし、JIS K7361−1に準拠して評価した。(Total light transmittance; Tt)
A film having a thickness of 50 μm was used as a sample and evaluated according to JIS K7361-1.
比較例2
比較例1で得たエポキシアクリレートベンゼンを実験例2と同様の条件で膜状の硬化物を得た。
次に、得られた硬化物の鉛筆硬度、ガラス転移点、および熱膨張係数(α1)の分析を実施例2と同様の条件で行った。その結果を表1に示した。Comparative Example 2
A film-like cured product was obtained from the epoxy acrylate benzene obtained in Comparative Example 1 under the same conditions as in Experimental Example 2.
Next, the pencil hardness, glass transition point, and thermal expansion coefficient (α1) of the obtained cured product were analyzed under the same conditions as in Example 2. The results are shown in Table 1.
本発明のエポキシアクリレートは、従来のエポキシアクリレートと比較して、耐熱性、低熱膨張性、高屈折率、透明性、耐候性に優れ、ソルダーレジスト用樹脂又は、無電解メッキレジスト用樹脂、ハードコート材料、UV硬化塗料、ガラス代替材料、液晶のカラーフィルター等の光学樹脂に有用なエポキシアクリレート、アクリル系組成物及び硬化物を与えることができる。 The epoxy acrylate of the present invention is superior in heat resistance, low thermal expansion, high refractive index, transparency, and weather resistance as compared with conventional epoxy acrylate, and is a resin for solder resist or resin for electroless plating resist, hard coat Epoxy acrylates, acrylic compositions and cured products useful for optical resins such as materials, UV curable paints, glass substitute materials, and liquid crystal color filters can be provided.
Claims (9)
(但し、Xは水素原子又はメチル基を表す。ZはC1〜C6のアルキル基を表し、全てが同一でも異なっていてもよい。nは2〜3の整数を示し、aは0〜4の整数を示す。)Epoxy acrylate represented by the following general formula (1).
(However, X represents a hydrogen atom or a methyl group. Z represents a C1-C6 alkyl group, all may be the same or different. N represents an integer of 2 to 3, and a represents 0-4. Indicates an integer.)
(但し、ZはC1〜C6のアルキル基を表し、全てが同一でも異なっていてもよい。Aは式(3)で表されるエステル結合含有基であり、Bは式(3)又は式(4)で表されるエステル結合含有基である。Xは水素原子又はメチル基を表す。aは0〜4の整数を示し、bは1〜2の整数を示す。)The epoxy acrylate according to claim 1, comprising an epoxy acrylate represented by the general formula (1) and an epoxy acrylate represented by the following general formula (2) as subcomponents.
(However, Z represents a C1-C6 alkyl group, all may be the same or different. A is an ester bond-containing group represented by Formula (3), and B is Formula (3) or Formula ( 4) An ester bond-containing group represented by 4), wherein X represents a hydrogen atom or a methyl group, a represents an integer of 0 to 4, and b represents an integer of 1 to 2.
(但し、ZはC1〜C6のアルキル基を表し、全てが同一でも異なっていてもよい。aは0〜4の数を示す。nは2〜3の数を示す。)The method for producing an epoxy acrylate according to claim 1, wherein an epoxycyclohexane compound represented by the following general formula (5) is reacted with acrylic acid or methacrylic acid.
(However, Z represents a C1-C6 alkyl group, and all may be the same or different. A represents a number from 0 to 4. n represents a number from 2 to 3.)
(但し、ZはC1〜C6のアルキル基を表し、全てが同一でも異なっていてもよい。aは0〜4の数を示す。nは2〜3の数を示す。)The epoxy acrylate production method according to claim 2, wherein an epoxycyclohexane compound represented by the following general formula (5) is reacted with acrylic acid or methacrylic acid.
(However, Z represents a C1-C6 alkyl group, and all may be the same or different. A represents a number from 0 to 4. n represents a number from 2 to 3.)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012556834A JP5758923B2 (en) | 2011-02-10 | 2012-02-01 | Epoxy acrylate, acrylic curable composition, cured product and method for producing the same |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011026955 | 2011-02-10 | ||
JP2011026955 | 2011-02-10 | ||
JP2012556834A JP5758923B2 (en) | 2011-02-10 | 2012-02-01 | Epoxy acrylate, acrylic curable composition, cured product and method for producing the same |
PCT/JP2012/052205 WO2012108305A1 (en) | 2011-02-10 | 2012-02-01 | Epoxy acrylate, acrylic curable composition, cured product and manufacturing processes therefor |
Publications (2)
Publication Number | Publication Date |
---|---|
JPWO2012108305A1 JPWO2012108305A1 (en) | 2014-07-03 |
JP5758923B2 true JP5758923B2 (en) | 2015-08-05 |
Family
ID=46638521
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2012556834A Expired - Fee Related JP5758923B2 (en) | 2011-02-10 | 2012-02-01 | Epoxy acrylate, acrylic curable composition, cured product and method for producing the same |
Country Status (3)
Country | Link |
---|---|
JP (1) | JP5758923B2 (en) |
TW (1) | TWI507392B (en) |
WO (1) | WO2012108305A1 (en) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB930431A (en) * | 1960-10-03 | 1963-07-03 | Rhone Poulenc Sa | Epoxide derivatives of trivinylcyclohexane |
US3251861A (en) * | 1966-05-17 | Di- and triepoxtoe derivatives of trivinylcyclohexane |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS62119551A (en) * | 1985-11-20 | 1987-05-30 | Hitachi Chem Co Ltd | Electrostatic charge image developing toner |
EP1205498A1 (en) * | 2000-11-13 | 2002-05-15 | Nippon Shokubai Co., Ltd. | (Meth)acrylate ester-based resin composition |
JP5676563B2 (en) * | 2010-03-18 | 2015-02-25 | 新日鉄住金化学株式会社 | Epoxy resin composition and cured product |
-
2012
- 2012-02-01 JP JP2012556834A patent/JP5758923B2/en not_active Expired - Fee Related
- 2012-02-01 WO PCT/JP2012/052205 patent/WO2012108305A1/en active Application Filing
- 2012-02-09 TW TW101104200A patent/TWI507392B/en not_active IP Right Cessation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3251861A (en) * | 1966-05-17 | Di- and triepoxtoe derivatives of trivinylcyclohexane | ||
GB930431A (en) * | 1960-10-03 | 1963-07-03 | Rhone Poulenc Sa | Epoxide derivatives of trivinylcyclohexane |
Also Published As
Publication number | Publication date |
---|---|
TWI507392B (en) | 2015-11-11 |
JPWO2012108305A1 (en) | 2014-07-03 |
WO2012108305A1 (en) | 2012-08-16 |
TW201245141A (en) | 2012-11-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6470620B2 (en) | (Meth) acrylate compound having fluorene skeleton and method for producing the same | |
JPH09272707A (en) | Actinic-radiation-curing (meth)acrylate composition | |
JP5719831B2 (en) | Epoxy acrylate, acrylic composition, cured product and method for producing the same | |
JP6265424B2 (en) | (Meth) acrylate compound and resin composition | |
EP1251118B1 (en) | Unsaturated monocarboxylic ester compound, process for producing the same, and composition curable with actinic energy ray | |
JP5620858B2 (en) | Epoxy acrylate, acrylic composition, cured product and method for producing the same | |
JP2017186513A (en) | Epoxy (meth)acrylate and curable composition thereof | |
JP5672475B2 (en) | (Meth) acrylic acid ester, resin composition and cured product thereof | |
JP5758923B2 (en) | Epoxy acrylate, acrylic curable composition, cured product and method for producing the same | |
JP4253977B2 (en) | Active energy ray-curable composition | |
JP2006335837A (en) | Photoradical crosslinking polymer, photocurable resin composition and method for producing photoradical crosslinking polymer | |
JP6346739B2 (en) | Acrylate compound, acrylic resin composition and cured product thereof, and optical material | |
JP2014198763A (en) | Acrylate compound, acrylic resin composition and acrylic resin cured product | |
JP2011173952A (en) | (meth)acrylate derivative composition and method for producing the same | |
JP2004231704A (en) | Curable composition | |
JP4409995B2 (en) | Energy ray curable resin composition | |
JP4563053B2 (en) | Poly (meth) acrylate resin, method for producing the same, and curable resin composition | |
JP2008308420A (en) | Carboxylic acid ester compound having alicyclic epoxy group and vinyl ether group, and method for producing the ester compound | |
JP6187846B1 (en) | Active energy ray-curable composition and plastic lens | |
JP2023113363A (en) | Epoxy (meth)acrylate compound and cured product | |
JP2013209572A (en) | Acrylic resin composition and cured product thereof | |
JPS62101610A (en) | Radiation-curable resin composition | |
JP2012025693A (en) | Method for producing urethane (meth)acrylate | |
JP2013209573A (en) | Acrylic resin composition and cured product thereof | |
JPH047320A (en) | Curable resin and curable resin composition containing the same |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20140919 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20150602 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20150604 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 5758923 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
LAPS | Cancellation because of no payment of annual fees |