KR100609771B1 - Water-soluble acrylic resin that does not contain formaldehyde and glass wool binder composition containing it - Google Patents
Water-soluble acrylic resin that does not contain formaldehyde and glass wool binder composition containing it Download PDFInfo
- Publication number
- KR100609771B1 KR100609771B1 KR1020040118244A KR20040118244A KR100609771B1 KR 100609771 B1 KR100609771 B1 KR 100609771B1 KR 1020040118244 A KR1020040118244 A KR 1020040118244A KR 20040118244 A KR20040118244 A KR 20040118244A KR 100609771 B1 KR100609771 B1 KR 100609771B1
- Authority
- KR
- South Korea
- Prior art keywords
- weight
- water
- acrylic resin
- catalyst
- soluble acrylic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 29
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 29
- 239000011230 binding agent Substances 0.000 title claims abstract description 23
- 239000000203 mixture Substances 0.000 title claims abstract description 15
- 239000011491 glass wool Substances 0.000 title claims abstract description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 24
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 239000004593 Epoxy Substances 0.000 claims abstract description 11
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims abstract description 11
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000077 silane Inorganic materials 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 9
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 9
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 8
- 150000007530 organic bases Chemical class 0.000 claims abstract description 8
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 15
- 239000013522 chelant Substances 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 7
- -1 carbonate polyol Chemical class 0.000 claims description 7
- 229960002887 deanol Drugs 0.000 claims description 7
- 239000012972 dimethylethanolamine Substances 0.000 claims description 7
- 229920005862 polyol Polymers 0.000 claims description 7
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical group CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 7
- IHEDBVUTTQXGSJ-UHFFFAOYSA-M 2-[bis(2-oxidoethyl)amino]ethanolate;titanium(4+);hydroxide Chemical compound [OH-].[Ti+4].[O-]CCN(CC[O-])CC[O-] IHEDBVUTTQXGSJ-UHFFFAOYSA-M 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 5
- 150000003077 polyols Chemical class 0.000 claims description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- 229940058015 1,3-butylene glycol Drugs 0.000 claims description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 claims description 2
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 claims description 2
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims description 2
- PAITUROHVRNCEN-UHFFFAOYSA-J 2-hydroxyacetate;zirconium(4+) Chemical compound [Zr+4].OCC([O-])=O.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O PAITUROHVRNCEN-UHFFFAOYSA-J 0.000 claims description 2
- LYPJRFIBDHNQLY-UHFFFAOYSA-J 2-hydroxypropanoate;zirconium(4+) Chemical compound [Zr+4].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O LYPJRFIBDHNQLY-UHFFFAOYSA-J 0.000 claims description 2
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 2
- DBXBTMSZEOQQDU-UHFFFAOYSA-M 3-hydroxyisobutyrate Chemical compound OCC(C)C([O-])=O DBXBTMSZEOQQDU-UHFFFAOYSA-M 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000002577 cryoprotective agent Substances 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 claims description 2
- 239000002270 dispersing agent Substances 0.000 claims description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 2
- 229960005082 etohexadiol Drugs 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 2
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 239000003755 preservative agent Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 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 description 2
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- 125000005595 acetylacetonate group Chemical group 0.000 claims 1
- 239000002518 antifoaming agent Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 229910052808 lithium carbonate Inorganic materials 0.000 claims 1
- 239000011810 insulating material Substances 0.000 abstract description 8
- 229920000877 Melamine resin Polymers 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 238000000935 solvent evaporation Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000011521 glass Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 8
- 238000007906 compression Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 3
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000011358 absorbing material Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 238000002156 mixing Methods 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 238000007348 radical reaction Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
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- 238000005728 strengthening Methods 0.000 description 2
- 208000024891 symptom Diseases 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- SPQMVUPFYWDFCB-UHFFFAOYSA-N 2-hydroperoxybutane Chemical compound CCC(C)OO SPQMVUPFYWDFCB-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- PMNLUUOXGOOLSP-UHFFFAOYSA-N 2-mercaptopropanoic acid Chemical class CC(S)C(O)=O PMNLUUOXGOOLSP-UHFFFAOYSA-N 0.000 description 1
- CUTWSDAQYCQTGD-UHFFFAOYSA-N 2-prop-2-enoyloxypropanoic acid Chemical compound OC(=O)C(C)OC(=O)C=C CUTWSDAQYCQTGD-UHFFFAOYSA-N 0.000 description 1
- XNXIYYFOYIUJIW-UHFFFAOYSA-N 3-methylbutylbenzene Chemical compound CC(C)CCC1=CC=CC=C1 XNXIYYFOYIUJIW-UHFFFAOYSA-N 0.000 description 1
- JTHZUSWLNCPZLX-UHFFFAOYSA-N 6-fluoro-3-methyl-2h-indazole Chemical compound FC1=CC=C2C(C)=NNC2=C1 JTHZUSWLNCPZLX-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical group OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 206010035664 Pneumonia Diseases 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 208000005279 Status Asthmaticus Diseases 0.000 description 1
- 206010043521 Throat irritation Diseases 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
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- 125000003700 epoxy group Chemical group 0.000 description 1
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- 239000003063 flame retardant Substances 0.000 description 1
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- 238000001879 gelation Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
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- PZDUWXKXFAIFOR-UHFFFAOYSA-N hexadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C=C PZDUWXKXFAIFOR-UHFFFAOYSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
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- FGGJBCRKSVGDPO-UHFFFAOYSA-N hydroperoxycyclohexane Chemical compound OOC1CCCCC1 FGGJBCRKSVGDPO-UHFFFAOYSA-N 0.000 description 1
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- 229920000126 latex Polymers 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
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- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
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- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 1
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- NKHAVTQWNUWKEO-NSCUHMNNSA-N monomethyl fumarate Chemical compound COC(=O)\C=C\C(O)=O NKHAVTQWNUWKEO-NSCUHMNNSA-N 0.000 description 1
- 229940005650 monomethyl fumarate Drugs 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- BESWQAXCVAOXFV-UHFFFAOYSA-N octyl hydroperoxide Chemical compound CCCCCCCCOO BESWQAXCVAOXFV-UHFFFAOYSA-N 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 230000002685 pulmonary effect Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000033764 rhythmic process Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
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- 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
- C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- 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
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- 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
- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
- C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
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- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
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- 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
- C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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Abstract
본 발명은 유리면등 불연단열재에 적용되는, 포름알데히드를 함유하지 않는 수용성 아크릴 수지 및 이를 포함하는 유리면 바인더용 경화 조성물에 관한 것이다. 본 발명에 따른 아크릴 수지는 a) 제 1 단계에서, 총 단량체에 대해 분자내에 카르복실산기를 함유하는 단량체 또는 그의 유도체를 수용액중에서 중합개시제의 존재하에 반응시켜 아크릴 중합체를 제조하고, b) 제 2 단계에서, 제 1 단계에서 수득한 아크릴 중합체를 무기 및 유기 염기중에서 선택된 1종 이상의 중화제의 존재하에 티타네이트계 촉매 및 지르코네이트계 촉매중에서 선택된 1종 이상의 촉매를 사용하여 에폭시 실란 또는 아미노 실란과 반응시켜 제조된 것으로 무독성이며, 특히 수용성으로 휘발성 유기 용제를 포함하지 않아 코팅시에 용제 증발에 의한 환경 오염을 일으키지 않으며 멜라민-포름알데히드 수지보다 더 안정한 불연단열재 바인더로서 사용될 수 있다.The present invention relates to a water-soluble acrylic resin containing no formaldehyde and a curable composition for a glass wool binder comprising the same, which is applied to a non-combustible heat insulating material such as glass wool. The acrylic resin according to the present invention comprises a) preparing an acrylic polymer in a first step by reacting a monomer or a derivative thereof containing a carboxylic acid group in a molecule with respect to the total monomers in the presence of a polymerization initiator in an aqueous solution, b) a second In the step, the acrylic polymer obtained in the first step is combined with epoxy silane or amino silane using at least one catalyst selected from titanate catalyst and zirconate catalyst in the presence of at least one neutralizing agent selected from inorganic and organic bases. It is prepared by reacting and is non-toxic, and especially water-soluble, it does not contain a volatile organic solvent, does not cause environmental pollution by solvent evaporation at the time of coating and can be used as a non-insulating material binder more stable than melamine-formaldehyde resin.
Description
본 발명은 포름알데히드를 함유하지 않는, 불연단열재에 적용되는 열 경화성 수용성 아크릴 수지 및 이를 함유하는 유리면 바인더 조성물에 관한 것이다. 더욱 상세하게는, 본 발명은 a) 제 1 단계에서, 총 단량체에 대해 분자내에 카르복실산기를 함유하는 단량체 또는 그의 유도체를 수용액중에서 중합개시제의 존재하에 반응시켜 아크릴 중합체를 제조하고, b) 제 2 단계에서, 제 1 단계에서 수득한 아크릴 중합체를 무기 및 유기 염기중에서 선택된 1종 이상의 중화제의 존재하에 티타네이트계 촉매 및 지르코네이트계 촉매중에서 선택된 1종 이상의 촉매를 사용하여 에폭시 실란 또는 아미노 실란과 반응시켜 제조된 수용성 아크릴 수지 및 이를 함유하는 유리면 바인더 조성물에 관한 것이다.The present invention relates to a thermosetting water-soluble acrylic resin to be applied to a non-combustible heat insulating material that does not contain formaldehyde and a glass wool binder composition containing the same. More specifically, the present invention provides a method for preparing an acrylic polymer by a) reacting a monomer or a derivative thereof containing a carboxylic acid group in a molecule with respect to the total monomers in the first step in the presence of a polymerization initiator in an aqueous solution, and b) In the second step, the acrylic polymer obtained in the first step is epoxy silane or amino silane using at least one catalyst selected from titanate catalyst and zirconate catalyst in the presence of at least one neutralizing agent selected from inorganic and organic bases. It relates to a water-soluble acrylic resin prepared by reaction with and a glass wool binder composition containing the same.
불연단열재로 사용중인 유리면은 고온에서 저온으로 흘러가는 열의 흐름을 억제시키기 위해 사용되는 재료로서 상온에서의 열전도율이 대략 0.1 Kcal/mh℃ 이 하인 단열재이다. 이는 규사외 6종의 유리 원료를 고온에서 용융시켜 고속 회전력을 이용해서 섬유화하고 일정한 형태로 성형한 인조광물섬유(Man Made Mineral Fiber: MMMF)로 미세한 섬유가 연속 기공을 형성하고 있어 보온, 단열, 흡음재로 사용되는 제품으로 섬유화된 제품에 열경화성 수지를 분사하여 매트 또는 보드의 형태로 성형 제조한 보온, 단열 및 흡음재이다.The glass surface used as the non-combustible insulation is a material used to suppress the flow of heat flowing from high temperature to low temperature, and is a heat insulating material having a thermal conductivity of about 0.1 Kcal / mh ° C or lower. It is a man-made mineral fiber (MMMF) made by melting six kinds of glass raw materials other than silica sand at high temperature to make fibers using high-speed rotational force and forming them in a uniform shape. It is a product used as sound absorbing material. It is a thermal insulation, heat insulation and sound absorbing material which is manufactured by forming a mat or board by spraying a thermosetting resin on a fiberized product.
불연단열재에 적용되는 바인더는 유리섬유등의 휨성이나 처짐성등을 막아주는 역할을 하며 제품의 인장강도도 증가시켜 주는 역할을 한다. 또한 대부분의 유리섬유는 고온에서 매트 또는 보드화 형태로 제조되므로 사용되는 바인더 역시 열에 강한 특성을 지녀야 한다.Binder applied to non-combustible insulation prevents warpage and deflection of glass fiber and increases tensile strength of products. In addition, since most glass fibers are manufactured in a mat or board form at a high temperature, the binder used must also be heat resistant.
종래의 기술을 살펴보면, 기존에 유리면등의 불연단열재의 집면 및 매트화시 사용되는 바인더로는 멜라민-포름알데히드 수지가 통상적으로 사용되어왔다. 그러나 이러한 멜라민-포름알데히드 수지는 유리면에 스프레이시 공기중에 포름알데히드를 유출시켜 작업 환경을 악화시키고 건조 경화시 상당한 양의 포름알데히드가 발생되어 증기형태로 대기중에 배출되는 단점이 있다. 또한 경화시 발생되는 포름알데히드가 유리면 내부에 남아 있어 시공 후 시간이 경과함에 따라 서서히 방출되어 실내 공기중에 유출되어 사람이 흡입하면 새집증후군을 일으키는 주요 원인이 되기도 하여 바람직하지 않다.Looking at the prior art, melamine-formaldehyde resin has been conventionally used as a binder used when collecting and matting non-combustible insulation such as glass. However, such a melamine-formaldehyde resin has a disadvantage in that formaldehyde in the air when sprayed on the glass surface to deteriorate the working environment and a significant amount of formaldehyde is generated in the dry hardening to be discharged to the atmosphere in the form of steam. In addition, formaldehyde, which is generated during curing, remains inside the glass surface and is gradually released as time passes after construction, and is discharged into the indoor air.
현대인의 경우 인공적 환경인 건축물의 실내에서 생활하는 시간이 전체의 80% 이상이어서 포름알데히드가 제거 또는 희석되지 못하고 실내에 점차적으로 누적될 경우 재실자의 건강에 직접적으로 큰 영향을 미칠 수 있음에도 불구하고 근래 까지는 실내 공기 환경의 중요성이 낮게 평가되어 그에 대한 대책이 별로 없었던 게 사실이다Although modern people spend more than 80% of the time living in the interior of artificial buildings, formaldehyde can not be removed or diluted and gradually accumulates in the room. Until now, the importance of the indoor air environment was underestimated, and there was little countermeasure.
포름알데히드에서 발생하는 냄새는 일반적으로 1ppm에서 느끼게 되지만 0.05ppm의 농도에서부터 감지하는 사람도 있다. 1980년 12월에 미국 국립노동안전위생연구소(NIOSH)와 산업안전국(OSHA)은 포름알데히드는 노동위생상의 발암물질로서 취급되어야 한다고 권고했다. 보통 포름알데히드의 농도가 1ppm 이하인 경우에는 눈, 코 또는 목의 자극이나, 상부 기도등에서 이상 증상을 나타내고, 5ppm이하에서는 천식 환자에게 심한 천식 발작을 일으킨다. 또한 20ppm 이하에서는 기침, 폐의 압박, 머리의 무거움 또는 심장 박동이 빨라지는 등의 증상을 호소하게 되며, 100ppm 이하의 고농도에서는 폐체액의 집적이나, 폐염증의 증상을 호소하고 심한 경우에는 사망에 이르게 될 수 있다.Odors from formaldehyde are usually felt at 1 ppm, but some people detect them at concentrations of 0.05 ppm. In December 1980, the National Institutes of Health and Human Services (NIOSH) and OSHA recommended that formaldehyde should be treated as a carcinogen in labor hygiene. When the concentration of formaldehyde is usually 1 ppm or less, abnormal symptoms occur in eye, nose or throat irritation or upper airway, and below 5 ppm causes severe asthma attacks in asthmatic patients. Also, less than 20ppm complains of coughing, lung pressure, heaviness in the head, or heart rhythm, etc. At high concentrations of 100ppm or less, it complains of accumulation of pulmonary fluid or symptoms of pulmonary inflammation. Can lead to.
이런 차원에서 주요선진국의 실내공기질에 대한 관리는 정부내 관련부처 및 민간단체에한 법적 규제 및 관리가 강화되고 있는 추세이며 이것에 발 맞추어 세계적으로 포름알데히드 대응 제품 개발이 활발하게 이루어지고 있다In this regard, the management of indoor air quality in major industrialized countries is strengthening legal regulation and management of relevant ministries and private organizations in the government, and accordingly, formaldehyde-adaptive products are being actively developed worldwide.
현재, 폴리올 및 다가산을 인산계 촉매하에서 반응시키는 에스테르 반응을 통한 제조방법(미국 특허 제 4693847호), 포화, 불포화, 방향족산등을 포함한 다가산과 인을 함유한 촉매를 사용하여 제조하는 방법(미국 특허 제 4,820,307호; 4,936,865호; 및 4,975,209호), 불포화 카르복실산 또는 그 혼합물을 사용하여 폴리머를 제조하고 중화제로써 하이드록실기를 함유한 폴리올 및 포스포늄 촉매를 이용하여 제조하는 방법(미국 특허 제 5318990호), 불포화 카르복실산 또는 그 혼합 물을 사용하여 폴리머를 제조하고 중화제로써 하이드록실기를 함유한 폴리올 및 포스포늄 촉매를 이용하여 제조하고 pH조절제로 무기산을 사용하는 방법(미국 특허 제 6331350호)이 주로 이용되고 있다. 이런한 방법들은 포름알데히드를 방출하지는 않으나 경화성이 느려 가교밀도를 저하시키고 제품의 강도 및 내수성이 저하되는 문제점이 있다.At present, a process for preparing polyol and polyacid by ester reaction for reacting with phosphoric acid-based catalyst (US Pat. No. 46,93,847), a process for preparing using a catalyst containing polyacid and phosphorus including saturated, unsaturated, aromatic acid, etc. US Pat. Nos. 4,820,307; 4,936,865; and 4,975,209), methods of preparing polymers using unsaturated carboxylic acids or mixtures thereof and using polyols and phosphonium catalysts containing hydroxyl groups as neutralizing agents (US patents). 5318990), a process for preparing polymers using unsaturated carboxylic acids or mixtures thereof, using polyols and phosphonium catalysts containing hydroxyl groups as neutralizing agents and using inorganic acids as pH adjusting agents (US Pat. 6331350) is mainly used. These methods do not emit formaldehyde, but have a problem in that the curing property is slow, thereby lowering the crosslinking density and lowering the strength and water resistance of the product.
본 발명자들은 상기와 같은 문제점을 지닌 포름알데히드의 유출을 없애고 불연단열재의 물성을 개선시킬 수 있는 바인더로써 무포름알데히드 수용성 아크릴 수지를 개발하기 위하여 연구에 연구를 거듭한 결과 분자내에 카르복실산기를 함유하는 단량체를 수용성 개시제에 의한 라디칼 반응으로 수용액중에서 용액 중합하여 수득한 수용성 아크릴 중합체가 접착력, 압축강도 및 난연성능이 우수하고, 무독성이며, 특히 수용성으로 휘발성 유기 용제를 포함하지 않아 코팅시에 용제 증발에 의한 환경 오염을 일으키지 않으며 멜라민-포름알데히드 수지보다도 안정한 불연단열재 바인더로 사용될 수 있음을 밝혀내고 본 발명을 완성하게 되었다.The present inventors have conducted research to develop a formaldehyde-free water-soluble acrylic resin as a binder that can eliminate the outflow of formaldehyde having the above problems and improve the properties of the incombustible insulation, and contains a carboxylic acid group in the molecule. The water-soluble acrylic polymer obtained by solution polymerization of a monomer in an aqueous solution by radical reaction with a water-soluble initiator is excellent in adhesive strength, compressive strength and flame retardancy, is non-toxic, and especially water-soluble, does not contain a volatile organic solvent and evaporates the solvent during coating. The present invention was completed by finding out that it can be used as a non-insulating material binder which is more stable than melamine-formaldehyde resin without causing environmental pollution.
따라서, 본 발명의 목적은 Therefore, the object of the present invention
a) 제 1 단계에서, 총 단량체에 대해 분자내에 카르복실산기를 함유하는 단량체 또는 그의 유도체를 수용액중에서 중합개시제의 존재하에 반응시켜 아크릴 중합체를 제조하고,a) in the first step, a monomer or derivative thereof containing a carboxylic acid group in the molecule relative to the total monomer is reacted in the presence of a polymerization initiator in an aqueous solution to prepare an acrylic polymer,
b) 제 2 단계에서, 제 1 단계에서 수득한 아크릴 중합체를 무기 및 유기 염기중에서 선택된 1종 이상의 중화제의 존재하에 티타네이트계 촉매 및 지르코네이 트계 촉매중에서 선택된 1종 이상의 촉매를 사용하여 에폭시 실란 또는 아미노 실란과 반응시켜 수용성 아크릴 수지를 제공하는데 있다.b) In the second step, the acrylic polymer obtained in the first step is epoxy silane or at least one catalyst selected from titanate catalyst and zirconate catalyst in the presence of at least one neutralizing agent selected from inorganic and organic bases. It is reacted with amino silane to provide a water-soluble acrylic resin.
본 발명의 또 다른 목적은 상기 제조방법에 의해 제조된 아크릴 중합체 10 ∼30 중량%, 방진유를 포함한 기타 첨가제 1 ~ 3중량% 및 배합수 70 ~ 85중량%를 함유하는 불연단열재용 유리면 바인더 조성물을 제공하는 것이다.Still another object of the present invention is a glass wool binder composition for a non-combustible insulating material containing 10 to 30% by weight of the acrylic polymer prepared by the above method, 1 to 3% by weight of other additives including dustproof oil and 70 to 85% by weight of the blended water. To provide.
본 발명의 목적은The object of the present invention
a) 제 1 단계에서, 총 단량체에 대해 분자내에 카르복실산기를 함유하는 단량체 또는 그의 유도체를 수용액중에서 중합개시제의 존재하에 반응시켜 아크릴 중합체를 제조하고,a) in the first step, a monomer or derivative thereof containing a carboxylic acid group in the molecule relative to the total monomer is reacted in the presence of a polymerization initiator in an aqueous solution to prepare an acrylic polymer,
b) 제 2 단계에서, 제 1 단계에서 수득한 아크릴 중합체를 무기 및 유기 염기중에서 선택된 1종 이상의 중화제의 존재하에 티타네이트계 촉매 및 지르코네이트계 촉매중에서 선택된 1종 이상의 촉매를 사용하여 에폭시 실란 또는 아미노 실란과 반응시켜 수용성 아크릴 수지를 제조함으로써 달성된다.b) In the second step, the epoxy silane is obtained by using the acrylic polymer obtained in the first step using at least one catalyst selected from titanate catalyst and zirconate catalyst in the presence of at least one neutralizing agent selected from inorganic and organic bases. Or by reacting with amino silane to produce a water soluble acrylic resin.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명에서 분자내에 카르복실산기를 함유하는 단량체 또는 그의 유도체는 불포화 이중결합을 포함하는 카르복실산 및 그의 무수물, 예를 들어 아크릴산, 메타크릴산, 비닐벤젠산, 이소펜틸 벤젠산, 크로톤산, 이타콘산, 말레산, 무수 말레산, 푸마르산, 아크릴옥시프로피온산, 메타크릴옥시프로피온산, 아크릴옥사아세트산, 메타크릴 무수물, 메타크릴옥시아세트산, 모노메틸산말레이트, 모노메틸산 이 타코네이트 및 모노메틸푸마레이트중에서 선택된 1종 이상을 사용할 수 있다. 이들의 함량은 총단량체 100중량부에 대해 50~100중량부로 사용된다. 50 중량부 미만으로 사용되면 경화속도 및 가교밀도가 저하되어 충분한 경화가 이루어지지않아 미경화될 소지가 있으며 내수성이 저하될 소지가 있다.In the present invention, a monomer containing a carboxylic acid group or a derivative thereof in the molecule includes carboxylic acids and anhydrides thereof including unsaturated double bonds such as acrylic acid, methacrylic acid, vinylbenzene acid, isopentyl benzene acid, crotonic acid, Itaconic acid, maleic acid, maleic anhydride, fumaric acid, acryloxypropionic acid, methacrylicoxypropionic acid, acryloxaacetic acid, methacrylic anhydride, methacrylicoxyacetic acid, monomethyl acid malate, monomethyl acid itaconate and monomethyl fumarate One or more selected from among them can be used. Their content is used in 50 to 100 parts by weight based on 100 parts by weight of total monomers. If it is used less than 50 parts by weight, the curing rate and crosslinking density is lowered, there is a possibility that not enough curing is made, there is a possibility that the uncured and the water resistance is lowered.
본 발명의 제 1 단계에서 중합시 사용되는 중합 개시제로는 암모늄이나 금속 퍼설페이트, 또는 퍼옥시드, 예를 들어 암모늄퍼설페이트, 소듐퍼설페이트, 포타슘퍼설페이트, 시클로헥실 하이드로퍼옥시드, 큐멘 하이드로퍼옥시드, n-옥틸 하이드로퍼옥시드, t-부틸 하이드로퍼옥시드, sec-부틸 하이드로퍼옥시드 및 1-페닐-2-메틸프로필 1-하이드로퍼옥시드중에서 선택된 1종 이상과 같은 라디칼 중합이 가능한 수용성 개시제를 사용할 수 있다. 중합 개시제의 종류는 반응온도에 맞게 적절하게 선정할 수 있고, 중합 개시제의 사용량은 분자량에 미치는 영향을 고려하여 적정량을 사용한다. 보통 용액중합에서 중합개시제의 사용량은 사용한 총단량체 100중량부에 대해서 0.5~15 중량부를 사용할 수 있으며, 바람직하게는 1~10 중량부 범위에서 사용할 수 있다. 0.5 중량부 미만으로 사용되면 반응속도가 저하되고 분자량이 너무 거대화될 수 있으며, 15 중량부를 초과하여 사용하면 분자량 및 점도가 너무 낮아져 강도 및 복원력이 저하되는 단점이 있다.The polymerization initiator used in the polymerization in the first step of the present invention is ammonium or metal persulfate, or peroxide, for example ammonium persulfate, sodium persulfate, potassium persulfate, cyclohexyl hydroperoxide, cumene hydroper Radical polymerization such as at least one selected from oxide, n-octyl hydroperoxide, t-butyl hydroperoxide, sec-butyl hydroperoxide and 1-phenyl-2-methylpropyl 1-hydroperoxide This possible water-soluble initiator can be used. The kind of polymerization initiator can be suitably selected according to reaction temperature, and the usage-amount of a polymerization initiator uses an appropriate amount in consideration of the effect on molecular weight. Usually, the amount of the polymerization initiator used in the solution polymerization may be 0.5 to 15 parts by weight based on 100 parts by weight of the total monomer used, preferably in the range of 1 to 10 parts by weight. When used in less than 0.5 parts by weight the reaction rate is lowered and the molecular weight may be too large, when used in excess of 15 parts by weight there is a disadvantage that the molecular weight and viscosity is too low to lower the strength and resilience.
본 발명의 제 1 단계에 사용되는 용액은 유기용제가 아닌 물을 사용한다. 용액중합의 반응온도는 분자량에 관계가 있으므로 분자량에 맞게 선정할 수 있으며, 단량체 및 개시제에 따라 변화될 수 있지만, 보통 80~100℃에서 실시할 수 있다. 또한 반응열의 조절에 따라 분자량의 변화가 생기므로 반응물의 양에 따라 중 합시간은 일반적으로 약 30분~8시간 범위이며, 바람직하게는 3~4시간이 적당하다.The solution used in the first step of the present invention uses water, not an organic solvent. Since the reaction temperature of the solution polymerization is related to the molecular weight, it may be selected according to the molecular weight, and may be changed depending on the monomer and the initiator, but it may be usually performed at 80 to 100 ° C. In addition, since the change in the molecular weight occurs according to the control of the reaction heat, the polymerization time is generally in the range of about 30 minutes to 8 hours, preferably 3 to 4 hours, depending on the amount of the reactants.
본 발명의 제 1 단계에서, 총단량체에 대해 모노에틸렌계 불포화 단량체 1 내지 50 중량부를 추가로 사용하는 것이 바람직하다.In the first step of the invention, it is preferred to further use 1 to 50 parts by weight of monoethylenically unsaturated monomer relative to the total monomers.
본 발명에 따른 모노에틸렌계 불포화 단량체는 아릴, 카복실산, 할로겐, 시아노, 아미노카보닐 및 알킬로 구성된 그룹중에서 선택된 하나 이상의 치환체에 의해 치환되거나 비치환된 에틸렌; 부틸렌; 비닐기를 가지는 설폰산; 비닐기를 가지는 아세트아미드; 하이드록시-치환되거나 비치환된 알킬 또는 알콕시-치환되거나 비치환된 폴리에틸렌글리콜에 의해 치환되거나 비치환된 (메트)아크릴레이트, 예를 들어 스티렌, 비닐 톨루엔, 에틸렌, 비닐 아세테이트, 염화비닐, 염화비닐리덴, 아크릴로니트릴, 아크릴아미드, 메타크릴아미드, 메틸아크릴레이트, 메틸메타크릴레이트, 에틸아크릴레이트, 에틸메타크릴레이트, 부틸아크릴레이트, 부틸메타크릴레이트, 2-에틸헥실아크릴레이트, 2-에틸헥실메타크릴레이트, 벤질아크릴레이트, 벤질메타크릴레이트, 라우릴아크릴레이트, 라우릴메타크릴레이트, 팔미틸아크릴레이트, 팔미틸메타크릴레이트, 스테아릴아크릴레이트, 스테아릴메타크릴레이트, 모노메틸푸마레이트, 비닐설폰산, 아크릴옥시알칸설폰산, N-비닐아세트아미드, 2-하이드록시에틸(메트)아크릴레이트, 메톡시폴리에틸렌글리콜 (메트)아크릴레이트, 폴리에틸렌글리콜 (메트)아크릴레이트 및 이소부틸렌중에서 선택된 1종 이상을 사용할 수 있다. 이들은 총단량체 100중량부에 대해 1~50중량부로 사용할 수 있다. 1 중량부 미만으로 사용하면 강도가 저하되는 문제가 있고, 50 중량부를 초과하여 사용하면 제품의 강도가 너무 높아져 쉽게 부서지는 단점이 있다.Monoethylenically unsaturated monomers according to the present invention include ethylene unsubstituted or substituted by one or more substituents selected from the group consisting of aryl, carboxylic acid, halogen, cyano, aminocarbonyl and alkyl; Butylene; Sulfonic acid having a vinyl group; Acetamide having a vinyl group; (Meth) acrylates unsubstituted or substituted by hydroxy-substituted or unsubstituted alkyl or alkoxy-substituted or unsubstituted polyethylene glycols, for example styrene, vinyl toluene, ethylene, vinyl acetate, vinyl chloride, vinyl chloride Leadene, acrylonitrile, acrylamide, methacrylamide, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethyl Hexyl methacrylate, benzyl acrylate, benzyl methacrylate, lauryl acrylate, lauryl methacrylate, palmityl acrylate, palmityl methacrylate, stearyl acrylate, stearyl methacrylate, monomethyl fumar Latex, vinylsulfonic acid, acryloxyalkanesulfonic acid, N-vinylacetamide, 2-hydroxyethyl (meth) acrylate Or at least one selected from methoxy polyethylene glycol (meth) acrylate, polyethylene glycol (meth) acrylate and isobutylene can be used. These can be used in 1-50 weight part with respect to 100 weight part of total monomers. If the amount is less than 1 part by weight, there is a problem that the strength is lowered. If the amount is used more than 50 parts by weight, the strength of the product is too high, which is easily broken.
본 발명의 아크릴 수지는 분자량조절을 위해 분자량 조절제를 사용할 수 있으며, 사용가능한 분자량 조절제로는 머캅탄, 폴리머캅탄 및 할로겐 화합물류 중에서 선택하며, 그 예로 알킬머캅탄 및 머캅토 프로피온산중에서 선택된 1종 이상을 사용할 수 있다. 그 사용량은 총단량체 100중량부에 대하여 1 ~ 10중량부 범위내이며, 1중량부 미만으로 사용할시에는 수지의 분자량이 너무 거대해져 겔화의 위험이 있고, 10중량부를 초과하여 사용할 시에는 분자량이 작아져 제품의 강도를 저하시킬 수 있다.The acrylic resin of the present invention may use a molecular weight regulator to control the molecular weight, and usable molecular weight regulators are selected from mercaptans, polymercaptans and halogen compounds, for example, at least one selected from alkylmercaptans and mercapto propionic acids. Can be used. The amount of use is in the range of 1 to 10 parts by weight based on 100 parts by weight of the total monomer, and when used at less than 1 part by weight, the molecular weight of the resin becomes too large, and there is a risk of gelation. It becomes small and can lower the intensity | strength of a product.
제 1 단계에서 제조된 아크릴 중합체의 수평균 분자량은 1,000 ∼ 10,000이며, 고형분은 30 ~ 70중량%인 것이 바람직하다.The number average molecular weight of the acrylic polymer prepared in the first step is 1,000 to 10,000, and the solid content is preferably 30 to 70% by weight.
수평균 분자량이 10,000을 초과하면 제품의 경화성은 좋아지나 부서지는 단점이 있으며, 고형분이 30중량%이하이면 강도 및 복원력이 저하될 우려가 있고 70중량%이상이면 제품의 유리면 분사시 분사가 불가능하며 부서지는 단점이 있다.If the number average molecular weight exceeds 10,000, the curability of the product is improved, but it has a disadvantage of breaking.If the solid content is less than 30% by weight, the strength and the restoring force may be lowered. There is a disadvantage of being broken.
제 2 단계는 제 1 단계에서 수득한 아크릴 중합체를 무기 및 유기 염기중에서 선택된 1종 이상의 중화제의 존재하에 티타네이트계 촉매 및 지르코네이트계 촉매중에서 선택된 1종 이상의 촉매를 사용하여 에폭시 실란 또는 아미노 실란과 반응시시키는 단계이다.The second step is the epoxy silane or amino silane using the acrylic polymer obtained in the first step using at least one catalyst selected from titanate catalyst and zirconate catalyst in the presence of at least one neutralizing agent selected from inorganic and organic bases. It is a step of reacting with.
상기 1단계에서 제조한 아크릴 중합체 100중량부에 대해 에폭시 또는 아미노 실란 1종 이상을 3 ~ 15중량부, 유기 또는 무기 염기 중화제 1종 이상을 10 ∼ 80 중량부, 촉매로 티타네이트계 또는 지르코네이트계의 촉매를 필수성분으로 0.1 ~ 5중량부 혼합하여 pH를 3.0~7.0으로 조절한다. 이때 얻어진 최종 수지는 고형분 함량이 40 ~ 60중량%이고, 산가는 200 ~ 1000㎎KOH/g이며, 점도는 100 ~ 500cps인 것이 바람직하다. 산가가 200보다 낮을 경우 유리면 성분과 무기물 성분의 반응 정도가 낮아 결과적으로 강도의 저하가 생길 수 있으며, 1000보다 높을 경우 과량의 산이 무기물과 미반응하여 유리면에 존재하여 제품의 내습성을 저하시켜 고온다습시 처짐현상이 발생할 수 있다. 또한, 고형분이 40중량% 미만이면 강도 및 복원력이 저하될 우려가 있고, 60%를 초과하면 제품의 유리면 분사시 분사가 불가능하며 부서지는 단점이 있고, pH가 3.0미만일때는 반응성이 너무 빠르거나, 공정설비의 부식을 초래할 수 있고, pH가 7을 초과하면 반응성이 느려져 미경화가 발생하거나 유리면의 강도를 저하시킬 수 있다3 to 15 parts by weight of one or more epoxy or amino silanes, 10 to 80 parts by weight of one or more organic or inorganic base neutralizers, and a titanate-based or zirco catalyst based on 100 parts by weight of the acrylic polymer prepared in step 1 The pH is adjusted to 3.0 to 7.0 by mixing 0.1 to 5 parts by weight of the nate catalyst as essential components. The final resin thus obtained has a solid content of 40 to 60% by weight, an acid value of 200 to 1000 mgKOH / g, and a viscosity of 100 to 500 cps. If the acid value is lower than 200, the degree of reaction between the glass surface component and the inorganic component is low, resulting in a decrease in strength. If the acid value is higher than 1000, the excess acid is not reacted with the inorganic material and exists on the glass surface, thereby lowering the moisture resistance of the product. Deflection may occur during high humidity. In addition, if the solid content is less than 40% by weight, the strength and the restoring force may be lowered. If the solid content is more than 60%, the spraying of the glass surface of the product is impossible and there is a disadvantage in breaking, and when the pH is less than 3.0, the reactivity is too fast, Corrosion of the process equipment may occur, and if the pH exceeds 7, the reactivity may be slowed, resulting in uncured or reduced strength of the glass surface.
본 발명의 제 2 단계에서 사용한 에폭시실란 또는 아미노실란은 예를 들어 3-글리시독시프로필트리메톡시실란, 3-글리시독시프로필메틸디메톡시실란, 2-(3,4-에폭시사이클로헥실)에틸트리메톡시실란, 3-아미노프로필트리에톡시실란, N-(2-아미노에틸)-3-아미노프로필트리메톡시실란 및 N-(2-아미노에틸)-3-아미노프로필메틸디메톡시실란중에서 선택된 1종 이상을 사용하는 것이 바람직하다. 제 1 단계에서 제조된 아크릴 중합체 100중량부에 대해 3 ~ 15중량부 사용하는 것을 특징으로 한다. 사용량이 3 중량부 미만이면 제품의 강도저하 및 복원력이 저하되는 단점이 있고, 15 중량부를 초과하면 제품의 표면이 깨지기 쉬운 단점이 있다.Epoxysilanes or aminosilanes used in the second step of the invention are, for example, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane It is preferable to use one or more selected from among them. 3 to 15 parts by weight based on 100 parts by weight of the acrylic polymer prepared in the first step is used. If the amount is less than 3 parts by weight, there is a disadvantage in that the strength and restoring force of the product is lowered. If the amount is more than 15 parts by weight, the surface of the product is easily broken.
상기와 같이 에폭시 실란 또는 아미노 실란을 사용하게 되면, 에폭시 또는 아미노기는 아크릴 중합체와 반응하여 코팅막을 형성하게 되고, 실란은 물중에서 가수분해 후 유리면 표면의 OH기와 축합반응하여 제품과의 접착력을 부여하여 제품 의 압축 및 복원력을 향상시켜주며 강도를 증강시키는 역할을 한다.When the epoxy silane or the amino silane is used as described above, the epoxy or amino group reacts with the acrylic polymer to form a coating film, and the silane condensation reaction with the OH group on the surface of the glass surface after hydrolysis in water gives an adhesive force with the product. It improves the compression and resilience of the product and increases the strength.
본 발명의 제 2 단계에서 사용한 중화제인 무기 또는 유기 염기로는 모노-, 디-, 또는 트리-알킬 또는 알칸올아민, 예를 들어 모노에탄올아민, 디에탄올아민, 디에틸아미노에탄올, 암모니아, 트리메틸아민, 트리에틸아민, 트리프로필아민 및 디메틸에탄올아민; 헤테로사이클릭 화합물, 예를 들어 모르폴린; 암모니아; 알코올, 예를 들어 에틸렌 글리콜, 디에틸렌 글리콜, 프로필렌 글리콜, 네오 펜틸 글리콜, 1,3-부틸렌 글리콜, 1,4-부틸렌 글리콜, 1,6-헥산디올, 트리메틸올 프로판, 트리메틸올 에탄, 글리세린, 2-메틸-1,3-프로판 디올, 2-부틸-2-에틸-1,3-프로판디올, 카보네이트폴리올, 톤폴리올; 알킬에스테르, 예를 들어 3-하이드록시-2-메틸 프로파노에이트, 하이드록시알칸, 예를 들어 1,2,3-트리하이드록시프로판; 및 금속 수산화물, 예를 들어 수산화나트륨, 수산화칼륨, 수산화리튬 및 탄산나트륨중에서 선택된 1종 이상을 사용할 수 있다. 제 1 단계에서 제조된 아크릴 중합체 100중량부에 대해 10~80중량부 사용하는 것을 특징으로 한다. 사용량이 10 중량부 미만이면 가교밀도의 저하로 인장력 및 복원력이 저하되고 미경화될 소지가 있고, 80 중량부를 초과하면 난연성이 저하될 우려가 있다.Inorganic or organic bases that are neutralizers used in the second step of the invention include mono-, di-, or tri-alkyl or alkanolamines, for example monoethanolamine, diethanolamine, diethylaminoethanol, ammonia, trimethyl Amines, triethylamine, tripropylamine and dimethylethanolamine; Heterocyclic compounds such as morpholine; ammonia; Alcohols such as ethylene glycol, diethylene glycol, propylene glycol, neopentyl glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,6-hexanediol, trimethylol propane, trimethylol ethane, Glycerin, 2-methyl-1,3-propane diol, 2-butyl-2-ethyl-1,3-propanediol, carbonate polyols, ton polyols; Alkyl esters such as 3-hydroxy-2-methyl propanoate, hydroxyalkanes such as 1,2,3-trihydroxypropane; And metal hydroxides such as one or more selected from sodium hydroxide, potassium hydroxide, lithium hydroxide and sodium carbonate. It is characterized by using 10 to 80 parts by weight based on 100 parts by weight of the acrylic polymer prepared in the first step. If the amount is less than 10 parts by weight, the tensile strength and the restoring force may be lowered and uncured due to the decrease in the crosslinking density. If the amount is more than 80 parts by weight, the flame retardancy may be reduced.
본 발명의 제 2 단계에서 반응 촉매로는 티타네이트계 및 지르코네이트계촉매 1종 이상을 필수 성분으로 사용한다. 아세틸아세토네이트 티타네이트 킬레이트, 에틸 아세토아세테이트 티타네이트 킬레이트, 트리에탄올아민 티타네이트 킬레이트, 라틱산 티타네이트 킬레이트 암모니움염, 옥틸렌글리콜 티타네이트, 지르코늄 락테이트, 지르코늄 글리콜레이트 및 n-부틸 지르코네이트 화합물중에서 선택된 1 종 이상을 사용하는 것이 바람직하며, 제 1 단계에서 제조된 아크릴 중합체 100중량부에 대해 0.1 ~ 5중량부 사용하는 것을 특징으로 한다. 0.1중량부 미만 사용시에는 경화 속도가 늦어져 충분한 강도가 저하되고, 5중량부를 초과하여 사용시에는 강도는 증가하나 황변 현상이 나타날 수 있다.As the reaction catalyst in the second step of the present invention, one or more of titanate-based and zirconate-based catalysts are used as essential components. Among acetylacetonate titanate chelate, ethyl acetoacetate titanate chelate, triethanolamine titanate chelate, lactate titanate chelate ammonium salt, octylene glycol titanate, zirconium lactate, zirconium glycolate and n-butyl zirconate compounds It is preferable to use at least one selected, characterized in that 0.1 to 5 parts by weight based on 100 parts by weight of the acrylic polymer prepared in the first step. When the amount is less than 0.1 part by weight, the curing speed is slowed down, and the sufficient strength is lowered. When the amount is more than 5 parts by weight, the strength is increased but yellowing may occur.
제 2 단계에서 제조된 아크릴 수지는 중화도가 80% 미만이 바람직하며 80% 이상일 경우 무기물과 반응하는 산의 양이 감소하여 유리면의 강도에 영향을 미칠 수 있다.The acrylic resin prepared in the second step is preferably less than 80% of the degree of neutralization, when the 80% or more may reduce the amount of acid reacting with the inorganic material may affect the strength of the glass surface.
본 발명에 따른 바인더 조성물은 상기 제조방법에 의해 제조된 아크릴 수지 10 ∼30 중량%, 단열재의 비산 및 집면을 강화하는 방진유를 포함한 기타 첨가제 1 ~ 3중량% 및 배합수 70 ~ 85중량%를 함유한다.The binder composition according to the present invention comprises 10 to 30% by weight of the acrylic resin prepared by the above production method, 1 to 3% by weight of other additives including dustproof oil for strengthening the scattering and collection of the insulating material and 70 to 85% by weight of the blended water. It contains.
상기 기타 첨가제로는 소포제, 방부제, 분산제, 안정제, 동결방지제 및 습윤침투제 중에서 선택된 1종 이상을 포함할 수 있다.The other additives may include at least one selected from antifoams, preservatives, dispersants, stabilizers, cryoprotectants and wet penetrants.
이하 실시예 및 비교예를 통하여 본 발명을 좀더 구체적으로 설명하겠는 바, 하기 실시예들이 본 발명의 범주를 한정하는 것은 아니다. Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, which are not intended to limit the scope of the present invention.
실시예 1: 수용성 아크릴 중합체의 제조Example 1: Preparation of Water-Soluble Acrylic Polymer
온도계가 장치된 5L 4구 플라스크에 이온수 609.74g를 투입하고 온도를 85℃로 승온한다. 85℃로 유지되면 질소를 5분간 사입하여 반응부를 질소 분위기로 한 후 질소를 제거한다. 암모늄퍼설페이트 47.2g을 반응기에 사입하고 30분간 숙성한다. 아크릴산 413.4g, 머캅토 프로피온산 9g을 180분간 적하한 후 1시간 유지한다. 반응이 완료되면 40℃로 냉각하고 디메틸에탄올아민 수용액 640g, 3-글리시독시프로필트리메톡시실란 50g, 트리에탄올아민 티타네이트 킬레이트 9g을 적하하여 pH를 3.0~7.0으로 조절한다. 최종적으로 제조된 수용성 아크릴 수지의 고형분은 44.1중량%이고 pH 4.7, 산가 270, 점도는 200cps이다.Into a 5 L four-necked flask equipped with a thermometer, 609.74 g of ionized water was added and the temperature was raised to 85 ° C. When the temperature is maintained at 85 ° C., nitrogen is injected for 5 minutes, the reaction part is placed in a nitrogen atmosphere, and nitrogen is removed. 47.2 g of ammonium persulfate are introduced into the reactor and aged for 30 minutes. 413.4 g of acrylic acid and 9 g of mercapto propionic acid are added dropwise for 180 minutes, and then maintained for 1 hour. After the reaction was completed, the mixture was cooled to 40 ° C, and 640 g of dimethylethanolamine aqueous solution, 50 g of 3-glycidoxypropyltrimethoxysilane, and 9 g of triethanolamine titanate chelate were added dropwise to adjust the pH to 3.0 to 7.0. Finally, the prepared water-soluble acrylic resin has a solid content of 44.1% by weight, a pH of 4.7, an acid value of 270, and a viscosity of 200 cps.
실시예 2: 수용성 아크릴 중합체의 제조Example 2: Preparation of Water-Soluble Acrylic Polymer
이온수 741g를 투입하고 85℃로 유지되면 암모늄퍼설페이트 60g을 반응기에 사입하고 30분간 숙성한다. 아크릴산 402.4g, 메틸메타크릴레이트 86.2g, 부틸아크릴레이트 86g, 머캅토 프로피온산 12g을 180분간 적하한 후 1시간 유지한다. 반응이 완료되면 40℃로 냉각하고 디메틸에탄올아민 수용액 789g, 3-글리시독시프로필트리메톡시실란 100g, 트리에탄올아민 티타네이트 킬레이트 촉매 12g을 적하하여 pH를 3.0~7.0으로 조절한다. 최종적으로 제조된 수용성 아크릴 수지의 고형분은 45.4중량%이고 pH 4.5, 산가 230, 점도는 250cps이다.After adding 741 g of ionized water and maintaining at 85 ° C., 60 g of ammonium persulfate was introduced into the reactor and aged for 30 minutes. 402.4 g of acrylic acid, 86.2 g of methyl methacrylate, 86 g of butyl acrylate, and 12 g of mercapto propionic acid are added dropwise for 180 minutes, and then maintained for 1 hour. After the reaction was completed, the mixture was cooled to 40 ° C, and 789 g of dimethylethanolamine aqueous solution, 100 g of 3-glycidoxypropyltrimethoxysilane and 12 g of triethanolamine titanate chelate catalyst were added dropwise to adjust the pH to 3.0 to 7.0. Finally, the prepared water-soluble acrylic resin has a solid content of 45.4% by weight, a pH of 4.5, an acid value of 230, and a viscosity of 250 cps.
실시예 3: 수용성 아크릴 중합체의 제조Example 3: Preparation of Water-Soluble Acrylic Polymer
이온수 700g를 투입하고 85℃로 유지되면 소듐퍼설페이트 61g을 반응기에 사입하고 30분간 숙성한후 아크릴산 400g, 메틸메타크릴레이트 68g, 2-에틸헥실아크릴레이트 30g, 머캅토 프로피온산 11g을 240분간 적하한 후 1시간 유지한다. 반응이 종료되면 40℃로 냉각하고 디메틸에탄올아민 수용액 754g, 3-글리시독시프로필트리메톡시실란 60g, 트리에탄올아민 티타네이트 킬레이트 11g을 적하하여 pH를 3.0~7.0으로 조절한다. 최종적으로 제조된 수용성 아크릴 수지의 고형분은 45.1중량%이고 pH 4.7, 산가 210, 점도는 320cps이다.When 700 g of ionized water was added and maintained at 85 ° C., 61 g of sodium persulfate was added to the reactor and aged for 30 minutes. 400 g of acrylic acid, 68 g of methyl methacrylate, 30 g of 2-ethylhexyl acrylate, and 11 g of mercaptopropionic acid were added dropwise for 240 minutes. After 1 hour. After the reaction was completed, the mixture was cooled to 40 ° C, and 754 g of dimethylethanolamine aqueous solution, 60 g of 3-glycidoxypropyltrimethoxysilane, and 11 g of triethanolamine titanate chelate were added dropwise to adjust the pH to 3.0 to 7.0. Finally, the prepared water-soluble acrylic resin has a solid content of 45.1 wt%, pH 4.7, an acid value of 210, and a viscosity of 320 cps.
실시예 4: 수용성 아크릴 중합체의 제조Example 4: Preparation of Water-Soluble Acrylic Polymer
이온수 581g를 투입하고 85℃로 유지되면 포타슘퍼설페이트 66g을 이온수 200g에 녹인 후 반응기에 사입하고 30분간 숙성한다. 아크릴산 480.4g, 부틸아크릴레이트 70g, 머캅토 프로피온산 13g을 180분간 적하한 후 1시간 유지한후 40℃로 냉각하고 트리에탄올아민 수용액 784g, 3-글리시독시프로필트리메톡시실란 98g, 트리에탄올아민 티타네이트 킬레이트 15g을 적하하여 pH를 3.0~7.0으로 조절한다. 최종적으로 제조된 수용성 아크릴 수지의 고형분은 44.8중량%이고 pH 4.3, 산가 270, 점도는 210cps이다.When 581 g of ionized water is added and maintained at 85 ° C., 66 g of potassium persulfate is dissolved in 200 g of ionized water, and then injected into the reactor and aged for 30 minutes. 480.4 g of acrylic acid, 70 g of butyl acrylate, 13 g of mercapto propionic acid were added dropwise for 180 minutes, held for 1 hour, cooled to 40 ° C., 784 g of aqueous triethanolamine solution, 98 g of 3-glycidoxypropyltrimethoxysilane, and triethanolamine titanate chelate 15 g is added dropwise to adjust the pH to 3.0 to 7.0. Finally, the produced water-soluble acrylic resin has a solid content of 44.8% by weight, pH 4.3, an acid value of 270, and a viscosity of 210 cps.
실시예 5: 수용성 아크릴 중합체의 제조Example 5: Preparation of Water-Soluble Acrylic Polymer
이온수 609g를 투입하고 85℃로 유지되면 암모늄퍼설페이트 47g을 반응기에 사입하고 30분간 숙성한다. 아크릴산 413g, 머캅토 프로피온산 9g을 180분간 적하한 후 1시간 유지한후 40℃로 냉각하고 1,2,3-트리하이드록시프로판 수용액 361g, 3-글리시독시프로필트리메톡시실란 49g, 트리에탄올아민 티타네이트 킬레이트 9g을 적하하여 pH를 3.0~7.0으로 조절한다. 최종적으로 제조된 수용성 아크릴 수지의 고형분은 44.3중량%이고 pH 3.2, 산가 370, 점도는 450cps이다.When 609 g of ionized water is added and maintained at 85 ° C., 47 g of ammonium persulfate is introduced into the reactor and aged for 30 minutes. 413 g of acrylic acid and 9 g of mercapto propionic acid were added dropwise for 180 minutes, held for 1 hour, cooled to 40 ° C, 361 g of 1,2,3-trihydroxypropane aqueous solution, 49 g of 3-glycidoxypropyltrimethoxysilane, and triethanolamine tita 9 g of nate chelates are added dropwise to adjust the pH to 3.0 to 7.0. Finally, the prepared water-soluble acrylic resin has a solid content of 44.3% by weight, a pH of 3.2, an acid value of 370, and a viscosity of 450 cps.
실시예 6: 수용성 아크릴 중합체의 제조Example 6: Preparation of Water-Soluble Acrylic Polymer
이온수 700g를 투입하고 85℃로 유지되면 소듐퍼설페이트 61g을 반응기에 사입하고 30분간 숙성한후 아크릴산 400g, 메틸메타크릴레이트 68g, 2-에틸헥실아크릴레이트 30g, 머캅토 프로피온산 11g을 240분간 적하한 후 1시간 유지한다. 반응이 종료되면 40℃로 냉각하고 디메틸에탄올아민 수용액 754g, 3-아미노프로필트리에톡시실란 57g, 라틱산 티타네이트 킬레이트 암모니움염 10g을 적하하여 pH를 3.0~7.0으로 조절한다. 최종적으로 제조된 수용성 아크릴 수지의 고형분은 45.4중량%이고 pH 4.7, 산가 210, 점도는 320cps이다.When 700 g of ionized water was added and maintained at 85 ° C., 61 g of sodium persulfate was added to the reactor and aged for 30 minutes. 400 g of acrylic acid, 68 g of methyl methacrylate, 30 g of 2-ethylhexyl acrylate, and 11 g of mercaptopropionic acid were added dropwise for 240 minutes. After 1 hour. After the reaction was completed, the mixture was cooled to 40 ° C, 754 g of aqueous dimethylethanolamine solution, 57 g of 3-aminopropyltriethoxysilane, and 10 g of lactic acid titanate chelate ammonium salt were added dropwise to adjust the pH to 3.0 to 7.0. Finally, the prepared water-soluble acrylic resin has a solid content of 45.4% by weight, a pH of 4.7, an acid value of 210, and a viscosity of 320 cps.
비교예 1Comparative Example 1
유리면 바인더로서 멜라민 포름알데히드 수지를 사용하였다(상품명: KCC-GP, KCC社)Melamine formaldehyde resin was used as the glass surface binder (trade name: KCC-GP, KCC Co., Ltd.)
비교예 2Comparative Example 2
온도계가 장치된 5L 4구 플라스크에 이온수 609.74g를 투입하고 온도를 85℃로 승온한다. 85℃로 유지되면 질소를 5분간 사입하여 반응부를 질소 분위기로 한 후 질소를 제거한다. 암모늄퍼설페이트 47.2g을 반응기에 사입하고 30분간 숙성한다. 아크릴산 413.4g, 머캅토 프로피온산 9g을 180분간 적하한 후 1시간 유지한다. 반응이 완료되면 40℃로 냉각하고 디메틸에탄올아민 수용액 640g, 인산 10g을 적하한다. 최종적으로 제조된 수용성 아크릴 수지의 고형분은 44.1중량%이고 pH 4.7, 산가 270, 점도는 210cps이다.Into a 5 L four-necked flask equipped with a thermometer, 609.74 g of ionized water was added and the temperature was raised to 85 ° C. When the temperature is maintained at 85 ° C., nitrogen is injected for 5 minutes, the reaction part is placed in a nitrogen atmosphere, and nitrogen is removed. 47.2 g of ammonium persulfate are introduced into the reactor and aged for 30 minutes. 413.4 g of acrylic acid and 9 g of mercapto propionic acid are added dropwise for 180 minutes, and then maintained for 1 hour. After the reaction was completed, the mixture was cooled to 40 ° C, and 640 g of dimethylethanolamine aqueous solution and 10 g of phosphoric acid were added dropwise. Finally, the prepared water-soluble acrylic resin has a solid content of 44.1% by weight, a pH of 4.7, an acid value of 270, and a viscosity of 210 cps.
비교예 3Comparative Example 3
온도계가 장치된 5L 4구 플라스크에 이온수 741g를 투입하고 온도를 85℃로 승온한다. 85℃로 유지되면 질소를 5분간 사입하여 반응부를 질소 분위기로 한 후 질소를 제거한다. 암모늄퍼설페이트 36.2g을 이온수 280.1g에 녹인 후 반응기에 사입하고 30분간 숙성한다. 아크릴산 402.4g, 메틸메타크릴레이트 86.2g, 부틸아크릴레이트 86g, 머캅토 프로피온산 6g을 120분간 적하한 후 1시간 유지한다. 반응기를 40℃로 냉각하고 포장한다. 최종적으로 제조된 수용성 아크릴 수지의 고형분은 45.4중량%이고 pH 4.5, 산가 230, 점도는 250cps이다.Into a 5 L four-necked flask equipped with a thermometer, 741 g of ionized water was added, and the temperature was raised to 85 ° C. When the temperature is maintained at 85 ° C., nitrogen is injected for 5 minutes, the reaction part is placed in a nitrogen atmosphere, and nitrogen is removed. Dissolve 36.2 g of ammonium persulfate in 280.1 g of ionized water, insert it into the reactor, and age for 30 minutes. 402.4 g of acrylic acid, 86.2 g of methyl methacrylate, 86 g of butyl acrylate, and 6 g of mercapto propionic acid were added dropwise for 120 minutes, and then maintained for 1 hour. The reactor is cooled to 40 ° C. and packed. Finally, the prepared water-soluble acrylic resin has a solid content of 45.4% by weight, a pH of 4.5, an acid value of 230, and a viscosity of 250 cps.
실험예: 수용성 아크릴 수지 바인더 조성물의 제조Experimental Example: Preparation of Water-Soluble Acrylic Resin Binder Composition
실시예1~6, 비교예1~3의 수지 1000g, 발수제 5g, 방진유 100g, 이온수 4700g를 넣고 고속분산기로 30분간 강력히 분산시키면서 믹싱 바인더를 제조한다. 제조된 바인더의 고형분은 7.9중량%이다.1000 g of resins of Examples 1 to 6 and Comparative Examples 1 to 3, 5 g of water repellent, 100 g of dust-proof oil, and 4700 g of ionized water were added thereto, and a mixing binder was prepared while strongly dispersing for 30 minutes with a high-speed disperser. Solid content of the prepared binder is 7.9% by weight.
이들을 시편 12개에 적용하여 아래 물성 측정방법에 따라 물성을 측정하였으며, 종합 물성표에 대한 결과를 하기 표 1에 나타내었다.These were applied to 12 specimens to measure physical properties according to the following physical property measurement method, and the results for the comprehensive physical properties table are shown in Table 1 below.
< 물성 측정 방법 > <Method of measuring physical property>
1.난연성1. Flame retardant
1) 기재시험 : KSF 2271에 의거하여 750℃로 조정된 로내에 유리면을 연소시키고 연소시 온도 상승이 800℃를 넘지 않아야 한다.1) Substrate test: The glass surface is burned in the furnace adjusted to 750 ℃ according to KSF 2271 and the temperature rise during combustion should not exceed 800 ℃.
2) 표면시험 : 유리면을 가열로에 거치시키고 온도를 가열하여 시편 이면의 온도가 표준온도 곡선을 초과하지 않아야 하며, 연기 발생 정도(CA)가 30이하이어야 한다.2) Surface test: The glass surface should be placed in a heating furnace and heated to ensure that the temperature on the back of the specimen does not exceed the standard temperature curve and the smoke generation rate (CA) is less than 30.
2. HCHO 방출속도2. HCHO Release Rate
1) 소형 쳄버법에 따라 시편을 소형 쳄버에 방치한 후 7일째의 쳄버 공기를 포집한다.1) Collect the air from the chamber on the 7th day after placing the specimen in the small chamber according to the small chamber method.
2) 포집한 공기를 분석(HPLC; 액체크로마토그래피)한다.2) Collected air is analyzed (HPLC).
3) 구체적인 시험방법은 공기청정협회에서 설정한 방법으로 시험을 하되 결과 판정은 7일째에 한다.3) The specific test method shall be tested by the method set by the Air Cleaning Association, but the result shall be determined on the 7th day.
3. 압축율3. Compression rate
1) 시료(400 ×400㎜)의 4면 중간부위의 두께(A)를 측정하여 평균을 취한다.1) Measure the thickness (A) of the middle of four sides of the sample (400 × 400㎜) and take the average.
2) 시료(400 ×400㎜)위에 무게를 알고 있는 철판(400 ×400㎜)을 올려놓고 분동(20㎏)을 올린다음 5분후 4면의 중간부위의 두께(B)를 측정하여 평균을 취한다.2) Place a weight plate (400 × 400㎜) on the sample (400 × 400㎜) and place the weight (20㎏) .After 5 minutes, measure the thickness (B) of the middle section of 4 sides and take the average. do.
3) 분동의 무게를 증량할 경우에는 철판 표면에 분동의 놓을 위치를 그려놓고 그위에 분동을 놓은후 위와 동일한 방법으로 두께를 측정한다.3) When increasing the weight of the weight, draw the weight on the surface of the iron plate, place the weight on it, and measure the thickness in the same way.
4) 압축율은 다음식에 따라 구한다.4) Compression ratio is calculated by the following equation.
압축율(%) = {[(압축전 두께(A) - 압축후 두께(B))]/압축전 두께(A)} ×100Compression Ratio (%) = {[(Pre-Compression Thickness (A)-Post-Compression Thickness (B))] / Pre-Compression Thickness (A)} × 100
5) 측정장비는 분동(20㎏)을 사용한다.5) The measuring equipment uses weight (20㎏).
4. 인장강도4. Tensile Strength
1) 강성도(stiffness) 측정시료 3EA를 폭 4㎝크기로 시료를 제작한다.1) Stiffness Measure 3EA sample to make 4cm wide.
2) 인장봉을 시료의 길이보다 짧게 위치시킨다.2) Place the tension bar shorter than the length of the sample.
3) 인장봉에 시료를 수평이 되도록 고정시킨뒤 지지봉에 시료를 수직이 되도록 조인다.3) Fix the sample horizontally on the tension bar and fasten the sample vertically on the support bar.
4) 인장강도 시험기의 속도를 15㎜/min로 하고, 로드 디스플레이를 영점을 잡은후, 작동시킨다.4) The tensile strength tester is set to 15 mm / min, and the load display is zeroed and then operated.
5) 시험기가 자동으로 멈춘뒤 디스플레이되는 최대하중을 측정하여 평균값을 취한다.5) After the tester stops automatically, measure the maximum load displayed and take the average value.
6) 인장강도는 다음식에 따라 구한다.6) The tensile strength is to be obtained according to the following formula.
인장강도(Kg/㎠) = [하중값(Kg)/(호칭두께) × (폭)] ×100Tensile Strength (Kg / ㎠) = [Load Value (Kg) / (Nominal Thickness) × (Width)] × 100
7) 측정장비는 인장강도 시험기를 사용한다.7) The measuring equipment uses a tensile strength tester.
5. 흡습율5. Hygroscopicity
1) 수조를 88℃의 온도로 세팅한다. 1) Set the bath to a temperature of 88 ° C.
2) 시료를 150 ×150㎜ 크기로 3EA를 자르고, 0.01g까지 정확하게 무게를 측정한다.2) Cut 3EA into 150 × 150 ㎜ size and weigh accurately to 0.01g.
3) 시료를 수조에 넣고 2시간동안 흡습시킨다. 3) Place the sample in a water bath and let it soak for 2 hours.
4) 2시간후 시료를 꺼내 0.01g까지 정확하게 무게(W2)를 측정하여 평균값을 취한다.4) After 2 hours, remove the sample and measure the weight (W2) accurately to 0.01g and take the average value.
본 발명에 따른 아크릴 수지는 카르복실산 성분을 함유한 비닐계 단량체 또는 그의 유도체와 에틸렌계 불포화 단량체를 티타네이트계 또는 지르코네이트계 촉매, 염기성 중화제 및 에폭시 실란 또는 아미노 실란을 이용하여 개시제에 의한 라디칼 반응으로 수용액중에서 용액 중합하여 제조됨으로써 무독성이며, 특히 수용성으로 휘발성 유기 용제를 포함하지 않아 코팅시에 용제 증발에 의한 환경 오염을 일으키지 않으며 멜라민-포름알데히드 수지보다 더 안정한 불연단열재 바인더로서 사용될 수 있다. The acrylic resin according to the present invention is a vinyl monomer containing a carboxylic acid component or a derivative thereof and an ethylenically unsaturated monomer using a titanate or zirconate catalyst, a basic neutralizer and an epoxy silane or an amino silane. It is non-toxic because it is prepared by solution polymerization in aqueous solution by radical reaction, and especially water-soluble does not contain volatile organic solvent, does not cause environmental pollution by solvent evaporation at the time of coating and can be used as non-insulating material binder more stable than melamine-formaldehyde resin. .
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KR101333105B1 (en) | 2011-12-23 | 2013-11-26 | (주)모린스코퍼레이션 | Manufacturing method of flame retardancy binder for glass fiber heat insulating materials forming |
KR20230033130A (en) | 2021-08-27 | 2023-03-08 | 벽산페인트 주식회사 | Binder Composition for Environmental-friendly Insulating Material and Method for Preparing the Same |
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US7829611B2 (en) * | 2006-08-24 | 2010-11-09 | Rohm And Haas Company | Curable composition |
KR102420583B1 (en) * | 2017-07-21 | 2022-07-13 | 주식회사 케이씨씨 | Aqueous binder composition and fibrous materials using the same |
CN118620121B (en) * | 2024-06-17 | 2025-04-04 | 恩莱登(北京)工业技术有限公司 | Thermosetting formaldehyde-free acrylic resin and preparation method and application thereof |
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US4997865A (en) | 1986-08-16 | 1991-03-05 | Basf Lacke & Farben Ag | Aqueous coating agent, process for its manufacture and its use for coating containers based on acrylic monomers, epoxy- polyesters and methylol functional curing agents |
US5322863A (en) | 1990-01-18 | 1994-06-21 | Basf Lacke + Farben Aktiengesellschaft | Coating compound, process for its production as well as use thereof |
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US4997865A (en) | 1986-08-16 | 1991-03-05 | Basf Lacke & Farben Ag | Aqueous coating agent, process for its manufacture and its use for coating containers based on acrylic monomers, epoxy- polyesters and methylol functional curing agents |
US5114993A (en) | 1986-08-16 | 1992-05-19 | Basf Lacke & Farben Ag | Aqueous coating agent, process for its preparation, and its use for coating cans, based on acrylic monomers, epoxy-polyesters and methylol functional curing agents |
US5322863A (en) | 1990-01-18 | 1994-06-21 | Basf Lacke + Farben Aktiengesellschaft | Coating compound, process for its production as well as use thereof |
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KR101333105B1 (en) | 2011-12-23 | 2013-11-26 | (주)모린스코퍼레이션 | Manufacturing method of flame retardancy binder for glass fiber heat insulating materials forming |
KR20230033130A (en) | 2021-08-27 | 2023-03-08 | 벽산페인트 주식회사 | Binder Composition for Environmental-friendly Insulating Material and Method for Preparing the Same |
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