KR101141967B1 - A high-strength quick-curing sheet composition and a photocurable sheet material - Google Patents
A high-strength quick-curing sheet composition and a photocurable sheet material Download PDFInfo
- Publication number
- KR101141967B1 KR101141967B1 KR1020100030960A KR20100030960A KR101141967B1 KR 101141967 B1 KR101141967 B1 KR 101141967B1 KR 1020100030960 A KR1020100030960 A KR 1020100030960A KR 20100030960 A KR20100030960 A KR 20100030960A KR 101141967 B1 KR101141967 B1 KR 101141967B1
- Authority
- KR
- South Korea
- Prior art keywords
- weight
- parts
- composition
- resin
- sheet
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 53
- 239000000463 material Substances 0.000 title claims abstract description 47
- 229920005989 resin Polymers 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 27
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003822 epoxy resin Substances 0.000 claims abstract description 25
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 25
- 229920006337 unsaturated polyester resin Polymers 0.000 claims abstract description 22
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 8
- 229910000077 silane Inorganic materials 0.000 claims abstract description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 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 31
- 239000003365 glass fiber Substances 0.000 claims description 29
- -1 benzyl dimethyl ketal Chemical compound 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 15
- 239000002562 thickening agent Substances 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000003085 diluting agent Substances 0.000 claims description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003063 flame retardant Substances 0.000 claims description 8
- 239000003112 inhibitor Substances 0.000 claims description 8
- 239000002518 antifoaming agent Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 6
- 239000011342 resin composition Substances 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 5
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 230000032050 esterification Effects 0.000 claims description 5
- 238000005886 esterification reaction Methods 0.000 claims description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 5
- 239000011976 maleic acid Substances 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 4
- VTWDKFNVVLAELH-UHFFFAOYSA-N 2-methylcyclohexa-2,5-diene-1,4-dione Chemical compound CC1=CC(=O)C=CC1=O VTWDKFNVVLAELH-UHFFFAOYSA-N 0.000 claims description 4
- 239000012965 benzophenone Substances 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 4
- 238000006068 polycondensation reaction Methods 0.000 claims description 4
- 239000013008 thixotropic agent Substances 0.000 claims description 4
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 3
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 3
- 239000003505 polymerization initiator Substances 0.000 claims description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 2
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 claims description 2
- QZKVUSSYPPWURQ-UHFFFAOYSA-N 1-methylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C QZKVUSSYPPWURQ-UHFFFAOYSA-N 0.000 claims description 2
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- WVRHNZGZWMKMNE-UHFFFAOYSA-N 2-hydroxy-1-[2-(2-methylpropyl)phenyl]-2-phenylethanone Chemical compound CC(C)CC1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 WVRHNZGZWMKMNE-UHFFFAOYSA-N 0.000 claims description 2
- NACPTFCBIGBTSJ-UHFFFAOYSA-N 2-hydroxy-2-phenyl-1-(2-propan-2-ylphenyl)ethanone Chemical compound CC(C)C1=CC=CC=C1C(=O)C(O)C1=CC=CC=C1 NACPTFCBIGBTSJ-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- WYYQKWASBLTRIW-UHFFFAOYSA-N 2-trimethoxysilylbenzoic acid Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1C(O)=O WYYQKWASBLTRIW-UHFFFAOYSA-N 0.000 claims description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- ZEDSKTISNTXEQI-UHFFFAOYSA-N [(2,6-dichlorobenzoyl)-(4-propylphenyl)phosphoryl]-(2,6-dichlorophenyl)methanone Chemical compound C1=CC(CCC)=CC=C1P(=O)(C(=O)C=1C(=CC=CC=1Cl)Cl)C(=O)C1=C(Cl)C=CC=C1Cl ZEDSKTISNTXEQI-UHFFFAOYSA-N 0.000 claims description 2
- DNRISHWSPBDRTH-UHFFFAOYSA-N [(2,6-dichlorobenzoyl)-phenylphosphoryl]-(2,6-dichlorophenyl)methanone Chemical compound ClC1=CC=CC(Cl)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(Cl)C=CC=C1Cl DNRISHWSPBDRTH-UHFFFAOYSA-N 0.000 claims description 2
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims 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 claims description 2
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 claims description 2
- 238000007664 blowing Methods 0.000 claims description 2
- 229930006711 bornane-2,3-dione Natural products 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000004014 plasticizer Substances 0.000 claims description 2
- 238000012719 thermal polymerization Methods 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 claims 1
- PRRGXULZOZTZDK-UHFFFAOYSA-N [(2,6-dichlorobenzoyl)-(2,5-dimethylphenyl)phosphoryl]-(2,6-dichlorophenyl)methanone Chemical compound CC1=CC=C(C)C(P(=O)(C(=O)C=2C(=CC=CC=2Cl)Cl)C(=O)C=2C(=CC=CC=2Cl)Cl)=C1 PRRGXULZOZTZDK-UHFFFAOYSA-N 0.000 claims 1
- ZNAAXKXXDQLJIX-UHFFFAOYSA-N bis(2-cyclohexyl-3-hydroxyphenyl)methanone Chemical compound C1CCCCC1C=1C(O)=CC=CC=1C(=O)C1=CC=CC(O)=C1C1CCCCC1 ZNAAXKXXDQLJIX-UHFFFAOYSA-N 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 claims 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 15
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 239000011521 glass Substances 0.000 abstract description 6
- 229920003023 plastic Polymers 0.000 abstract description 6
- 239000004033 plastic Substances 0.000 abstract description 6
- 239000002023 wood Substances 0.000 abstract description 5
- 239000011810 insulating material Substances 0.000 abstract description 4
- 230000003014 reinforcing effect Effects 0.000 abstract description 4
- 229920001971 elastomer Polymers 0.000 abstract description 3
- 239000005060 rubber Substances 0.000 abstract description 3
- 238000001723 curing Methods 0.000 description 28
- 230000007797 corrosion Effects 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 9
- 229910000831 Steel Inorganic materials 0.000 description 8
- 238000005452 bending Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000000835 fiber Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000010959 steel Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000004695 Polyether sulfone Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 229920006393 polyether sulfone Polymers 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010276 construction Methods 0.000 description 6
- 239000012783 reinforcing fiber Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004567 concrete Substances 0.000 description 5
- 150000001991 dicarboxylic acids Chemical class 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 238000000016 photochemical curing Methods 0.000 description 5
- 230000002787 reinforcement Effects 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- 206010034972 Photosensitivity reaction Diseases 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- 229920003986 novolac Polymers 0.000 description 3
- 230000036211 photosensitivity Effects 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 239000012779 reinforcing material Substances 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000012784 inorganic fiber Substances 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- 229920003067 (meth)acrylic acid ester copolymer Polymers 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 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
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-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
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 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
- WFIDIRCFDVVTML-UHFFFAOYSA-N CCOC(C=C1)=C(C(C(C(Cl)=CC=C2)=C2Cl)=O)C(C(C(C(Cl)=CC=C2)=C2Cl)=O)=C1P(C(C(C(Cl)=CC=C1)=C1Cl)=O)(C(C(C(Cl)=CC=C1)=C1Cl)=O)=O Chemical compound CCOC(C=C1)=C(C(C(C(Cl)=CC=C2)=C2Cl)=O)C(C(C(C(Cl)=CC=C2)=C2Cl)=O)=C1P(C(C(C(Cl)=CC=C1)=C1Cl)=O)(C(C(C(Cl)=CC=C1)=C1Cl)=O)=O WFIDIRCFDVVTML-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920001747 Cellulose diacetate Polymers 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 150000004054 benzoquinones Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009933 burial Methods 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- PGFGNMIDBOQRTR-UHFFFAOYSA-N diisocyanatomethane;hexane Chemical compound CCCCCC.O=C=NCN=C=O PGFGNMIDBOQRTR-UHFFFAOYSA-N 0.000 description 1
- JXCHMDATRWUOAP-UHFFFAOYSA-N diisocyanatomethylbenzene Chemical compound O=C=NC(N=C=O)C1=CC=CC=C1 JXCHMDATRWUOAP-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229920006241 epoxy vinyl ester resin Polymers 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 229940093858 ethyl acetoacetate Drugs 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009408 flooring Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000011499 joint compound Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- YXLVLOWNJCOOAU-ZCFIWIBFSA-N methyl (2r)-2-ethyl-3-oxobutanoate Chemical compound CC[C@H](C(C)=O)C(=O)OC YXLVLOWNJCOOAU-ZCFIWIBFSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920002601 oligoester Polymers 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000002990 reinforced plastic Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000008961 swelling Effects 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
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 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
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5397—Phosphine oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
Abstract
본 발명은 에폭시아크릴레이트수지, 이소타입불포화폴리에스테르수지 및 실란계접착보조수지를 기재로 하여 종래의 광개시제와 함께 장파장의 빛으로 경화 가능한 광개시제를 이용하여 광경화시 보강 및 내식에 필요한 균일하고 충분한 경화층의 두께를 확보하고, 경화 전에는 유연성과 충분한 가사시간 및 작업시간을 가지고 시공하기 쉽도록 임의의 크기나 형상으로 가위, 칼 등으로 다양하게 재단하여 금속, 플라스틱, 고무, 유리, 도자기, 석재, 목재 등과 같은 각종 기재의 다양한 표면상태나 복잡한 형상에 적용되어 경화 후에는 접착강도, 내구성 등 기계적, 화학적 특성이 우수한 각종 건조물, 기계류, 자동차, 선박, 가정용품 등의 구조부재, 배관류, 라이닝재 등의 보강 또는 보수재, 단열재, 보온재로 사용할 수 있는 신속 광경화 시트 조성물을 포함하는 광경화 시트재에 관한 것이다.The present invention relates to an epoxy resin composition which is based on epoxy acrylate resin, isotypes unsaturated polyester resin and silane-based adhesion auxiliary resin and which can be cured with long-wavelength light with a conventional photoinitiator, The thickness of the hardened layer is secured, and before the hardening, various cuts are made by scissors, knives and the like in any size or shape so as to be easy to apply with flexibility, sufficient working time and working time, and metal, plastic, rubber, glass, Such as wood, wood, etc., which are excellent in mechanical and chemical properties such as adhesion strength and durability after curing, and are used for structural members such as automobiles, ships, housewares, Rapid light curing sheet composition which can be used as a reinforcing or repairing material, an insulating material, The present invention relates to a photo-curable sheet material.
Description
본 발명은, 화학저장탱크, 오일탱크, 제방벽, 식품공장, 의약품 공장, 전자재료 관련공장의 콘크리트 시설물, 지상 또는 지하 파이프라인, 지붕, 등과 같은 콘크리트, 철제, GRP, FRP, PVC, 유리 또는 목재 구조물 등에 피복되어 보강재, 내식재, 라이닝재, 단열재, 보온재 등으로 사용되는 고강도 신속 광경화 시트 조성물 및 이를 포함하는 광경화 시트재에 관한 것으로, 보다 구체적으로 이소 타입 불포화폴리에스테르 수지 및 에폭시아크릴레이트를 주제로 하는 광경화성 혼합수지를 Glass Fiber 매트에 함침시키거나 상기 혼합수지에 Glass Fiber를 첨가하여 제조된 고강도 신속 광경화 시트재에 관한 것이다.
The present invention relates to a process for the production of concrete, iron ore, GRP, FRP, PVC, glass or the like, such as chemical storage tanks, oil tanks, barrier walls, food factories, pharmaceutical factories, The present invention relates to a high-strength quick-cured sheet composition used as a reinforcing material, an inner material, a lining material, a heat insulating material, a heat insulating material, etc. coated with a wood structure or the like and a photocurable sheet material containing the same. More specifically, the present invention relates to an isotactic unsaturated polyester resin, Speed photo-curable sheet material produced by impregnating a glass fiber mat with a photo-curing mixed resin with a rate of a subject or adding glass fiber to the mixed resin.
화학저장탱크, 오일탱크 및 파이프라인과 같은 기체 또는 액체 화학물질의 저장 및 운송 또는 이송수단과 식품공장, 의약품 공장, 전자재료 관련공장의 콘크리트 시설물 및 해안제방벽들은 내구성과 부식방지를 위해 그 재료로서 콘크리트, 스틸, 스테인리스 스틸, 강화플라스틱 등이 이용되고 있을 뿐만 아니라, 이러한 재료들은 상하수도, 원유, 화학 약품, 도시가스 등 광범위한 인프라 시설에도 사용되고 있어 우리의 생활에 밀접한 관련이 있다.
The means of storage and transportation or transport of gaseous or liquid chemicals such as chemical storage tanks, oil tanks and pipelines and the concrete facilities and coastal barriers of food factories, pharmaceutical factories, As well as concrete, steel, stainless steel, and reinforced plastic are used, these materials are also used in a wide range of infrastructure facilities such as water and sewage, crude oil, chemicals, and city gas, and are closely related to our lives.
그러나, 예를 들어 원유 수송에서는 스틸 파이프가 주로 사용되고 있지만, 석유에 포함되는 부식성 불순물 등에 의해서 파이프의 부식이 발생하여 원유가 누설되는 경우가 있다. 또한, 상수도나 하수도에서는 콘크리트 흄관이 주로 사용되고 있지만, 장기간의 매설 사용으로 외적 압력에 의한 물리적 파손이 발생할 수 있으며, 특히 하수도에서는 오염물질의 분해에 수반되는 아황산 가스의 발생 및 유황 산화균에 의한 황산이온의 발생으로 콘크리트 파이프 내면으로부터의 부식, 노후화가 문제가 되고 있어 기존 매설된 흄관의 보강 보수문제가 상존하고 있다.
However, for example, steel pipes are mainly used in crude oil transportation, but corrosive impurities contained in petroleum may corrode the pipes and leak the crude oil. In addition, concrete hume pipes are mainly used in waterworks and sewerage, but physical damages due to external pressure may occur due to long-term burial use. In particular, in sewage, the occurrence of sulfur dioxide gas accompanying decomposition of pollutants, Corrosion of the inner surface of the concrete pipe due to the generation of ions, and aging of the pipe are problematic.
또한, 신설관의 내식성 향상과 함께 기존 매설관의 국부적 보수로서 파이프내부의 부식방지코팅이나 라이닝을 시공하는 경우가 있지만, 기존 매설관의 수명한계가 있고, 기존 관의 강도보강을 위해 강도 및 내구성을 갖춘 내식성이 있는 플라스틱 파이프를 노후관중에 새롭게 삽입하는 방법도 시도되고 있지만 기존 관의 보수에는 큰 공사상의 제약과 함께 비용적인 면도 한계가 있는 문제점이 있다.
In addition, corrosion resistance of the new pipe is improved and local repair of the existing pipe is applied to the inside of the pipe for corrosion prevention coating or lining. However, there is a limit in the life of the existing buried pipe and strength and durability A new method of inserting a corrosion-resistant plastic pipe having a thickness of 10 mm or more into a worn-out pipe has been attempted. However, there is a problem that existing pipes are limited in terms of cost and cost.
현재 가장 주목받고 있는 현장 시공이 가능한 보수 방법으로서 미리 열강화성 수지에 요변성 부여제를 첨가한 것을 함침한 FRP 프리프레그를 노후관내에 삽입하거나 노후시설물 외부에 압착해, 열수 또는 열풍으로 경화시키는 방법(P.Chaneliere, U.Bultjer, Diegrabenlose Sanierungｖon Abwasserleitungen. Ein interessanntes Einsatzgebiet fur ungesattigtePolyesterharze.Composites 3, 18(1992), D.Johnson et al., 45 th.SPI, 12－D(1990)이 알려져 있지만, 이 방법으로 사용되는 프리프레그는, 함침 수지 조성물에 신장성이 있는 필름의 한쪽 면에 촙스트렌드매트, 부직포 등의 강화 섬유를 접합한 원통형 펠트 또는 직물에 불포화 폴리에스텔, 비닐에스테르 수지 또는 에폭시 수지를 함침시킨 필름이 원통형 외부에 적층한 것으로서, 관내에서 붙여 수압 또는 공기압 등으로 관벽에 압착하고, 열수 또는 열풍으로 경화시켜 보강하는 것을 특징으로 한다.
As a repair method that can be applied to the field, which is currently attracting the most attention, a FRP prepreg impregnated with a thixotropic agent is added to a thermosetting resin in advance, or it is pressed into the outside of the old structure and cured by hot water or hot air (Johnson, et al., 45 th. SPI, 12-D (1990)) are known, however, this is not the case. Prepreg used as the method is a method in which impregnated polyester resin, vinyl ester resin or epoxy resin is impregnated into a cylindrical felt or fabric in which reinforcement fibers such as a wax trend mat or a nonwoven fabric are bonded to one side of a stretchable film, Which is laminated on the outside of a cylindrical shape, is adhered in a pipe and is pressed on a pipe wall by water pressure or air pressure, and hot water or hot air So as to reinforce it.
그러나, 상기 방법은 원통형 프리프레그가 유연하기 때문에 현장 시공이 가능하고, 또한 관벽에 압착한 상태로 경화하되기 때문에 방식 경화 외에 보강 경화를 겸비한 성능을 나타내지만, 유기 과산화물을 배합한 래디컬 경화형의 열강화성 수지 또는 경화제를 배합한 에폭시 수지를 사용하고 있으므로 프리프레그로서의 가사시간 또는 저장 시간이 짧은 단점이 있으며, 또한 경화를 위해서는 다량의 열매체 및 다량의 열량을 필요로 하는 등의 문제가 있다.
However, since the cylindrical prepreg is flexible, the above method can be applied on the spot and cured in the state of being pressed on the wall of the pipe. Therefore, the method exhibits performance combined with reinforcement curing in addition to system curing. However, a radical curing type There is a disadvantage in that a pot life or storage time as a prepreg is short because an epoxy resin containing a methacrylic resin or a curing agent is used and that a large amount of heat medium and a large amount of heat are required for curing.
한편, 유리 섬유 또는 유리 매트에 불포화 폴리에스테르수지를 함침시킨 복합재료를 이용해 자외선을 경화 수단으로서 사용하는 방법(Kunststoffe German Plastics.83(10), 55(1993)이 알려져 있으나, 이 방법은 열매체 및 열량은 불필요한 반면, 방식성을 향상시키기 위해서 FRP층을 두껍게 하는 경우 자외선 투과가 어려워져 미경화가 발생하거나 경화 속도의 차이로 인한 크랙이 발생할 가능성이 매우 높아 내식성을 저하시키는 단점이 있고, 따라서, 자외선 투과성을 확보하기 위해서는 필러 또는 충전재를 소량 밖에 첨가할 수 없기 때문에 경화물의 치수 안정성이나 비용적인 면에서 불리한 문제점이 있다.
On the other hand, a method of using ultraviolet rays as a curing means (Kunststoffe German Plastics. 83 (10), 55 (1993)) using a composite material obtained by impregnating a glass fiber or glass mat with an unsaturated polyester resin is known, On the other hand, when the thickness of the FRP layer is increased in order to improve the anticorrosion property, there is a disadvantage in that ultraviolet ray transmission becomes difficult and uncracking occurs or cracking due to difference in hardening rate is very high, In order to ensure permeability, only a small amount of filler or filler can be added, which is disadvantageous in terms of dimensional stability and cost of the cured product.
또한, 일본 공개특허공보 소63-186744호에는 투명성 시트를 일면에 적층하여 이루어진 광경화성 프리프레그가 개시되어 있는데, 이 광경화성 프리프레그는 투명성 시트에 의해 경화물 표면이 평활해져 외관을 깨끗하게 할 수 있지만, 기재 접착을 위해 프라이머를 도포할 필요가 있고, 기재에 따라서는 충분한 접착성을 확보하지 못할 우려가 있으며, 또한, 시공 작업이 번거로운 단점이 있다.
Further, Japanese Unexamined Patent Publication (Kokai) No. 63-186744 discloses a photo-curable prepreg comprising a transparent sheet laminated on one side. This photo-curable prepreg has a transparent sheet to smooth the surface of the cured product, However, it is necessary to apply the primer to bond the base material. Depending on the base material, sufficient adhesion can not be ensured, and the construction work is troublesome.
일본 공개특허공보 소57-99375호에는 경화성 성형재료층을 특정한 2염기산이나 올리고에스테르를 수지 골격 중에 함유한 광경화성 에폭시비닐에스테르 수지를 사용하여 얇은 강판에 접착시키고, 이어서 광 조사하여 경화시킴으로써 얇은 강판을 보강하는 방법이 개시되어 있는데, 이 보강방법으로는 경화성 성형재료층의 얇은 강판에 대한 접착 강도를 어느 정도 향상시킬 수 있지만, 기재에 따라서는 충분한 접착성을 확보하지 못할 우려가 있고, 접착 불량이 충분히 억제되지 않을 우려가 있거나 시공 작업이 번잡하기도 하다.
Japanese Unexamined Patent Publication (Kokai) No. 57-99375 discloses a method in which a layer of a curable molding material is adhered to a thin steel sheet using a photo-curable epoxy vinyl ester resin containing a specific dibasic acid or an oligoester in a resin skeleton, A method of reinforcing a steel sheet is disclosed. This reinforcing method can improve the adhesion strength of the curable molding material layer to a thin steel sheet to some extent, but there is a possibility that sufficient adhesion can not be ensured depending on the substrate, There is a possibility that the defects are not sufficiently suppressed or the construction work is troublesome.
일본 공개특허공보 소59-1250호에는 경화성 프리프레그에 경화성 및 친유성을 지닌 프라이머를 도포하고, 이어서 그 도포면을 강판에 밀착시킨 후 프리프레그 및 프라이머를 경화시키는 프리프레그 강판에 대한 점착방법이 개시되어 있지만, 이 점착방법에서는 프라이머로 프리프레그를 다소 팽윤시킴으로써 프리프레그 강판에 대한 접착 불량이 어느 정도 억제된다. 그러나, 기재에 따라서는 충분한 접착성을 확보하지 못할 우려가 있고, 프리프레그나 프라이머가 시공 도중에 경화되기 때문에 시공 시간이 제약받거나 프리프레그를 기재에 충분히 밀착시킬 수 없다는 면에서도 접착 불량이 충분히 억제되지 않을 우려가 있으며, 프라이머를 사용하여 시공할 필요가 있어 시공 작업이 번잡한 단점이 있다.
Japanese Unexamined Patent Publication (Kokai) No. 59-1250 discloses an adhesion method for a prepreg steel sheet in which a primer having a hardenable and lipophilic property is applied to a hardenable prepreg, and then the coated surface is adhered to the steel sheet and the prepreg and the primer are cured. However, in this adhesion method, the defective adhesion to the prepreg steel sheet is suppressed to some extent by slightly swelling the prepreg with the primer. However, there is a fear that sufficient adhesion can not be ensured depending on the substrate, and since the prepreg or primer is cured during the application, the application time is restricted or the adhesion failure can not be sufficiently suppressed even in the case where the prepreg can not be sufficiently adhered to the substrate There is a concern that the construction work needs to be carried out using a primer, which is a complicated construction work.
이와 같이 종래의 열경화형의 수지 조성물에서는, 프리프레그로서의 가사시간 혹은 저장 안정성에 문제가 있고, 현장 시공을 실시하는 경우에는 균일한 경화를 위해서는 다량의 열매체를 확보하는 것이 필요하므로 시공할 수 있는 시설물 또는 파이프의 길이, 시설물 면적 또는 파이프지름 등에 제한이 있었으며, 종래의 자외선 경화형 수지 조성물에서는 상기 열경화형 수지 조성물을 사용하는 경우에는 불가결한 대량의 열원 또는 열분포를 균일화하기 위한 보조 설비 등을 필요로 하지는 않지만, 자외선 경화시 보강 및 내식에 필요한 FRP층의 두께를 확보하는 것이 곤란한 문제가 있으며, 특히, 불포화폴리에스테르계 광중합 경화성 수지는 경화시 수축성 및 광중합시 불균일하게 중합되는 경향이 있으므로 경화 후 표면에 웨이브를 유발시키는 문제가 있으므로 광경화시 수축성 감소, 치수안정 및 균일한 경화로 인한 표면 매끄러움성이 우수한 고강도 신속 광경화 시트 조성물 및 이를 포함하는 광경화 시트재의 개발이 절실히 요구되어 왔다.
Thus, in the conventional thermosetting resin composition, there is a problem in the pot life or the storage stability as the prepreg, and in the case of performing the field construction, it is necessary to secure a large amount of heat medium for uniform curing, Or pipe length, facility area, or pipe diameter. In the case of using the thermosetting resin composition, the conventional ultraviolet curable resin composition requires an auxiliary equipment for uniformizing a large amount of heat source or thermal distribution which is indispensable However, there is a problem that it is difficult to secure the thickness of the FRP layer necessary for reinforcement and corrosion resistance in ultraviolet curing. Particularly, unsaturated polyester type photopolymerizable curable resin tends to polymerize unevenly during shrinkage and light polymerization, Problems triggering waves Since the photo-reduction upon shrink properties, dimensional stability and excellent in surface smoothness property due to uniform rapid hardening high strength sheet photocurable composition and a photocurable sheet material development comprising the same it has been urgently required.
본 발명은 상기 문제점을 해결하고자 발명된 것으로, 열원을 이용하지 않고도 종래 이용되어온 광개시제와 함께 장파장의 빛으로 경화 가능한 광개시제를 이용하여 광경화시 보강 및 내식에 필요한 경화층의 두께를 충분히 확보하고, 경화 전에는 유연성과 충분한 가사시간 및 작업시간을 가지고 시공하기 쉽도록 임의의 크기나 형상으로 가위, 칼 등으로 다양하게 재단하여 금속, 플라스틱, 고무, 유리, 도자기, 석재, 목재 등과 같은 각종 기재의 다양한 표면상태나 복잡한 형상에 적용되어 경화 후에는 접착강도, 내구성 등 기계적, 화학적 특성이 우수한 각종 건조물, 기계류, 자동차, 선박, 가정용품 등의 구조부재, 배관류, 라이닝재 등의 보강 또는 보수재, 단열재, 보온재로 사용될 수 있는 고강도 신속 광경화 시트 조성물 및 이를 포함하는 광경화 시트재를 제공하는 것을 해결하려는 과제로 한다.
The present invention has been made to solve the above-described problems, and it is an object of the present invention to provide a photoinitiator that can cure with light of a long wavelength in combination with a photoinitiator conventionally used without using a heat source to sufficiently secure a thickness of a cured layer necessary for reinforcement and corrosion resistance during photo- Prior to curing, it is possible to cut a variety of scales and knives in any size or shape to make it easy to apply with flexibility, sufficient pot life and working time, and to produce various kinds of materials such as metal, plastic, rubber, glass, ceramics, stone, Reinforcing or repairing structural materials, pipes, linings, etc. of various kinds of dry materials, machinery, automobiles, vessels, household goods and the like which are excellent in mechanical and chemical properties such as adhesion strength and durability after being applied to surface condition or complicated shape, , A high-strength quick-curing sheet composition which can be used as a heat insulating material, and a photocuring And a challenge to solve is to provide a teujae.
본 발명은 상기 과제를 해결하기 위하여, 에폭시아크릴레이트수지 45~70중량부, 이소타입불포화폴리에스테르수지 0.1~25중량부, 실란계접착보조수지 0.01~5중량부, 포스핀(phosphine)계 광개시제 0.01~5중량부, 알파히드록시케톤(α-Hydroxyketone)계 광개시제 0.01~5중량부, 17~25 마이크로 직경의 E-유리섬유 또는 E-유리섬유매트 0.1~50중량부, 17~25 마이크로 직경의 C-유리섬유 또는 C-유리섬유매트 0.1~50중량부, 증점제 0.1~5중량부, 점도강하제 0.01~3중량부, 소포제 0.01~5중량부를 포함하여 구성되는 것을 특징으로 하는 고강도 신속 광경화 시트 조성물을 제공하는 것을 과제의 해결수단으로 한다.
In order to solve the above-described problems, the present invention provides an epoxy resin composition comprising 45 to 70 parts by weight of an epoxy acrylate resin, 0.1 to 25 parts by weight of an isotactic unsaturated polyester resin, 0.01 to 5 parts by weight of a silane- 0.01 to 5 parts by weight of an alpha hydroxyketone photoinitiator, 0.1 to 50 parts by weight of E-glass fiber or E-glass fiber mat of 17 to 25 micro-diameter, 17 to 25 micro-diameter 0.1 to 5 parts by weight of a thickener, 0.01 to 3 parts by weight of a viscosity-decreasing agent, and 0.01 to 5 parts by weight of a defoaming agent, based on 100 parts by weight of the C-glass fiber or C- To provide a sheet composition.
또한, 본 발명은 상면에 광차단 이형필름층, 상기 고강도 광경화 시트 조성물층 및 하면에 광차단 이형필름층을 포함하여 구성되는 것을 특징으로 하는 고강도 신속 광경화 시트 조성물을 포함하는 광경화 시트재를 제공하는 것을 과제의 해결수단으로 한다.
The present invention also provides a photocurable sheet material comprising a light-shielding release film layer on the top surface, a high-strength light-curable sheet composition layer on the top surface, and a light- As a solution to the problem.
본 발명에 따른 고강도 신속 광경화 시트 조성물을 포함하는 광경화 시트재는 에폭시아크릴레이트수지, 이소타입불포화폴리에스테르수지 및 실란계접착보조수지를 기재로 하여 종래의 광개시제와 함께 장파장의 빛으로 경화 가능한 광개시제를 이용하여 광경화시 보강 및 내식에 필요한 균일하고 충분한 경화층의 두께를 확보하고, 경화 전에는 유연성과 충분한 가사시간 및 작업시간을 가지고 시공하기 쉽도록 임의의 크기나 형상으로 가위, 칼 등으로 다양하게 재단하여 금속, 플라스틱, 고무, 유리, 도자기, 석재, 목재 등과 같은 각종 기재의 다양한 표면상태나 복잡한 형상에 적용되어 경화 후에는 접착강도, 내구성 등 기계적, 화학적 특성이 우수한 각종 건조물, 기계류, 자동차, 선박, 가정용품 등의 구조부재, 배관류, 라이닝재 등의 보강 또는 보수재, 단열재, 보온재로 사용할 수 있는 특유한 효과가 있다.
The photo-curable sheet material comprising the high-strength quick-cured sheet composition according to the present invention is a photo-initiator material which is cured with light of a long wavelength with a conventional photoinitiator, based on epoxy acrylate resin, isotype unsaturated polyester resin and silane- It is necessary to secure a uniform and sufficient thickness of the hardened layer required for reinforcement and corrosion in photocuring and to vary the size and shape of the hardened layer to a desired size and shape with scissors and knives Which is excellent in mechanical and chemical properties such as adhesion strength and durability after being applied to various surface conditions and complex shapes of various substrates such as metal, plastic, rubber, glass, ceramics, stone and wood, , Structural members such as vessels, housewares, piping, lining materials, etc. There is a peculiar effect that can be used as waterproof material, insulation material, and insulation material.
도 1은 본 발명의 고강도 광경화 시트재 사시도BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a perspective view of a high-
본 발명은 에폭시아크릴레이트수지 45~70중량부, 이소타입불포화폴리에스테르수지 0.1~25중량부, 실란계접착보조수지 0.01~5중량부, 포스핀(phosphine)계 광개시제 0.01~5중량부, 알파히드록시케톤(α-Hydroxyketone)계 광개시제 0.01~5중량부, 17~25 마이크로 직경의 E-유리섬유 또는 E-유리섬유매트 0.1~50중량부, 17~25 마이크로 직경의 C-유리섬유 또는 C-유리섬유매트 0.1~50중량부, 증점제 0.1~5중량부, 점도강하제 0.01~3중량부, 소포제 0.01~5중량부를 포함하여 구성되는 고강도 신속 광경화 시트 조성물을 기술구성의 특징으로 한다.
The present invention relates to a resin composition comprising 45 to 70 parts by weight of an epoxy acrylate resin, 0.1 to 25 parts by weight of an isotactic unsaturated polyester resin, 0.01 to 5 parts by weight of a silane-based adhesive auxiliary resin, 0.01 to 5 parts by weight of a phosphine- 0.01 to 5 parts by weight of a? -Hydroxyketone type photoinitiator, 0.1 to 50 parts by weight of E-glass fiber or E-glass fiber mat of 17 to 25 micro-diameter, C-glass fiber of 17 to 25 micro- A glass fiber mat, 0.1 to 5 parts by weight of a thickener, 0.01 to 3 parts by weight of a viscosity-decreasing agent, and 0.01 to 5 parts by weight of a defoaming agent.
또한, 본 발명은 상면에 광차단 이형필름층, 상기 고강도 광경화 시트 조성물층 및 하면에 광차단 이형필름층을 포함하여 구성되는 고강도 신속 광경화 시트 조성물을 포함하는 광경화 시트재를 기술구성의 특징으로 한다.
The present invention also provides a photocurable sheet material comprising a light-shielding releasing film layer on the top surface, a high-strength light-curing sheet composition layer on the top surface thereof, and a light- .
이하에서는 첨부한 도면을 참조하여 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있도록 본 발명의 실시예를 상세히 설명한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며, 여기에서 설명하는 실시예에 한정되지 않는다.
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
본 발명에 사용하는 고강도 신속 광경화 시트 조성물중의 수지는 에폭시아크릴레이트수지, 이소타입불포화폴리에스테르수지를 혼합 사용한다. 이들의 수지를 본 발명에 채택, 사용하는 이유는 광반응에 의해 경화하는 반응기를 가질 뿐만 아니라, 이소타입불포화폴리에스테르수지는 비용이 저렴하고, 에폭시아크릴레이트수지는 강도 및 내식성이 뛰어나기 때문이다.
The resin in the high-strength quick-cured sheet composition used in the present invention is a mixture of an epoxy acrylate resin and an iso-type unsaturated polyester resin. The reason why these resins are adopted and used in the present invention is not only that they have a reactor for curing by a photoreaction but also that the isotactic unsaturated polyester resin is inexpensive and the epoxy acrylate resin is excellent in strength and corrosion resistance .
에폭시수지는 내열성, 내약품성, 내용제성, 접착성, 내마모성 등이 우수하고 전기적, 기계적 성질이 우수해서 표면코팅, 전기절연, 적층구조물, 건축, 접착제 등의 여러 분야에 사용되고 있으며, 대표적으로는 비스베놀A형 에폭시가 알려져 있고, 다음과 그림과 같이 제조되며, 일반적으로 이 Type의 수지는 벤젠핵(Bisphenol A)이 있기 때문에 자유회전이 힘들다. 이것이 내약품성과 접착성 강인성 고온특성을 좋게 한다. 또한 분자내에 Ether기를 가지고 있어 내약품성이 우수하고, 가소성이 있다. 친수성의 수산기와 소수성의 탄화수소기가 규칙적으로 배열되어 있어 접착성이 우수하다. 그러나, 황변현상이 발생하고, 경화시간이 길며, 결정성 폴리머나 극성이 없는 PE, PP, 실리콘, 아크릴에는 접착이 불량하고 주제 경화제를 혼용하여야 하는 단점이 있어서 광경화용으로는 사용이 불가능하다.
Epoxy resins are excellent in heat resistance, chemical resistance, solvent resistance, adhesiveness, abrasion resistance, etc. and have excellent electrical and mechanical properties and are used in various fields such as surface coating, electrical insulation, laminated structure, construction and adhesive, Vene A type epoxy is known, and is manufactured as shown in the following figure. In general, this type of resin is free from free rotation because it has a benzene nucleus (Bisphenol A). This improves the chemical resistance and adhesion toughness and high temperature properties. It also has an ether group in the molecule and is excellent in chemical resistance and plasticity. Hydrophilic hydrophilic groups and hydrophobic hydrocarbon groups are regularly arranged, and the adhesion is excellent. However, yellowing occurs, curing time is long, and PE, PP, silicone, and acrylic, which have no crystalline polymer or polarity, are poor in adhesion and have a disadvantage of using a mixture of a main curing agent and can not be used for light curing.
이러한 에폭시수지에 이중결합을 갖는 아크릴기를 도입하여 감광성을 갖는 에폭시아크릴레이트 광경화형수지는 현대사회에서 요구되는 에너지절약 및 환경친화적인 특성으로 인해 많은 사업분야에서 사용되며, 그 특징으로는 복잡한 모양의 구조물에 적용하기가 어려우며 가격이 비싼 단점이 있으나, 일반적인 열경화 반응과는 달리 저온에서 빠르게 경화되어 에너지가 절감되고, 경화특성이 우수하며, 희석제로 용매 대신 반응성 아크릴계 단량체를 사용하는 액상 형태이므로 대기오염에 의한 환경문제를 야기시키지 않는 장점이 있다.
The epoxy acrylate photocurable resin having photosensitivity by introducing an acrylic group having a double bond in such an epoxy resin is used in many business fields due to energy saving and environmentally friendly characteristics required in the modern society, It is difficult to apply to structures and has a disadvantage of high cost. However, unlike general thermosetting reaction, it rapidly cures at low temperature to save energy and has excellent hardening property. Since it is liquid form using reactive acrylic monomer instead of solvent as diluent, There is an advantage that it does not cause environmental problems caused by pollution.
이러한 장점 때문에 UV경화형 코팅제나 접착제는 목재, 플라스틱, 바닥재, 금속 등 탑코팅이나 접착용도에 다량 사용되고 있으며, 최근에 환경문제가 대두되면서 전자부품 등의 정밀소재부문에 그 적용분야와 수요가 급속히 증가되고 있고, 일반적으로 많이 사용되고 있는 비스페놀A 에폭시아크릴레이트는 내약품성, 경도가 우수하고, 경화속도가 빠르며, 상대적으로 가격이 싸다는 장점이 있으나, 황변하기 쉽고 깨어지기 쉬우며 점도가 많이 높다는 단점이 있으므로 광경화용 단독으로 사용하기에는 물성면에서 한계가 있다.
Because of these advantages, UV-curable coatings and adhesives are widely used for top coating and bonding applications such as wood, plastic, flooring, and metal. Recently, as environmental problems have arisen, their applications and demand have rapidly increased And the commonly used bisphenol A epoxy acrylate is excellent in chemical resistance and hardness, has a high curing speed and relatively low cost, but has a disadvantage that it is easy to yellowish, is easily broken and has a high viscosity Therefore, there is a limit in physical properties for use as a photocuring alone.
비스페놀A에폭시아크릴레이트와 같은 방향족계에폭시아크릴레이트는 방향족계 에폭시기를 가지는 화합물과 아크릴산 등의 카르복실기에 의한 개환 반응에 의해 생성하는 중합성 이중 결합을 가지는 수지로서, 구체적으로는 에폭시 수지와 아크릴산 또는 메타크릴산을 성분으로서 얻을 수 있는 에폭시(메타)아크릴레이트로 얻거나 또는 포화디카르본산 및／또는 불포화디카르본산과 다가알코올에서 얻어진 말단 카르복실기의 폴리에스테르에 α,β－불포화 카르본산 에스테르기를 함유하는 방향족계 에폭시화합물을 반응시켜 얻을 수 있다.
Aromatic epoxy acrylates such as bisphenol A epoxy acrylate are resins having a polymerizable double bond formed by a ring-opening reaction between a compound having an aromatic epoxy group and a carboxyl group such as acrylic acid, and specifically, an epoxy resin, (Meth) acrylate obtainable as a component of acrylic acid, or an epoxy (meth) acrylate obtainable as a component of acrylic acid or a polyester having a terminal carboxyl group obtained from a saturated dicarboxylic acid and / or an unsaturated dicarboxylic acid and a polyhydric alcohol And then reacting the resulting mixture with an aromatic epoxy compound.
방향족계 에폭시아크릴레이트의 원료로서 이용되는 방향족계 에폭시수지로서는, 예를 들면 비스페놀A형 에폭시수지, 비스페놀F형 에폭시수지, 비스페놀S형 에폭시수지 등의 비스페놀형 에폭시수지류, 페놀노볼락형 에폭시수지, 크레졸노볼락형 에폭시수지, 알킬페놀형 에폭시수지 등의 노볼락형 에폭시수지류, 알킬페놀형 에폭시수지, 레졸신형 에폭시수지, N-글리시딜아민형 에폭시수지 등을 들 수 있으며, 이들 에폭시수지는 각각 단독으로 사용하여도 좋고, 2종류 이상을 조합하여 사용하여도 좋다.
Examples of the aromatic epoxy resin used as a raw material of the aromatic epoxy acrylate include bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin and bisphenol S type epoxy resin, phenol novolak type epoxy resin Novolak type epoxy resins such as cresol novolak type epoxy resins and alkylphenol type epoxy resins, alkylphenol type epoxy resins, resole type epoxy resins and N-glycidylamine type epoxy resins. These epoxy resins The resins may be used alone or in combination of two or more.
본 발명에서 사용되는 에폭시수지에 반응시키는 불포화 카르본산은 아크릴산, 메타크릴산인데, 다른 불포화 디카르본산, 예를 들면 푸마르산, 무수 말레산, 말레산, 이타콘산 등을 소량 병용하거나 이들 단독 또는 2종류 이상을 같이 사용할 수 있으며, 광중합 에폭시아크릴레이트의 반응물의 하나로서 사용되는 불포화 일염기산은 중합속도를 감안, 메틸(메타)아크릴산을 사용하는 것이 보다 바람직하다.
The unsaturated carboxylic acid to be reacted with the epoxy resin used in the present invention is acrylic acid or methacrylic acid. Other unsaturated dicarboxylic acids such as fumaric acid, maleic anhydride, maleic acid, itaconic acid, etc., (Meth) acrylic acid can be used in combination with the unsaturated monobasic acid used as one of the reactants of the photopolymerizable epoxy acrylate.
상기 방향족계 에폭시수지와 (메타)아크릴산의 반응비율은, 몰비로 보통, 0.9~1.1:1.1~0.9의 범위이며, 이때의 반응은 보통, 110~130℃에서 행하여지고, 희석제로서 스테렌모노머 또는 아크릴모노머가 사용되며, 중축합반응 촉진제 및 에스테르화 촉매로서 트리에틸아민, 디메틸아닐린, 트리스(디메틸아미노메틸)페놀 등의 3급 아민류, 트리메틸벤질암모늄크로라이드, 트리에틸벤질암모늄크로라이드, 피리디늄크로라이드 등의 4급 암모늄염류 또는 수산화리튬, 염화리튬 등의 무기염류가 이용된다.
The reaction ratio of the aromatic epoxy resin to the (meth) acrylic acid is usually in the range of 0.9 to 1.1: 1.1 to 0.9 at a molar ratio, and the reaction is usually carried out at 110 to 130 ° C. As the diluent, Acrylic monomers are used. As the polycondensation reaction promoter and the esterification catalyst, tertiary amines such as triethylamine, dimethylaniline and tris (dimethylaminomethyl) phenol, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, pyridinium Quaternary ammonium salts such as chlorides, and inorganic salts such as lithium hydroxide and lithium chloride are used.
또한, 필요에 따라서 중합금지제가 이용되고, 중합금지제로서는 하이드로퀴논, 메틸하이드로퀴논 등의 하이드로퀴논류, 벤조퀴논, 메틸-p-벤조퀴논 등의 벤조퀴논류, t-부틸카테콜 등의 카테콜류, 2,6-디-t-부틸-4-메틸페놀, 4-메톡시페놀 등의 페놀류, 페노티아진 등을 들 수 있다.
In addition, if necessary, a polymerization inhibitor is used. Examples of the polymerization inhibitor include hydroquinones such as hydroquinone and methylhydroquinone, benzoquinones such as benzoquinone and methyl-p-benzoquinone, ketones such as t- Phenols such as 2,6-di-t-butyl-4-methylphenol and 4-methoxyphenol, phenothiazine and the like.
상기 에폭시아크릴레이트의 제조는 비스페놀A타입 에폭시수지 30~60중량부와, 비스페놀A 10~30중량부 및 중축합 반응촉진제 0.1~3중량부를 질소 분위기하에서 150℃으로 2시간 반응시킨 후, 110℃까지 냉각하고, 메틸메타크릴레이트 15~35중량부, 말레산 0.1~5중량부, 에스테르화 촉매 0.1~3중량부, 중합금지제 0.01~0.1중량부, 증점제 0.1~5중량부, 희석제를 전체조성물 100중량부당 35중량부 투입 희석시키고, 공기를 불어넣으며 110~130℃으로 3~4시간 반응시켜 제조한다.
The epoxy acrylate was prepared by reacting 30 to 60 parts by weight of a bisphenol A type epoxy resin, 10 to 30 parts by weight of bisphenol A and 0.1 to 3 parts by weight of a polycondensation reaction accelerator at 150 DEG C for 2 hours under a nitrogen atmosphere, , 0.1 to 5 parts by weight of methyl methacrylate, 0.1 to 5 parts by weight of maleic acid, 0.1 to 3 parts by weight of an esterification catalyst, 0.01 to 0.1 parts by weight of a polymerization inhibitor, 0.1 to 5 parts by weight of a thickener, Diluted 35 parts by weight per 100 parts by weight of the composition and blowing in air at 110 to 130 DEG C for 3 to 4 hours.
상기 에폭시아크릴레이트의 함유량은 전체 고강도 신속 광경화 시트 조성물 100중량부 기준으로 45~70중량부 포함하는 것이 바람직한데, 45중량부 미만에서는 경화물의 내약품성(특히 강산화성의 고농도 초산에 대한 저항성)이 저하하고, 70중량부를 넘는 경우는 수지조성물의 점도가 상승하기 때문에 유리섬유 등의 보강섬유에 균일한 함침이 어렵고 시트 보강재로서의 작업성이 저하되기 때문에 바람직하지 않다.
The content of the epoxy acrylate is preferably 45 to 70 parts by weight based on 100 parts by weight of the entire high-strength quick-cured sheet composition. When the amount of the epoxy acrylate is less than 45 parts by weight, the chemical resistance of the cured product (especially resistance to high- If the amount exceeds 70 parts by weight, the viscosity of the resin composition is increased. Therefore, uniform impregnation with reinforcing fibers such as glass fibers is difficult and workability as a sheet reinforcing material is lowered.
한편, 본 발명에서 사용되는 이소타입불포화폴리에스테르수지는 글리콜과 불포화 다염기산, 포화 다염기산을 가열, 에스테르화한 불포화 폴리에스테르를 공중합 가능한 스티렌 등의 모노머류에 용해한 것으로, 구체적으로는 무수프탈산, 이소프탈산, 테레프탈산, 테트라히드로프탈산, 아디핀산, 세바신산 등의 활성 불포화 결합을 가지지 않은 디카르본산과 푸마르산, 무수말레산, 말레산, 이타콘산 등의 활성 불포화 결합을 가지고 있는 디카르본산을 에틸렌글리콜, 프로필렌글리콜, 1,2－부탄디올, 1,3－부탄디올, 1, 5－펜탄디올, 1,6－헥산디올, 2－메틸-1,3－프로판디올, 2,2－디메틸-1,3－프로판디올, 네오펜틸글리콜 등의 다가 알코올을 에스테르화하여 제조되는 것이다.
On the other hand, the isotactic unsaturated polyester resin used in the present invention is obtained by dissolving an unsaturated polyester obtained by heating and esterifying glycol, an unsaturated polybasic acid and a saturated polybasic acid in monomers such as styrene copolymerizable therewith. Specifically, phthalic anhydride, , Dicarboxylic acids having active unsaturated bonds such as terephthalic acid, tetrahydrophthalic acid, adipic acid and sebacic acid and dicarboxylic acids having active unsaturated bonds such as fumaric acid, maleic anhydride, maleic acid and itaconic acid, Propylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, Propanediol, neopentyl glycol, and the like.
상기 이소타입불포화폴리에스테르수지 제조는 네오펜틸 글리콜 10~40중량부, 프로필렌글리콜 15~35중량부, 이소프탈산 10~30중량부, 말레산무수물 20~45중량부를 200℃에서 Fascat 4100(Tin계 촉매) 존재하에서 가열 에스테르화 반응시킨 후, 중합금지제를 첨가하고 160℃로 냉각한 다음 희석제로서 스티렌 모노머를 전체 조성물 100중량부당 35중량부를 투입 혼합하여 제조한다.
10 to 40 parts by weight of neopentyl glycol, 15 to 35 parts by weight of propylene glycol, 10 to 30 parts by weight of isophthalic acid and 20 to 45 parts by weight of maleic anhydride were mixed at 200 ° C in a Fascat 4100 Catalyst), the polymerization inhibitor is added, the mixture is cooled to 160 DEG C, and 35 parts by weight of styrene monomer as a diluent is added per 100 parts by weight of the total composition.
상기 이소타입불포화폴리에스테르수지의 함유량은 전체 고강도 신속 광경화 시트 조성물 100중량부 기준으로 0.1~25중량부 포함하는 것이 바람직한데, 25중량부를 초과하면 불완전한 경화가 발생한다. 따라서, 상기 광중합성 불포화 폴리에스테르수지는 경화시 수축성 및 광중합시 불균일하게 중합되는 경향이 있고, 경화 후 표면에 웨이브를 유발시키는 문제가 있으므로 본 발명에서는 상기 광중합성 불포화 폴리에스테르수지와 에폭시아크릴레이트를 혼합하여 사용하는 것이 핵심 특징이다.
The content of the isotactic unsaturated polyester resin is preferably 0.1 to 25 parts by weight based on 100 parts by weight of the entire high-strength quick-cured sheet composition, and if it exceeds 25 parts by weight, imperfect curing occurs. Therefore, the photopolymerizable unsaturated polyester resin tends to be polymerized non-uniformly during shrinking and light polymerization, and causes a wave on the surface after curing. Therefore, in the present invention, the photopolymerizable unsaturated polyester resin and epoxy acrylate It is a key feature to mix and use.
또한, 본 발명에서 사용되는 이소타입불포화폴리에스테르수지 및 에폭시아크릴레이트는 불포화도(불포화기 당량; 불포화기 1개 당의 분자량)이 100~800 정도의 것을 사용하는 것이 바람직한데, 불포화도 100 미만의 것은 합성이 곤란하고, 불포화도 800이 초과하면 고경도의 경화물을 얻을 수 없다.
The isotactic unsaturated polyester resin and epoxy acrylate used in the present invention preferably have an unsaturation degree (equivalent of unsaturated group: molecular weight per unsaturated group) of about 100 to 800, Is difficult to synthesize, and when the degree of unsaturation exceeds 800, a hard hardened material can not be obtained.
본 발명에서 사용되는 스틸렌 모노머로 대표되는 불포화기를 가지는 희석제는 본 발명의 고강도 신속 광경화 시트재를 제조할 때에 섬유보강재 및 필러와의 혼련성, 함침성을 높이고, 시트재의 경도, 강도, 내약품성, 내수성 등을 향상시키기 위해서 중요한 것인 바, 이소타입불포화폴리에스테르수지 합성시 또는 에폭시아크릴레이트 합성시 각각 30~40중량부 사용하고, 사용량이 30 중량부 미만에서는 경화성이 저하되고, 40 중량부를 초과하면 고경도의 제품을 얻지 못하고, 내열성이 부족하므로 시트재로서 바람직하지 않다. 상기 희석제로서 스틸렌 모노머 이외의 불포화기를 가지는 모노머로서 아크릴 모노머 등 중합성 모노머를 사용하는 것도 가능하다.
The diluent having an unsaturated group represented by a styrene monomer represented by the styrene monomer used in the present invention can improve the kneading property and impregnation property with the fiber reinforcing material and the filler when the high strength and quick lightening sheet material of the present invention is produced and the hardness, , And water resistance. When the isotactic unsaturated polyester resin is synthesized or the epoxy acrylate is synthesized, 30 to 40 parts by weight are used, respectively. When the amount is less than 30 parts by weight, curability is deteriorated and 40 parts by weight , A product having a high hardness can not be obtained and heat resistance is not sufficient, so that it is not preferable as a sheet material. It is also possible to use a polymerizable monomer such as an acrylic monomer as the monomer having an unsaturated group other than the styrene monomer as the diluent.
또한, 본 발명에서 접착보조수지로 사용하는 실란화합물은 조성물의 접착성을 향상시키기 위한 것으로, 카르복실기, 메타크릴로일기, 이소시아네이트기, 에폭시기 등의 반응성 치환기를 갖는 실란 화합물(관능성 실란커플링제)을 사용할 수 있다. 이러한 관능성 실란 커플링제의 구체적인 예로는 트리메톡시실릴안식향산, γ-메타크릴옥시프로필트리메톡시실란, 비닐트리아세톡시실란, 비닐트리메톡시실란, γ-이소시아나토프로필트리에톡시실란, γ-글리시독시프로필트리메톡시실란, β-(3,4-에폭시사이클로헥실)에틸트리메톡시실란 등을 들 수 있으며, 사용량은 전체 조성물 100중량부를 기준으로 0.01~5중량부를 사용하며, 5중량부를 초과사용하는 경우에는 오히려 접착성이 저하될 수 있다.
The silane compound used as the adhesive auxiliary resin in the present invention is a silane compound (functional silane coupling agent) having reactive substituents such as a carboxyl group, a methacryloyl group, an isocyanate group and an epoxy group, Can be used. Specific examples of such a functional silane coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatopropyltriethoxysilane, ? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like. The amount is 0.01 to 5 parts by weight based on 100 parts by weight of the total composition, If it is used in excess of 5 parts by weight, the adhesiveness may be deteriorated.
본 발명의 고강도 신속 광경화 시트 조성물에 사용되는 광개시제는 황변 현상이 없고, 특히 고온 고습에서 산 또는 염기가 유리되어 흑점 또는 부식이 발생하지 않는 광개시제를 사용하는 것이 유리하다. 즉, 일반적으로 자외선 경화를 위해 사용되는 광개시제인 알파-하이드록시케톤(hydroxyketone) 광개시제를 사용할 경우에는 황변발생이 발생하므로 장파장 영역에서 감광성이 우수한 가시관경화를 위한 아실포스핀계 광개시제를 병용하여 사용한다.
The photoinitiator used in the high-strength quick-cured sheet composition of the present invention is advantageous to use a photoinitiator free from yellowing phenomenon, particularly free from acid or base at high temperature and high humidity, and free from black spots or corrosion. That is, when a photoinitiator such as a hydroxyketone photoinitiator, which is generally used for ultraviolet curing, is used, an acylphosphine photoinitiator for curing the photosensitizer having excellent photosensitivity in the long wavelength region is used in combination because yellowing occurs.
상기 포스핀계 광개시제는 광투과성이 뛰어나고, 광조사에 의해 아실 래디컬과 포스피노일 래디컬을 발생하므로 종래의 광개시제보다도 광중합 효율이 높으며, 내부경화에 유리한 특성이 있으므로 시트재의 두께 제한 또는 광투과를 위한 필러량의 제한 등의 문제점을 해소할 수 있다.
Since the phosphine-based photoinitiator has excellent light transmittance and generates acyl radicals and phosphinoylradicals upon irradiation with light, it has a higher photopolymerization efficiency than conventional photoinitiators and is advantageous for internal hardening. Therefore, It is possible to solve the problems such as limitation of the amount of the liquid.
따라서 본 발명의 고강도 신속 광경화 시트 조성물에는 자외선 광개시제인 알파-하이드록시케톤(hydroxyketone) 광개시제와 내부 경화에 유리한 가시광 개시제인 아실포스핀(phosphine) 광개시제를 조합하여 사용하는 것이 바람직하다.
Therefore, it is preferable to use a combination of an alpha-hydroxyketone photoinitiator, which is an ultraviolet photoinitiator, and an acylphosphine photoinitiator, which is a visible light initiator, which is advantageous for internal hardening, in the high-strength quick-cured sheet composition of the present invention.
통상 사용가능한 자외선 광개시제의 예로서는, 벤조인에테르계의 이소프로필벤조인에테르, 이소부틸벤조인에테르, 벤조인에틸에테르, 벤조인메틸에테르, 히드록시클로헥실페닐케톤, 벤질디메틸케탈, 케톤벤조페논, 2-클로로티옥산톤, 메틸티옥산톤, 벤조페논, 2,2-디에톡시아세트페논, α-히드록시이소부틸페논, 아실로포스핀옥사이드, 비스아실포스핀 옥사이드, 캄포퀴논 등을 대표예로서 들 수 있다.
Examples of commonly usable ultraviolet photoinitiators include benzoin ethers such as isopropyl benzoin ether, isobutyl benzoin ether, benzoin ethyl ether, benzoin methyl ether, hydroxyclohexyl phenyl ketone, benzyl dimethyl ketal, ketone benzophenone, 2-chlorothioxanthone, methylthioxanthone, benzophenone, 2,2-diethoxyacetophenone,? -Hydroxyisobutylphenone, acylphosphine oxide, bisacylphosphine oxide, camphorquinone, .
또한, 가시광개시제로서는, 아실포스핀옥사이드 화합물이 유효한데, 그 예로서는, 비스(2,6-디클로르벤조일)-페닐포스핀옥사이드, 비스(2,6-디클로르벤조일)-2,5-디메틸페닐포스핀옥사이드, 비스(2,6-디클로르벤조일)-4-에톡시페닐포스핀옥사이드, 비스(2,6-디클로르벤조일)-4-프로필페닐포스핀옥사이드, 비스(2,6-디메톡시벤조일)-2,4,4-트리메틸펜틸포스핀옥사이드, 2,4,6-트리메틸벤조일-디페닐포스핀옥사이드 등을 들 수 있다.
As the visible photoinitiator, an acylphosphine oxide compound is effective. Examples thereof include bis (2,6-dichlorobenzoyl) -phenylphosphine oxide, bis (2,6-dichlorobenzoyl) Bis (2,6-dichlorobenzoyl) -4-ethoxyphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis Dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and the like.
상기 광개시제 조합사용량은 시트재의 경화조건에 따라 조성물 총 중량 중 0.01~10중량부 사용한다. 0.01중량부보다 적으면 완전 경화가 일어나지 않고, 10중량부를 초과하면 고온고습 신뢰성에 표면 흑점 또는 부식이 발생할 수 있다. 또한 아실포스핀계 광개시제는 내부 경화에는 도움되지만 전체 광개시제중 50중량%를 초과하면 흑점이나 부식이 다량 발생할 수 있다.
The amount of the photoinitiator combination used is 0.01 to 10 parts by weight based on the total weight of the composition depending on the curing conditions of the sheet member. If the amount is less than 0.01 part by weight, complete curing will not occur. If the amount is more than 10 parts by weight, surface blackness or corrosion may occur at high temperature and high moisture reliability. Acylphosphine-based photoinitiators are also useful for internal hardening, but more than 50% by weight of the total photoinitiators may cause black spots or corrosion.
본 발명에 사용되는 보강섬유는 특별히 한정되지 않지만, 보강 섬유를 혼합하거나, 조성물을 보강 섬유에 함침시켜 사용하며, 예컨대 유리섬유, 탄소섬유, 금속섬유, 세라믹으로 이루어진 섬유 등과 같은 무기섬유; 아라미드, 폴리에스테르, 비닐론, 페놀, 테프론 등으로 이루어진 유기섬유; 천연섬유 등을 들 수 있다. 또한, 이들 섬유의 형태로는 특별히 한정되지 않지만, 예컨대 크로스(직물) 형상, 촙핑된 스트랜드 매트, 프리포머블(preformable) 매트, 연속 스트랜드 매트, 서페이싱 매트 등과 같은 매트 형상; 촙핑된 스트랜드 형상; 로빙 형상; 부직포 형상 등을 들 수 있다. 이것들은 단독으로 사용하거나 2종 이상을 병용할 수도 있다. 이것들 중에서도 유리섬유가 바람직하다.
The reinforcing fiber used in the present invention is not particularly limited, but may be an inorganic fiber such as a mixture of reinforcing fibers, a composition impregnated with reinforcing fibers, and fibers made of glass fiber, carbon fiber, metal fiber or ceramic; An organic fiber composed of aramid, polyester, vinylon, phenol, and Teflon; Natural fibers and the like. The form of these fibers is not particularly limited, but may be, for example, a mat shape such as a cloth (cross) shape, a twisted strand mat, a preformable mat, a continuous strand mat, a surfacing mat or the like; A doped strand shape; Roving shape; Non-woven fabric, and the like. These may be used alone or in combination of two or more. Of these, glass fibers are preferred.
유리섬유는 17~25 마이크로 직경의 E-유리섬유 또는 E-유리섬유매트와 17~25 마이크로 직경의 C-유리섬유 또는 C-유리섬유매트를 혼용하는 것이 특히 바람직하다. 왜냐하면, E-유리섬유 또는 E-유리섬유매트는 전기적 물성, 내구성, 강도 등의 물성에서 유리하고, C-유리섬유 또는 C-유리섬유매트는 산침식 등 화학적 물성에 강하기 때문에 본 발명의 시트재의 물성에 중요하다.
It is particularly preferred that the glass fibers are mixed with 17 to 25 micro-diameter E-glass fibers or E-glass fiber mats and 17 to 25 micro-diameter C-glass fibers or C-glass fiber mats. Because E-glass fiber or E-glass fiber mat is advantageous in physical properties such as electrical property, durability and strength, and C-glass fiber or C-glass fiber mat is strong against chemical properties such as acid erosion, It is important for physical properties.
상기 E 및 C-유리섬유의 사용량은 각각 전체 조성물 100중량부에 대하여 0.1~50중량부로 사용하는 것이 바람직하다. 0.1중량부 미만이어도 50중량부를 초과하여도 경화물의 기본 성능이 저하될 우려가 있다.
The amount of the E and C-glass fibers used is preferably 0.1 to 50 parts by weight based on 100 parts by weight of the total composition. Even if it is less than 0.1 part by weight or more than 50 parts by weight, the basic performance of the cured product may be deteriorated.
또한, 본 발명에서 사용되는 조성물에는 증점제를 포함하는 것이 바람직하다. 그 증점제로서는, 알칼리 토류금속의 산화물, 수산화물, 금속알콕시드류가 대표적인 것이다. 예를들면, 알칼리 토류금속의 산화마그네슘, 수산화마그네슘, 산화칼륨, 수산화칼슘, 금속알콕시드류를 들 수 있고, 금속알콕시드류의 예로서는, 알루미늄 이소프로필레이트, 메틸아세토아세테이트 알루미늄 디부틸레이트, 메틸에틸아세토아세테이트 알루미늄 디부틸레이트, 프로필아세토아세테이트 알루미늄 디이소프로필레이트, 에틸아세토아세테이트 알루미늄 디에톡시 에틸레이트, 에틸아세토아세테이트 알루미늄 디이소프로필레이트 및 알루미늄트리스(에틸아세토아세테이트)를 들 수 있다. 그리고, 톨루일렌디이소시아네이트, 키실렌디이소시아네이트, 헥산메틸렌디이소시아네이트, 디페닐메탄디이소시아네이트 등의 이소시아네이트 등의 단독 또는 적절한 혼합물을 알칼리 토류금속과 병용하는 것도 가능하다. 그 사용량은 조성물 총중량 100 중량부에 대하여 0.1~5중량부 사용한다. 증점제량이 0.1 중량부 미만에서는, 실질적으로 증점의 효과가 없고, 5 중량부를 넘는 양을 사용하면 고점도가 되어 시트의 제조가 어렵게 된다.
The composition used in the present invention preferably contains a thickening agent. As the thickening agent, oxides, hydroxides and metal alkoxides of alkaline earth metals are representative. Examples of the alkaline earth metals include magnesium oxide, magnesium hydroxide, potassium oxide, calcium hydroxide and metal alkoxides. Examples of metal alkoxides include aluminum isopropylate, methyl acetoacetate aluminum dibutylate, methyl ethyl acetoacetate Aluminum dibutylate, propyl acetoacetate aluminum diisopropylate, ethylacetoacetate aluminum diethoxyethylate, ethylacetoacetate aluminum diisopropylate, and aluminum tris (ethylacetoacetate). It is also possible to use an alkaline earth metal alone or in combination with an isocyanate such as toluylene diisocyanate, xylene diisocyanate, hexane methylene diisocyanate or diphenyl methane diisocyanate. The amount to be used is 0.1 to 5 parts by weight based on 100 parts by weight of the total weight of the composition. When the amount of the thickening agent is less than 0.1 part by weight, the effect of substantially no thickening is not obtained. When the amount of the thickening agent is more than 5 parts by weight, the viscosity becomes high and the production of the sheet becomes difficult.
선택적으로, 본 발명에는 소포제, 요변성 부여제나 그 외 첨가제를 이용할 수도 있다. 소포제는 예를들면, 실리콘계, 불소계, 아크릴계 등의 화합물을 들 수 있으며, 그 사용량은 0.01~5중량부로 사용하며, 요변성 부여제는, 예를 들면 실리카, 마이카, 탄산칼슘 등의 공지의 요변성 부여제를 첨가할 수 있고, 또한, 그 외 첨가제로서 예를 들면 탄산칼슘, 탈크, 진흙, 유리가루, 실리카, 수산화 알루미늄, 황산바륨, 산화 티탄 등의 무기첨가제도 사용할 수 있는데, 그 사용량은 함침성, 거품발생여부, 성형시 유동성 또는 밀착성 등에 따라 조정하여 사용한다.
Alternatively, antifoaming agents, thixotropic agents and other additives may be used in the present invention. The antifoaming agent may be, for example, a silicone compound, a fluorine compound or an acrylic compound. The amount of the antifoaming agent to be used is 0.01 to 5 parts by weight. The thixotropic agent may be, for example, silica, Inorganic additives such as calcium carbonate, talc, mud, glass powder, silica, aluminum hydroxide, barium sulfate and titanium oxide can be used as the other additives. It should be adjusted according to impregnation property, bubble generation, fluidity or adhesion at molding.
또한, 본 발명에는 난연제를 사용할 수 있으며, 난연제로는 특별히 한정되지 않지만, 예컨대 할로겐계 난연제, 인계 난연제; 무기계 난연제 등의 비할로겐계 난연제 등을 사용할 수 있다. 이것들 중에서도 환경을 오염시키지 않기 때문에 비할로겐계 난연제를 사용하는 것이 바람직하며, 인계 난연제인 트리페닐포스페이트(TPP; Triphenyl Phospite)가 특히 바람직하다.
Further, a flame retardant may be used in the present invention. Examples of the flame retardant include, but are not limited to, halogen-based flame retardants, phosphorus-based flame retardants; And non-halogen flame retardants such as inorganic flame retardants. Of these, non-halogen flame retardants are preferred because they do not pollute the environment, and triphenyl phosphite (TPP), which is a phosphorus flame retardant, is particularly preferable.
또한, 본 발명에서는 한층 더 저수축화제를 병용하는 것도 가능하다. 저수축화제로서는, 공지의 예를 들면 폴리스티렌, 폴리초산비닐, 폴리메틸 메타크릴레이트, 폴리에틸렌 등을 사용할 수 있는데, 그 사용량은 점도, 성형성, 내약품성에 다라 조정하여 사용한다. 또한, 본 발명의 조성물에 경화 촉진 및 고경도 경화물을 얻는 목적으로 열중합 개시제도 첨가 가능하고, 구체적으로는 t-부틸퍼옥시피발레이트, 라우로일퍼옥사이드 등의 각종 과산화물, 아조비스이소부티로니트릴 등의 친유성 아조비스 화합물 등도 사용 가능하다. 더우기 본 발명의 조성물에는, 일반적으로 도료용 첨가제로서 이용되고 있는 레벨링제, 가소제, 산화 방지제, 점도강하제 등을 필요에 따라서, 경화물의 경도를 해치지 않는 정도로 첨가할 수 있다.
Further, in the present invention, it is also possible to use a lower shrinking agent in combination. As the low shrinking agent, for example, polystyrene, polyvinyl acetate, polymethyl methacrylate, polyethylene and the like can be used. The amount of the low shrinking agent is adjusted depending on the viscosity, moldability and chemical resistance. Further, for the purpose of accelerating curing and obtaining a hard cured product in the composition of the present invention, a thermal polymerization initiator system can be added. Specific examples thereof include various peroxides such as t-butyl peroxypivalate and lauroyl peroxide, azobisisobutyl And a lipophilic azo compound such as ronitril can also be used. Further, a leveling agent, a plasticizer, an antioxidant, a viscosity reducing agent and the like generally used as an additive for paints can be added to the composition of the present invention to such an extent as not to impair the hardness of the cured product.
본 발명의 시트재 경화에 사용되는 광파장은 380~1200nm의 영역이다. 380nm보다 짧은 자외선 영역은 광투과성이 극단적으로 저하되고 안전성이 문제가 되며, 1200 nm보다 긴 파장의 영역은 감광성이 저하되기 때문에 바람직하지 않다. 상기 광파장의 광원으로서는, 예를 들면 할로겐 램프, 크세논램프, 수은 램프, 메탈할라이드 램프, 태양광 등을 들 수 있으며, 그 중에서도 가시광선용 메탈할라이드 램프 또는 할로겐 램프가 바람직한데, 이는 본 발명의 알파-하이드록시케톤(hydroxyketone) 광개시제와 아실포스핀(phosphine) 광개시제의 분해에 유효한 파장을 방사함과 동시에 열선의 작용에 의해 피조사물의 온도가 상승해 경화 반응을 촉진하므로 바람직하다.
The light wavelength used for curing the sheet material of the present invention is in the range of 380 to 1200 nm. In an ultraviolet ray region shorter than 380 nm, the light transmittance is extremely lowered and safety is a problem, and a region with a wavelength longer than 1200 nm is not preferable because the photosensitivity is lowered. As the light source of the light wavelength, for example, a halogen lamp, a xenon lamp, a mercury lamp, a metal halide lamp, a sunlight and the like can be used. Among them, a metal halide lamp or a halogen lamp for visible light is preferable, A hydroxyketone photoinitiator and an acylphosphine photoinitiator, and at the same time, the temperature of the irradiated object rises due to the action of heat rays to promote the curing reaction.
또한, 본 발명의 시트재의 제조는, 보강섬유를 조성물에 혼합하거나, 또는 보강섬유매트에 조성물을 함침한 후, 양면에 이형재을 적층하여 제조하는데, 상기 이형재는 시트재가 가공 또는 시공되는 동안에 조성물이 경화됨으로써 가공성이 손상되는 일이 없도록 차광하는 작용(차광성)을 가지며, 또한 시트재를 충분히 가공하거나 시공할 수 있는 유연성을 갖고, 상기 이형재에 의해 시트재의 광경화가 방지되어 가공시간을 충분히 취할 수 있고, 시공 후에 이형재를 제거함으로써 시트재를 신속히 경화시킬 수 있게 된다.
The sheet material of the present invention is produced by mixing the reinforcing fiber into the composition or by impregnating the reinforcing fiber mat with the composition and then laminating the releasing material on both sides of the sheet material. (Light-shielding property) so as not to impair the processability, and also has the flexibility to sufficiently process or apply the sheet material, and the photo-curing of the sheet material is prevented by the release material, , It is possible to quickly cure the sheet material by removing the release material after the application.
상기 이형재의 형태로는 특별히 한정되지 않지만, 예컨대 종이나 수지 재료에 차광재를 증착, 코팅 또는 분산한 필름 등을 들 수 있으며, 이것들을 적층한 것일 수도 있다. 예컨대, 이러한 종이나 수지 재료에 차광재를 증착한 필름으로는, 알루미늄 등의 금속에 의한 증착막을 일면 또는 양면에 형성한 필름 등을 들 수 있고, 차광재로서 안료 등을 분산한 도막이나 잉크막을 일면 또는 양면에 코팅하거나, 차광재를 분산하여 제조한 차광필름일 수도 있다.
The shape of the releasing member is not particularly limited, and for example, a film or the like in which a light shielding material is vapor-deposited, coated or dispersed in a paper or resin material, or the like may be laminated. Examples of the film on which a light shielding material is vapor-deposited on such a species or a resin material include a film formed on one side or both sides of a vapor-deposited film of a metal such as aluminum and the like. A coating film or ink film Or may be a light-shielding film produced by dispersing a light-shielding material.
상기 종이로는 특별히 한정되지 않지만, 예컨대 천연섬유, 합성섬유, 무기섬유 등으로 형성된 것을 들 수 있고, 실리콘 처리 등으로 표면 처리된 것이나 프레스 가공, 엠보스 가공 등을 실시한 것일 수도 있으며, 상기 필름으로는 시공성을 손상시키지 않을 정도의 강도 및 유연성 그리고 조성물에 함유된 단량체나 희석제에 대한 내구성을 갖는 것이면 특별히 한정되지 않는다.
The paper is not particularly limited, and examples of the paper include those formed from natural fibers, synthetic fibers, inorganic fibers, etc., and may be those which have been subjected to a surface treatment by a silicone treatment, a press treatment, an embossing treatment or the like. Is not particularly limited as long as it has strength and flexibility so as not to impair the workability and has durability against the monomer or diluent contained in the composition.
상기 필름수지 재료로는 특별히 한정되지 않지만, 예컨대 폴리에틸렌, 폴리프로필렌, 폴리부텐, 폴리스티렌, 에틸렌-α-올레핀 공중합체 등과 같은 폴리올레핀; 폴리에틸렌테레프탈레이트, 폴리부틸렌테레프탈레이트 등과 같은 폴리에스테르; 테트라플루오로에틸렌, 폴리플루오르화비닐리덴, 폴리모노클로로트리플루오로에틸렌 등과 같은 불소수지; 폴리부타디엔, 폴리카보네이트, 폴리아세탈, 폴리아미드, 폴리페닐렌에테르, 폴리페닐렌술파이드, 폴리에테르술폰, 폴리우레탄, 폴리이미드, 폴리에테르에테르케톤, 폴리메틸펜텐, 아이오노머 수지, 폴리비닐부틸랄, 폴리비닐알콜, 셀룰로오스디아세테이트, 폴리염화비닐, 폴리염화비닐리덴, 염화비닐공중합체, 에틸렌-아세트산비닐 공중합체, 에틸렌-(메타)아크릴산 공중합체, 에틸렌-(메타)아크릴산에스테르 공중합체 등을 들 수 있고, 이것들은 단독으로 사용하거나 2종 이상을 병용할 수도 있다.
Examples of the film resin material include, but are not limited to, polyolefins such as polyethylene, polypropylene, polybutene, polystyrene, ethylene-? -Olefin copolymer and the like; Polyesters such as polyethylene terephthalate, polybutylene terephthalate and the like; Fluorine resins such as tetrafluoroethylene, polyvinylidene fluoride, polymonochlorotrifluoroethylene and the like; Polyimide, polyether ether ketone, polymethylpentene, ionomer resin, polyvinyl butyral, polyether sulfone, polyether sulfone, polyether sulfone, polyether sulfone, polyether sulfone, polyether sulfone, polyether sulfone, polybutadiene, polycarbonate, polyacetal, polyamide, polyphenylene ether, (Meth) acrylic acid copolymers, ethylene- (meth) acrylic acid ester copolymers, and the like can be used in combination with a polyvinyl alcohol, cellulose diacetate, polyvinyl chloride, polyvinylidene chloride, vinyl chloride copolymer, ethylene-vinyl acetate copolymer, These may be used alone or in combination of two or more.
상기 필름의 두께로는 특별히 한정되지 않지만, 예컨대 5～2000㎛인 것이 바람직하다. 5㎛ 미만인 경우, 이형재가 박리를 견딜만한 충분한 강도를 갖고 있지 않을 우려가 있고, 2000㎛를 초과하는 경우, 시트재의 시공성이 손상될 우려가 있으므로 바람직한 두께는 10～500㎛이다.
The thickness of the film is not particularly limited, but is preferably 5 to 2000 占 퐉. If the thickness is less than 5 mu m, the releasing material may not have sufficient strength to withstand peeling. If the thickness exceeds 2000 mu m, the workability of the sheet material may be impaired, and the preferable thickness is 10 to 500 mu m.
본 발명의 광경화성 시트는 경화 전에는 충분한 가공이나 시공할 수 있는 가소성이나 유연성을 가지고, 경화 후에는 충분한 벤딩 강도나 벤딩 탄성율 등의 강도, 내구성을 가지며, 수지나 첨가제 또는 충전제 종류에 따라 내후성, 내수성, 내마모성, 높은 전기특성 등과 같은 충분한 기본 성능을 가지고 있는 광경화 SMC시트 또는 프리프레그 시트인 것이 바람직하며, 시트재의 두께는 피복 또는 보수하려고 하는 기재에 따라 다르지만, 통상 0.1～10㎜인 것이 바람직하다. 0.1㎜ 미만인 경우 경화물이 충분한 강도를 갖지 않을 우려가 있고, 10㎜를 초과하는 경우에는 가공성이나 시공성이 저하되고, 특히, 광경화성이 저하될 우려가 있다. 추가적인 두께를 확보하기 위하여 상기 시트재 상부에 적층하여 사용할 수 있음은 물론이다.
The photo-curable sheet of the present invention has plasticity and flexibility that can be sufficiently processed and applied before curing, has strength and durability such as sufficient bending strength and bending elasticity after curing, and weather resistance, water resistance , An abrasion resistance, a high electric characteristic, and the like. The thickness of the sheet material varies depending on the substrate to be coated or to be repaired, but is preferably 0.1 to 10 mm . If the thickness is less than 0.1 mm, the cured product may not have sufficient strength. If it exceeds 10 mm, the workability and workability may be deteriorated. In particular, the photo-curability may deteriorate. It is needless to say that they may be stacked on top of the sheet material in order to secure an additional thickness.
실시예Example
[합성예 1］(비스페놀A에폭시아크릴레이트의 합성)[Synthesis Example 1] (Synthesis of bisphenol A epoxy acrylate)
교반기, 환류 냉각기, 질소 가스 도입관, 온도계를 구비한 반응기에 비스페놀A타입 에폭시수지 35중량부와, 비스페놀A 20중량부 및 중축합 반응의 촉진제로서 트리에틸아민 1중량부를 질소 분위기하에서 150℃으로 2시간 반응시킨 후, 110℃까지 냉각하고, 메틸메타크릴레이트 35중량부, 말레산 3중량부, 에스테르화 촉매로서 Ancamin K-54[트리스(디메틸아미노메틸)페놀] 1중량부, 중합금지제로서 하이드로퀴논 0.1중량부, 증점제로서 4,4-메틸렌디페닐디이소시아네이트 0.1중량부, 희석제로서 스틸렌 모노머를 전체조성물 100중량부당 10중량부 투입 희석시키고, 공기를 불어넣으며 110~130℃으로 3~4시간 반응시켜, 산가가 5 이하가 된 시점에서 반응을 종료하고, 스틸렌 모노머를 25중량부 추가하여 비스페놀A에폭시아크릴레이트를 합성하였다.
35 parts by weight of a bisphenol A type epoxy resin, 20 parts by weight of bisphenol A and 1 part by weight of triethylamine as an accelerator for the polycondensation reaction were added to a reactor equipped with a stirrer, a reflux condenser, a nitrogen gas introducing tube and a thermometer at 150 캜 The mixture was allowed to react for 2 hours and then cooled to 110 ° C. 35 parts by weight of methyl methacrylate, 3 parts by weight of maleic acid, 1 part by weight of Ancamin K-54 [tris (dimethylaminomethyl) phenol] 0.1 part by weight of hydroquinone as a thickener, 0.1 part by weight of 4,4-methylenediphenyl diisocyanate as a thickener, and 10 parts by weight of a styrene monomer as a diluent were diluted by 10 parts by weight per 100 parts by weight of the total composition. After 4 hours of reaction, the reaction was terminated when the acid value became 5 or less, and 25 parts by weight of styrene monomer was added to synthesize bisphenol A epoxy acrylate.
[합성예 2］(이소타입 불포화 폴리에스테르수지의 합성)[Synthesis Example 2] (Synthesis of isotype-unsaturated polyester resin)
교반기, 환류 냉각기, 질소 가스 도입관, 온도계를 구비한 40리터의 반응 용기 중에 네오펜틸 글리콜 40중량부, 프로필렌글리콜 35중량부, 이소프탈산 30중량부, 말레산무수물 45중량부를 200℃에서 Fascat 4100(Tin계 촉매) 존재하 가열, 산가가 15가 될 때까지 에스테르화 반응시킨 후, 중합금지제로서 하이드로퀴논을 반응물 100중량부에 대하여 0.1중량부를 첨가하고 160℃로 냉각한 다음, 희석제로서 스티렌 모노머를 전체 조성물 100중량부를 기준으로 35중량부를 투입 혼합하여 이소타입불포화폴리에스테르수지를 합성하였다.
40 parts by weight of neopentyl glycol, 35 parts by weight of propylene glycol, 30 parts by weight of isophthalic acid and 45 parts by weight of maleic anhydride were placed in a 40-liter reaction vessel equipped with a stirrer, a reflux condenser, (Tin-based catalyst), 0.1 part by weight of hydroquinone was added as a polymerization inhibitor to 100 parts by weight of the reaction product, and the mixture was cooled to 160 DEG C, and then styrene And 35 parts by weight of monomer based on 100 parts by weight of the total composition were charged and mixed to synthesize isotype unsaturated polyester resin.
실시예 1Example 1
합성예 1에서 얻은 비스페놀A에폭시아크릴레이트 60중량부, 합성예 2에서 얻은 이소타입불포화폴리에스테르수지 25중량부 및 접착보조수지 KBM-503(3-Methacryloxypropyltrimethoxysilane) 5중량부의 혼합수지에 알파히드록시 케톤계 광개시제 Ir-184？(스위스 Ciba specialty chemical사 제품) 3중량부 및 포스핀옥사이드계 광개시제 TPO？(이탈리아의 Lambert사 제품) 3중량부, 증점제로서 MgO 3중량부, 점도강하제 BYK-103(Phosphoric acid esters) 0.5중량부, 소포제 BYK-A515(Solution of foam-destroying polymers, silicone free) 3중량부를 혼합하여 고강도 신속 광경화 시트 조성물을 제조하였다. 다음, 상기 고강도 신속 광경화 시트 조성물 100중량부에 대하여 25 마이크로 직경의 E-유리섬유매트 10중량부 및 25 마이크로 직경의 C-유리섬유매트 10중량부로 적층된 유리섬유층에 상기 조성물을 함침시키고, 두께 10 mm, 1m x 1m의 고강도 신속 광경화 시트를 제조한 후, 시트표면을 2 kW 메탈할라이드 램프로 1 m의 거리에서 5분간 광조사하고, 그 결과를 표 1에 나타내었다.
60 parts by weight of the bisphenol A epoxy acrylate obtained in Synthesis Example 1, 25 parts by weight of the isotactic unsaturated polyester resin obtained in Synthesis Example 2 and 5 parts by weight of the adhesive auxiliary resin KBM-503 (3-Methacryloxypropyltrimethoxysilane) 3 parts by weight of a photoinitiator Ir-184? (Manufactured by Ciba Specialty Chemical, Switzerland) and 3 parts by weight of a phosphine oxide photoinitiator TPO? (Manufactured by Lambert of Italy), 3 parts by weight of MgO as a thickener, BYK- acid esters) and 3 parts by weight of a defoaming agent BYK-A515 (solution of foam-destroying polymers, silicone free) were mixed to prepare a high-strength quick-cured sheet composition. Then, the composition was impregnated into a glass fiber layer laminated with 100 parts by weight of the high-strength quick-cured sheet composition and 10 parts by weight of a 25-micro-diameter E-glass fiber mat and 10 parts by weight of a 25- The sheet surface was irradiated with a 2-kW metal halide lamp at a distance of 1 m for 5 minutes, after which a high-intensity light-cured sheet having a thickness of 10 mm and a height of 1 m x 1 m was produced.
비교예 1 Comparative Example 1
실시예 1에서 사용한 혼합수지중에서 합성예 1에서 얻은 비스페놀A에폭시아크릴레이트를 제외한 이소타입불포화폴리에스테르수지만을 사용한 것을 제외하고는 실시예 1과 같이 동일하게 실시하고 그 결과를 표 1에 나타내었다.
The same procedure was followed as in Example 1 except that only the isotactic unsaturated polyester resin except for the bisphenol A epoxy acrylate obtained in Synthesis Example 1 was used in the mixed resin used in Example 1 and the results are shown in Table 1 .
비교예 2 Comparative Example 2
실시예 1에서 사용한 혼합수지중에서 합성예 2에서 얻은 이소타입불포화폴리에스테르수지를 제외한 비스페놀A에폭시아크릴레이트만을 사용한 것을 제외하고는 실시예 1과 같이 동일하게 실시하고 그 결과를 표 1에 나타내었다.
The results are shown in Table 1, except that only the bisphenol A epoxy acrylate except the isotactic unsaturated polyester resin obtained in Synthesis Example 2 was used in the mixed resin used in Example 1. The results are shown in Table 1.
비교예 3 Comparative Example 3
실시예 1에서 사용한 혼합수지중에서 실란 접착보조수지를 제외하고는 실시예 1과 같이 동일하게 실시하고 그 결과를 표 1에 나타내었다.
The same procedure as in Example 1 was carried out except for the silane adhesion auxiliary resin among the mixed resins used in Example 1, and the results are shown in Table 1.
[물성평가][Property evaluation]
① 경화성 측정① Cure measurement
바콜경도계(형식:GYXJ934-1)로 경도를 측정하고, 경도 50이상인 경우를 경화성의 양호로 평가하였다.The hardness was measured with a Barcol hardness tester (model: GYXJ934-1), and when the hardness was 50 or more, the hardness was evaluated as good.
② 표면건조시간② Surface drying time
지촉시험으로서 20℃ 실온에서 탈지면 약 2~3㎠를 시트 표면에 눌러붙여도 탈지면이 점착에 의해 시트 표면에 남지않을 때까지의 시간을 측정하였다.As a touch test, the time until the cotton sheet was not left on the surface of the sheet by sticking was measured, even when the cotton sheet was pressed on the sheet surface at a room temperature of 20 캜 for about 2 to 3
③ 인장강도, 인장탄성율③ Tensile strength, tensile modulus
시트경화체 물성으로서, 인장강도, 인장탄성율은 JIS-K-7113에 의하여 각각 측정하였다.The tensile strength and tensile elastic modulus as properties of the sheet-hardened body were measured according to JIS-K-7113.
④ 구부림 강도, 구부림 탄성율④ Bending strength, bending elasticity
시트경화체 물성으로서, 구부림 강도, 구부림 탄성율은 JIS-K-7203에 의하여각각 측정하였다.As the properties of the sheet-hardened body, the bending strength and the bending elastic modulus were measured according to JIS-K-7203.
상기 표 1에서 나타난 바와 같이, 본 발명의 고강도 신속 광경화 시트재는 불포화폴리에스테르수지 또는 에폭시아크릴레이트수지를 단독으로 사용한 경우보다 같은 시간동안 광조사 하더라도 경화성, 인장강도, 구부림강도 등에서 뛰어난 특성을 나타냄을 알 수 있으며, 단일 광개시제를 사용한 경우에 비하여 광중합속도 및 균일한 광중합면에서 우수한 효과를 나타내었다.
As shown in Table 1, the high-strength quick-setting sheet material of the present invention exhibits excellent properties in curability, tensile strength, bending strength, etc. even when irradiated with light for the same period of time as in the case of using an unsaturated polyester resin or an epoxy acrylate resin alone And showed excellent effects on the photopolymerization rate and homogeneous photopolymerization surface as compared with the case of using a single photoinitiator.
1 : 고강도 신속 광경화 시트재
2 : 고강도 광경화 시트 조성물층
3, 4 : 자외선 차단 이형필름층1: High-strength quick-curing sheet material
2: High Strength Photocurable Sheet Composition Layer
3, 4: UV protection film layer
Claims (13)
A resin composition comprising 45 to 70 parts by weight of an epoxy acrylate resin, 0.1 to 25 parts by weight of an isotactic unsaturated polyester resin, 0.01 to 5 parts by weight of a silane-based adhesive auxiliary resin, 0.01 to 5 parts by weight of a phosphine-based photoinitiator, 0.01 to 5 parts by weight of an? -hydroxyketone type photoinitiator, 0.1 to 50 parts by weight of E-glass fiber or E-glass fiber mat of 17 to 25 micro-diameter, C-glass fiber or C-glass fiber of 17 to 25 micro- 0.1 to 50 parts by weight of a mat, 0.1 to 5 parts by weight of a thickener, 0.01 to 3 parts by weight of a viscosity-decreasing agent, and 0.01 to 5 parts by weight of a defoaming agent.
상기 에폭시아크릴레이트는 비스페놀A타입 에폭시수지 30~60중량부와, 비스페놀A 10~30중량부 및 중축합 반응촉진제 0.1~3중량부를 질소 분위기하에서 150℃으로 2시간 반응시킨 후, 110℃까지 냉각하고, 메틸메타크릴레이트 15~35중량부, 말레산 0.1~5중량부, 에스테르화 촉매 0.1~3중량부, 중합금지제 0.01~0.1중량부, 증점제 0.1~5중량부, 희석제를 전체조성물 100중량부당 35중량부 투입 희석시키고, 공기를 불어넣으며 110~130℃으로 3~4시간 반응시켜 제조된 것을 특징으로 하는 고강도 신속 광경화 시트 조성물
The method according to claim 1,
The epoxy acrylate is prepared by reacting 30 to 60 parts by weight of a bisphenol A type epoxy resin, 10 to 30 parts by weight of bisphenol A and 0.1 to 3 parts by weight of a polycondensation reaction accelerator at 150 DEG C for 2 hours under a nitrogen atmosphere, 0.1 to 5 parts by weight of maleic acid, 0.1 to 3 parts by weight of an esterification catalyst, 0.01 to 0.1 part by weight of a polymerization inhibitor, 0.1 to 5 parts by weight of a thickener, 0.1 to 5 parts by weight of a diluent, And 35 parts by weight per part by weight of diluted sulfuric acid and blowing air into the flask at 110 to 130 DEG C for 3 to 4 hours.
상기 에스테르화 촉매는 트리에틸아민, 디메틸아닐린, 트리스(디메틸아미노메틸)페놀, 트리메틸벤질암모늄크로라이드, 트리에틸벤질암모늄크로라이드, 피리디늄크로라이드, 수산화리튬, 염화리튬중에서 선택된 1종 이상인 것을 특징으로 하는 고강도 신속 광경화 시트 조성물
3. The method of claim 2,
The esterification catalyst is at least one member selected from triethylamine, dimethylaniline, tris (dimethylaminomethyl) phenol, trimethylbenzylammonium chloride, triethylbenzylammonium chloride, pyridinium chloride, lithium hydroxide and lithium chloride High-speed quick-setting sheet composition
상기 중합금지제는 하이드로퀴논, 메틸하이드로퀴논, 벤조퀴논, 메틸-p-벤조퀴논, t-부틸카테콜, 2,6-디-t-부틸-4-메틸페놀, 4-메톡시페놀, 페노티아진 중에서 선택된 1종 이상인 것을 특징으로 하는 고강도 신속 광경화 시트 조성물
3. The method of claim 2,
The polymerization inhibitor may be at least one selected from the group consisting of hydroquinone, methylhydroquinone, benzoquinone, methyl-p-benzoquinone, t-butylcatechol, 2,6- Wherein the photo-curable composition comprises at least one selected from the group consisting of
상기 실란계접착보조수지는 트리메톡시실릴안식향산, γ-메타크릴옥시프로필트리메톡시실란, 비닐트리아세톡시실란, 비닐트리메톡시실란, γ-이소시아나토프로필트리에톡시실란, γ-글리시독시프로필트리메톡시실란, β-(3,4-에폭시사이클로헥실)에틸트리메톡시실란 중에서 선택되는 1종 이상인 것을 특징으로 하는 고강도 신속 광경화 시트 조성물
The method according to claim 1,
The silane-based adhesion-assisting resin may be at least one selected from the group consisting of trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatopropyltriethoxysilane, (3,4-epoxycyclohexyl) ethyltrimethoxysilane. The high-strength quick-curing sheet composition according to any one of claims 1 to 3,
상기 이소타입불포화폴리에스테르수지 제조는 네오펜틸 글리콜 10~40중량부, 프로필렌글리콜 15~35중량부, 이소프탈산 10~30중량부, 말레산무수물 20~45중량부를 200℃에서 Tin계 에스테르화 촉매 존재하에서 가열 에스테르화 반응시킨 후, 중합금지제를 첨가하고 160℃로 냉각한 다음 희석제로서 스티렌 모노머를 전체 조성물 100중량부당 35중량부를 투입 혼합하여 제조된 것을 특징으로 하는 고강도 신속 광경화 시트 조성물
The method according to claim 1,
10 to 40 parts by weight of neopentyl glycol, 15 to 35 parts by weight of propylene glycol, 10 to 30 parts by weight of isophthalic acid and 20 to 45 parts by weight of maleic anhydride are mixed at 200 DEG C with a Tin esterification catalyst In the presence of a polymerization initiator, adding a polymerization inhibitor, cooling to 160 DEG C, and then adding 35 parts by weight of a styrene monomer as a diluent to 100 parts by weight of the total composition.
상기 이소타입불포화폴리에스테르수지 및 에폭시아크릴레이트는 불포화도(불포화기 당량; 불포화기 1개 당의 분자량)가 100~800인 것을 사용하는 것을 특징으로 하는 고강도 신속 광경화 시트 조성물
The method according to claim 1,
Wherein the isotactic unsaturated polyester resin and the epoxy acrylate each have an unsaturation degree (unsaturated group equivalent: molecular weight per unsaturated group) of from 100 to 800.
상기 알파히드록시케톤(α-Hydroxyketone)계 광개시제는 이소프로필벤조인에테르, 이소부틸벤조인에테르, 벤조인에틸에테르, 벤조인메틸에테르, 히드록시클로헥실페닐케톤, 벤질디메틸케탈, 케톤벤조페논, 2-클로로티옥산톤, 메틸티옥산톤, 벤조페논, 2,2-디에톡시아세트페논, α-히드록시이소부틸페논, 아실로포스핀옥사이드, 비스아실포스핀 옥사이드, 캄포퀴논 중에서 선택된 1종 이상을 사용하는 것을 특징으로 하는 고강도 신속 광경화 시트 조성물
The method according to claim 1,
The α-hydroxyxyketone photoinitiator may be at least one selected from the group consisting of isopropyl benzoin ether, isobutyl benzoin ether, benzoin ethyl ether, benzoin methyl ether, hydroxycyclohexyl phenyl ketone, benzyl dimethyl ketal, ketone benzophenone, 2-chloroethoxytone, methylthioxanthone, benzophenone, 2,2-diethoxyacetophenone,? -Hydroxyisobutylphenone, acylphosphine oxide, bisacylphosphine oxide, camphorquinone By weight or more based on the total weight of the composition.
상기 포스핀(phosphine)계 광개시제는 비스(2,6-디클로르벤조일)-페닐포스핀옥사이드, 비스(2,6-디클로르벤조일)-2,5-디메틸페닐포스핀옥사이드, 비스(2,6-디클로르벤조일)-4-에톡시페닐포스핀옥사이드, 비스(2,6-디클로르벤조일)-4-프로필페닐포스핀옥사이드, 비스(2,6-디메톡시벤조일)-2,4,4-트리메틸펜틸포스핀옥사이드, 2,4,6-트리메틸벤조일-디페닐포스핀옥사이드 중에서 선택된 1종 이상을 사용하는 것을 특징으로 하는 고강도 신속 광경화 시트 조성물
The method according to claim 1,
The phosphine-based photoinitiator may be at least one selected from the group consisting of bis (2,6-dichlorobenzoyl) -phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4- 4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and the like.
상기 고강도 신속 광경화 시트 조성물에는 난연제, 요변성 부여제, 레벨링제, 저수축화제, 열중합개시제, 가소제, 산화 방지제, 무기첨가제로부터 선택된 1종 이상 더 포함하는 것을 특징으로 하는 고강도 신속 광경화 시트 조성물
10. The method according to any one of claims 1 to 9,
Wherein the high-strength quick-setting sheet composition further contains at least one selected from a flame retardant, a thixotropic agent, a leveling agent, a low shrinkage agent, a thermal polymerization initiator, a plasticizer, an antioxidant, Composition
Wherein the high strength quick-cured sheet composition layer comprises a light-shielding release film layer on the top side, a high-intensity light-fast curing sheet composition layer and a light-blocking release film layer on the underside, Characterized in that the composition is a composition layer.
상기 광차단 이형필름은 차광재를 일면 또는 양면에 코팅하거나, 차광재를 분산하여 제조한 필름으로서 필름두께 10～500㎛인 것을 특징으로 하는 고강도 신속 광경화 시트재
12. The method of claim 11,
The light-shielding release film is a film prepared by coating a light-shielding material on one side or both sides or by dispersing a light-shielding material, and has a film thickness of 10 to 500 μm.
상기 고강도 신속 광경화 시트재는 광경화 SMC시트 또는 프리프레그 시트로서 두께가 0.1～10㎜인 것을 특징으로 하는 고강도 신속 광경화 시트재12. The method of claim 11,
Wherein said high-strength quick-cured sheet material is a photocurable SMC sheet or prepreg sheet having a thickness of 0.1 to 10 mm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020100030960A KR101141967B1 (en) | 2010-04-05 | 2010-04-05 | A high-strength quick-curing sheet composition and a photocurable sheet material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020100030960A KR101141967B1 (en) | 2010-04-05 | 2010-04-05 | A high-strength quick-curing sheet composition and a photocurable sheet material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20110111734A KR20110111734A (en) | 2011-10-12 |
| KR101141967B1 true KR101141967B1 (en) | 2012-05-04 |
Family
ID=45027700
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020100030960A KR101141967B1 (en) | 2010-04-05 | 2010-04-05 | A high-strength quick-curing sheet composition and a photocurable sheet material |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR101141967B1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101340457B1 (en) | 2013-06-28 | 2013-12-11 | (주)세풍폴리머 | Compositions of uv cured prepreg and preparation process of same |
| KR101425402B1 (en) | 2012-12-17 | 2014-08-14 | 애경화학 주식회사 | Urethane Hybrid Vinyl Ester Resin For Using UV curable Sheet and Manufacturing the Same |
| KR20190020894A (en) * | 2017-08-22 | 2019-03-05 | 최창원 | Timber molding method |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102013012206A1 (en) | 2013-07-16 | 2015-01-22 | Lohmann Gmbh & Co. Kg | Process for the production of molded parts by means of adhesive strips |
| KR102225655B1 (en) | 2019-07-16 | 2021-03-12 | (주)켐베이스 | UV curable sheet resin composition for repairing concrete and waterproof sheet and preparation mehtod thereof |
| KR102585468B1 (en) * | 2023-03-20 | 2023-11-21 | 주식회사 코에원텍 | Manufacturing method for a photocuring insulating sheet having insulation and a product thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6207726B1 (en) | 1998-02-13 | 2001-03-27 | Showa Denko Kabushiki Kaisha | Photocurable prepreg composition and production method thereof |
| JP2004244618A (en) | 2003-01-22 | 2004-09-02 | Kansai Paint Co Ltd | Coating composition for optical fiber and coated optical fiber |
| KR20070030674A (en) * | 2005-09-13 | 2007-03-16 | 도아 그라우트 고교 가부시끼가이샤 | A curable resin composition for sewerage and irrigation channel, and a liner or a tubular liner prepared using the same |
| KR20090013920A (en) * | 2007-08-03 | 2009-02-06 | 도레이새한 주식회사 | Heat-resistant adhesive sheet |
-
2010
- 2010-04-05 KR KR1020100030960A patent/KR101141967B1/en active IP Right Grant
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6207726B1 (en) | 1998-02-13 | 2001-03-27 | Showa Denko Kabushiki Kaisha | Photocurable prepreg composition and production method thereof |
| JP2004244618A (en) | 2003-01-22 | 2004-09-02 | Kansai Paint Co Ltd | Coating composition for optical fiber and coated optical fiber |
| KR20070030674A (en) * | 2005-09-13 | 2007-03-16 | 도아 그라우트 고교 가부시끼가이샤 | A curable resin composition for sewerage and irrigation channel, and a liner or a tubular liner prepared using the same |
| KR20090013920A (en) * | 2007-08-03 | 2009-02-06 | 도레이새한 주식회사 | Heat-resistant adhesive sheet |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101425402B1 (en) | 2012-12-17 | 2014-08-14 | 애경화학 주식회사 | Urethane Hybrid Vinyl Ester Resin For Using UV curable Sheet and Manufacturing the Same |
| KR101340457B1 (en) | 2013-06-28 | 2013-12-11 | (주)세풍폴리머 | Compositions of uv cured prepreg and preparation process of same |
| KR20190020894A (en) * | 2017-08-22 | 2019-03-05 | 최창원 | Timber molding method |
| KR101967794B1 (en) | 2017-08-22 | 2019-04-10 | 최창원 | Timber molding method |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20110111734A (en) | 2011-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101163731B1 (en) | Flame retardant photocurable resin composition and photocurable sheet material comprising same | |
| KR101163732B1 (en) | Flame retardant photocurable resin composition and photocurable sheet material comprising same | |
| KR101141967B1 (en) | A high-strength quick-curing sheet composition and a photocurable sheet material | |
| JP5512069B2 (en) | Curable resin composition, lining material and tubular lining material | |
| JP2002059525A (en) | Permeable waterproof coated structure and its building method | |
| JPH11210981A (en) | Photo-curing material for covering or repairing inside face of tubular molded product and its covering method | |
| JP4884732B2 (en) | Curable resin composition, lining material and tubular lining material | |
| JP3131947B2 (en) | Unsaturated polyester resin composition, waterproof material composition, waterproof coating structure using the same, and waterproof coating method | |
| EP1762581A1 (en) | Curable resin composition, lining material and tube-shaped lining material | |
| KR101185166B1 (en) | Self-propelled steel aggregate parking lot room temperature curing type eco-friendly waterproof and anti-slip flooring composition | |
| KR101806228B1 (en) | Vinylester resin composition for UV curable sheet and preparation method thereof | |
| KR101091160B1 (en) | High strength fast photocurable sheet composition and photocurable sheet material comprising same | |
| WO2014191308A1 (en) | Composite composition containing a polycyclic ether polypol | |
| JP2004181934A (en) | Method for frp lining | |
| JP3289302B2 (en) | Waterproofing material composition for civil engineering construction, waterproof composite covering structure, construction method of waterproof composite covering structure for civil engineering building, and asphalt waterproofing repair method | |
| JP2007077217A (en) | Curable resin composition, lining material and tubular lining material | |
| KR100776718B1 (en) | A curable resin composition for sewerage and irrigation channel, and a liner or a tubular liner prepared using the same | |
| JP2001335612A (en) | Curing material for covering or repairing inside face of tubular molded product and its covering method | |
| JP4465259B2 (en) | Tubular lining material | |
| JP6238461B2 (en) | Curable material for repairing inner surface of tubular molded body and repair method | |
| JP3278001B2 (en) | Adhesive composition and bonding method using the same | |
| JP2006272837A (en) | Laminated structure | |
| JP3639778B2 (en) | Waterproof material composition, waterproof coating structure, and construction method thereof | |
| KR102225655B1 (en) | UV curable sheet resin composition for repairing concrete and waterproof sheet and preparation mehtod thereof | |
| JPH11270147A (en) | Method for reinforcing structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20150424 Year of fee payment: 4 |
|
| FPAY | Annual fee payment |
Payment date: 20160212 Year of fee payment: 5 |
|
| FPAY | Annual fee payment |
Payment date: 20170308 Year of fee payment: 6 |
|
| FPAY | Annual fee payment |
Payment date: 20180406 Year of fee payment: 7 |
|
| FPAY | Annual fee payment |
Payment date: 20190425 Year of fee payment: 8 |