TW201702327A - Primer composition and process for producing same - Google Patents
Primer composition and process for producing same Download PDFInfo
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- TW201702327A TW201702327A TW105111102A TW105111102A TW201702327A TW 201702327 A TW201702327 A TW 201702327A TW 105111102 A TW105111102 A TW 105111102A TW 105111102 A TW105111102 A TW 105111102A TW 201702327 A TW201702327 A TW 201702327A
- Authority
- TW
- Taiwan
- Prior art keywords
- meth
- acrylic
- group
- primer composition
- monomer
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 100
- 238000000034 method Methods 0.000 title claims description 11
- 239000000178 monomer Substances 0.000 claims abstract description 91
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000002245 particle Substances 0.000 claims abstract description 60
- 239000000463 material Substances 0.000 claims abstract description 58
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 41
- 239000003999 initiator Substances 0.000 claims abstract description 36
- -1 acrylate ester Chemical class 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 14
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 12
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims abstract description 9
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 68
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 56
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 39
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 35
- 239000007822 coupling agent Substances 0.000 claims description 34
- 239000004816 latex Substances 0.000 claims description 33
- 229920000126 latex Polymers 0.000 claims description 33
- 239000000758 substrate Substances 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 229920000058 polyacrylate Polymers 0.000 claims description 27
- 150000001412 amines Chemical class 0.000 claims description 21
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 15
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 12
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 8
- 239000005871 repellent Substances 0.000 claims description 8
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 7
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 230000002940 repellent Effects 0.000 claims description 7
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001451 organic peroxides Chemical class 0.000 claims description 5
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims 2
- 125000005250 alkyl acrylate group Chemical group 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 11
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 abstract description 4
- 239000006087 Silane Coupling Agent Substances 0.000 abstract 2
- 239000000839 emulsion Substances 0.000 abstract 1
- 150000003254 radicals Chemical class 0.000 description 32
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- 125000000962 organic group Chemical group 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000003125 aqueous solvent Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 9
- 150000003512 tertiary amines Chemical class 0.000 description 8
- 125000005842 heteroatom Chemical group 0.000 description 7
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- 239000002612 dispersion medium Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011505 plaster Substances 0.000 description 5
- 239000012966 redox initiator Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MTDLVDBRMBSPBJ-UHFFFAOYSA-N C(C1CO1)OCCCC(C(OCC)(OCC)OCC)CCCCCCCC Chemical compound C(C1CO1)OCCCC(C(OCC)(OCC)OCC)CCCCCCCC MTDLVDBRMBSPBJ-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy 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
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 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
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- NKYRAXWYDRHWOG-UHFFFAOYSA-N 12-hydroxydodecyl prop-2-enoate Chemical compound OCCCCCCCCCCCCOC(=O)C=C NKYRAXWYDRHWOG-UHFFFAOYSA-N 0.000 description 1
- 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 1
- WULAHPYSGCVQHM-UHFFFAOYSA-N 2-(2-ethenoxyethoxy)ethanol Chemical compound OCCOCCOC=C WULAHPYSGCVQHM-UHFFFAOYSA-N 0.000 description 1
- PFHOSZAOXCYAGJ-UHFFFAOYSA-N 2-[(2-cyano-4-methoxy-4-methylpentan-2-yl)diazenyl]-4-methoxy-2,4-dimethylpentanenitrile Chemical compound COC(C)(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)(C)OC PFHOSZAOXCYAGJ-UHFFFAOYSA-N 0.000 description 1
- MFAWEYJGIGIYFH-UHFFFAOYSA-N 2-[4-(trimethoxymethyl)dodecoxymethyl]oxirane Chemical compound C(C1CO1)OCCCC(C(OC)(OC)OC)CCCCCCCC MFAWEYJGIGIYFH-UHFFFAOYSA-N 0.000 description 1
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 description 1
- IUPSARVXBUSQKA-UHFFFAOYSA-N 2-hydroxyhexyl 2-methylprop-2-enoate Chemical compound CCCCC(O)COC(=O)C(C)=C IUPSARVXBUSQKA-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- SXPGQGNWEWPWQZ-UHFFFAOYSA-N 4-(triethoxymethyl)dodecan-1-amine Chemical compound NCCCC(C(OCC)(OCC)OCC)CCCCCCCC SXPGQGNWEWPWQZ-UHFFFAOYSA-N 0.000 description 1
- DFYGYTNMHPUJBY-UHFFFAOYSA-N 4-(trimethoxymethyl)dodecane-1-thiol Chemical compound SCCCC(C(OC)(OC)OC)CCCCCCCC DFYGYTNMHPUJBY-UHFFFAOYSA-N 0.000 description 1
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 description 1
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- AAVQACKPQVDAEK-UHFFFAOYSA-N C(C(=C)C)(=O)OCCCC(C(OCC)(OCC)OCC)CCCCCCCC Chemical compound C(C(=C)C)(=O)OCCCC(C(OCC)(OCC)OCC)CCCCCCCC AAVQACKPQVDAEK-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Chemical group 0.000 description 1
- 102100026735 Coagulation factor VIII Human genes 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229920002675 Polyoxyl Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- URLYGBGJPQYXBN-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methyl prop-2-enoate Chemical compound OCC1CCC(COC(=O)C=C)CC1 URLYGBGJPQYXBN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000004181 carboxyalkyl group Chemical group 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000011850 water-based material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
-
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- C09D133/04—Homopolymers or copolymers of esters
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Abstract
Description
本發明有關底漆組成物及其製造方法。 The present invention relates to a primer composition and a method of producing the same.
以往，為了保護建築物免受雨等之影響，有於如灰泥等之基底上設置防水材。而且為使基底不與防水材剝離，而於基底與防水材之間設置底漆層，而提高基底與防水材之密著性。作為此種底漆層中可使用之組成物，已提案有例如由丙烯酸系乳膠所成之底漆組成物(例如專利文獻1)。專利文獻1中，丙烯酸系乳膠中含有之丙烯酸粒子係藉由使具有(甲基)丙烯醯基之聚合性單體在聚合起始劑的過硫酸鹽存在下聚合而製造。 In the past, in order to protect buildings from rain and the like, a waterproof material is provided on a base such as plaster. Further, in order to prevent the substrate from being peeled off from the waterproof material, a primer layer is provided between the substrate and the waterproof material to improve the adhesion between the substrate and the waterproof material. As a composition which can be used for such a primer layer, for example, a primer composition made of an acrylic latex has been proposed (for example, Patent Document 1). In Patent Document 1, the acrylic particles contained in the acrylic latex are produced by polymerizing a polymerizable monomer having a (meth)acryl fluorenyl group in the presence of a persulfate of a polymerization initiator.
[專利文獻1]日本特開2014-172992號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2014-172992
由丙烯酸系乳膠所成之底漆組成物由於分散介質為水，故將底漆組成物塗佈於基底後，有必要自底漆層使水乾燥。若上述乾燥不充分而以水殘留於底漆層中之狀態於底漆層上設置防水材時，有難以展現基底與防水材之密著力的問題。 Since the primer composition made of the acrylic latex is water, it is necessary to apply water from the primer layer after the primer composition is applied to the substrate. When the above-described drying is insufficient and a water repellent material is provided on the primer layer in a state where water remains in the primer layer, there is a problem that it is difficult to exhibit the adhesion between the substrate and the waterproof material.
如此，如專利文獻1調製由丙烯酸系乳膠所成之底漆組成物，將該底漆組成物塗佈於基底且短時間(25℃條件下30分鐘)乾燥，而於底漆層中殘留水分之狀態，於其上設置防水材使基底與防水材密著進行評價後，明瞭有基底與防水材之密著力降低之情況。 Thus, as disclosed in Patent Document 1, a primer composition made of an acrylic latex is prepared, and the primer composition is applied to a substrate and dried in a short time (30 minutes at 25 ° C) to leave moisture in the primer layer. In the state in which the waterproof material was placed thereon to evaluate the adhesion between the base and the waterproof material, it was revealed that the adhesion between the base and the waterproof material was lowered.
因此，本發明之目的在於提供即使乾燥時間短，基底與防水材之密著性亦優異之底漆組成物。 Therefore, an object of the present invention is to provide a primer composition which is excellent in adhesion between a substrate and a water repellent material even when the drying time is short.
本發明人等為解決上述課題而積極研究之結果，發現根據包含含特定(甲基)丙烯酸粒子之(甲基)丙烯酸系乳膠與具有環氧丙基之矽烷偶合劑之組成物，可獲得期望效果，因而完成本發明。 As a result of active research to solve the above problems, the present inventors have found that it is possible to obtain a desired composition based on a composition comprising a (meth)acrylic latex containing a specific (meth)acrylic particle and a decane coupling agent having a glycidyl group. The effect thus completes the present invention.
本發明係基於上述見解而完成者，具體而言，藉由以下構成而解決上述課題者。 The present invention has been completed based on the above findings, and specifically, the above-described problems are solved by the following configuration.
1.一種底漆組成物，其係用以密著基底與防水材， 包含含(甲基)丙烯酸粒子之(甲基)丙烯酸系乳膠與具有環氧丙基的矽烷偶合劑(A)，(甲基)丙烯酸粒子係於自由基起始劑的存在下使具有(甲基)丙烯醯基之聚合性單體(B)聚合所得的聚合物粒子，聚合性單體(B)係含有(甲基)丙烯酸烷基酯單體(b1)、具有羧基之(甲基)丙烯酸系單體(b2)與具有羥基之含羥基的聚合性單體(b3)，前述自由基起始劑係選自由二鹵系自由基起始劑(二鹵化合物)、偶氮化合物及有機過氧化物所成之群的至少一種，矽烷偶合劑(A)對於前述(甲基)丙烯酸烷基酯單體(b1)的莫耳比(A/b1)為0.020以下，(甲基)丙烯酸粒子對於組成物總量的含量為15質量%以上。 A primer composition for adhering a substrate to a waterproof material, a (meth)acrylic latex containing (meth)acrylic acid particles and a decane coupling agent (A) having a glycidyl group, and the (meth)acrylic acid particles are provided in the presence of a radical initiator Polymer particles obtained by polymerizing a polymerizable monomer (B) of an acrylonitrile group, and the polymerizable monomer (B) contains an alkyl (meth)acrylate monomer (b1) and a carboxyl group (meth) An acrylic monomer (b2) and a hydroxyl group-containing polymerizable monomer (b3) having a hydroxyl group selected from a dihalogen radical initiator (dihalogen compound), an azo compound, and an organic group At least one of the group of peroxides, the molar ratio (A/b1) of the decane coupling agent (A) to the alkyl (meth) acrylate monomer (b1) is 0.020 or less, (meth)acrylic acid The content of the particles in the total amount of the composition is 15% by mass or more.
2.如上述1的底漆組成物，其中(甲基)丙烯酸烷基酯單體(b1)係包含甲基丙烯酸甲酯(MMA)與丙烯酸2-乙基己酯(2HEA)，甲基丙烯酸甲酯對於丙烯酸2-乙基己酯的莫耳比(MMA/2HEA)為1.470~2.310。 2. The primer composition according to the above 1, wherein the alkyl (meth)acrylate monomer (b1) comprises methyl methacrylate (MMA) and 2-ethylhexyl acrylate (2HEA), methacrylic acid The molar ratio of methyl ester to 2-ethylhexyl acrylate (MMA/2HEA) was 1.470 to 2.310.
3.如上述1或2的底漆組成物，其中(甲基)丙烯酸系單體(b2)對於(甲基)丙烯酸烷基酯單體(b1)的莫耳比(b2/b1)，為0.038~0.075。 3. The primer composition according to the above 1 or 2, wherein the molar ratio (b2/b1) of the (meth)acrylic monomer (b2) to the alkyl (meth)acrylate monomer (b1) is 0.038~0.075.
4.如上述1~3中任一項的底漆組成物，其中具有羥 基的含羥基聚合性單體(b3)對於(甲基)丙烯酸烷基酯單體(b1)的莫耳比(b3/b1)為0.050~0.100。 4. The primer composition according to any one of the above 1 to 3, which has a hydroxyl group The molar ratio (b3/b1) of the hydroxyl group-containing polymerizable monomer (b3) to the alkyl (meth)acrylate monomer (b1) is from 0.050 to 0.100.
5.如上述1~4中任一項的底漆組成物，其中(甲基)丙烯酸粒子所具有之羧基係藉由第三級胺(C)離子化。 5. The primer composition according to any one of the above 1 to 4, wherein the carboxyl group of the (meth)acrylic acid particles is ionized by the third-order amine (C).
6.如上述5的底漆組成物，其中第三級胺(C)對於(甲基)丙烯酸系單體(b2)的莫耳比(C/b2)，為0.560~1.140。 6. The primer composition according to the above 5, wherein the molar ratio (C/b2) of the third-stage amine (C) to the (meth)acrylic monomer (b2) is from 0.560 to 1.140.
7.如上述1~6中任一項的底漆組成物，其中防水材為胺基甲酸酯防水材。 7. The primer composition according to any one of the above 1 to 6, wherein the waterproof material is a urethane waterproof material.
8.如上述1~7中任一項的底漆組成物，其中前述基底為無機系硬質材料。 8. The primer composition according to any one of 1 to 7, wherein the substrate is an inorganic hard material.
9.一種底漆組成物，其係用以密著基底與防水材，包含含(甲基)丙烯酸粒子之(甲基)丙烯酸系乳膠與具有環氧丙基的矽烷偶合劑(A)，構成(甲基)丙烯酸粒子之聚合物係具有烷基與羥基與羧基，且主骨架為聚(甲基)丙烯酸骨架的(甲基)丙烯酸系聚合物，矽烷偶合劑(A)對於具有烷基之重複單位的莫耳比為0.020以下，(甲基)丙烯酸粒子對於組成物總量的含量為15質量%以上。 A primer composition for adhering a substrate to a waterproof material, comprising a (meth)acrylic latex containing (meth)acrylic particles and a decane coupling agent (A) having a glycidyl group. The polymer of (meth)acrylic acid particles is a (meth)acrylic polymer having an alkyl group and a hydroxyl group and a carboxyl group, and the main skeleton is a poly(meth)acrylic acid skeleton, and the decane coupling agent (A) has an alkyl group. The molar ratio of the repeating unit is 0.020 or less, and the content of the (meth)acrylic acid particles to the total amount of the composition is 15% by mass or more.
10.一種底漆組成物之製造方法，其係藉由在自由基起始劑的存在下使具有(甲基)丙烯醯基之聚合性單體 (B)聚合製造(甲基)丙烯酸系聚合物，並混合(甲基)丙烯酸系聚合物與水與具有環氧丙基之矽烷偶合劑(A)，而製造如上述1~4及7~9中任一項的底漆組成物。 A method for producing a primer composition by polymerizing a monomer having a (meth) acrylonitrile group in the presence of a radical initiator (B) Polymerizing a (meth)acrylic polymer and mixing a (meth)acrylic polymer with water and a decane coupling agent (A) having a glycidyl group, and producing the above 1 to 4 and 7~ A primer composition of any of the following 9.
11.如上述10的底漆組成物之製造方法，其中進一步含第三級胺(C)。 11. The method for producing a primer composition according to the above 10, which further comprises a tertiary amine (C).
上述9中記載之底漆組成物中含有之(甲基)丙烯酸系乳膠與上述1中記載之底漆組成物中含有之(甲基)丙烯酸系乳膠對應。關於其以外之成分亦同樣。 The (meth)acrylic latex contained in the primer composition described in the above 9 corresponds to the (meth)acrylic latex contained in the primer composition described in the above paragraph 1. The same applies to the ingredients other than the other.
上述9中記載之底漆組成物中，(甲基)丙烯酸系聚合物所具有之具有烷基之重複單位與自後述之(甲基)丙烯酸烷基酯單體(b1)所形成之重複單位對應。 In the primer composition according to the above 9, the repeating unit having an alkyl group and the repeating unit formed from the alkyl (meth)acrylate monomer (b1) described later in the (meth)acrylic polymer. correspond.
本發明之底漆組成物即使乾燥時間短，基底與防水材之密著性亦優異。 The primer composition of the present invention is excellent in adhesion to a substrate and a water repellent material even when the drying time is short.
依據本發明之製造方法，可製造即使乾燥時間短，基底與防水材之密著性亦優異之底漆組成物。 According to the production method of the present invention, it is possible to produce a primer composition which is excellent in adhesion between the substrate and the water repellent material even when the drying time is short.
針對本發明於以下詳細說明。 The invention is described in detail below.
又，本說明書中，所謂(甲基)丙烯酸酯表示丙烯酸酯或甲基丙烯酸酯，所謂(甲基)丙烯醯基表示丙烯醯基或甲基丙烯醯基，所謂(甲基)丙烯酸表示丙烯酸或甲基 丙烯酸。 Further, in the present specification, the (meth) acrylate means acrylate or methacrylate, the (meth) acryl fluorenyl means acryl fluorenyl or methacryl fluorenyl, and the so-called (meth) acrylate means acrylic or methyl acrylic acid.
又，本說明書中使用「~」表示之數值範圍意指包含將「~」前後記載之數值設為下限值與上限值之範圍。 In addition, the numerical range represented by "~" in this specification means the range which has the numerical value of the before and after the [~.
又，本說明書中，所使用之各成分若未特別限制，則可分別單獨使用或組成2種以上使用與該成分相當之物質。成分包含2種以上之物質時，所謂上述成分之含量係指2種以上物質之合計含量。 In addition, in the present specification, each component to be used may be used singly or in combination of two or more kinds depending on the component, unless otherwise specified. When the component contains two or more kinds of substances, the content of the above-mentioned components means the total content of two or more substances.
本說明書中未特別限制有機基。作為有機基舉例為例如可具有雜原子之烴基。作為烴基，舉例為例如脂肪族烴基、芳香族烴基、該等之組合。作為雜原子舉例為例如氧原子、氮原子、硫原子。雜原子亦可與氫原子、碳原子或其他雜原子組合形成官能基。 The organic group is not particularly limited in the present specification. As the organic group, for example, a hydrocarbon group which may have a hetero atom is exemplified. The hydrocarbon group is exemplified by, for example, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof. The hetero atom is exemplified by, for example, an oxygen atom, a nitrogen atom, or a sulfur atom. A hetero atom can also be combined with a hydrogen atom, a carbon atom or other hetero atom to form a functional group.
本說明書中，製造(甲基)丙烯酸粒子時所使用之單體之單體比係反映於構成(甲基)丙烯酸粒子之聚合物所具有之重複單位之比。 In the present specification, the monomer ratio of the monomer used in the production of the (meth)acrylic acid particles is reflected in the ratio of the repeating units of the polymer constituting the (meth)acrylic acid particles.
本發明之底漆組成物(本發明之組成物)係用以密著基底與防水材之底漆組成物，包含含(甲基)丙烯酸粒子之(甲基)丙烯酸系乳膠與具有環氧丙基的矽烷偶合劑(A)，(甲基)丙烯酸粒子係於自由基起始劑的存在下使具有(甲基)丙烯醯基之聚合性單體(B)聚合所得的聚合物粒子， 聚合性單體(B)係含有(甲基)丙烯酸烷基酯單體(b1)、具有羧基之(甲基)丙烯酸系單體(b2)與具有羥基之含羥基的聚合性單體(b3)，自由基起始劑係選自由二鹵系自由基起始劑、偶氮化合物及有機過氧化物所成之群的至少一種，矽烷偶合劑(A)對於前述(甲基)丙烯酸烷基酯單體(b1)的莫耳比(A/b1)，為0.020以下，(甲基)丙烯酸粒子對於組成物總量的含量，為15質量%以上。 The primer composition of the present invention (the composition of the present invention) is a primer composition for adhering a substrate and a waterproof material, comprising a (meth)acrylic latex containing (meth)acrylic particles and having a propylene oxide The decane coupling agent (A) and the (meth)acrylic acid particles are polymer particles obtained by polymerizing a (meth)acryl fluorenyl polymerizable monomer (B) in the presence of a radical initiator. The polymerizable monomer (B) contains a (meth)acrylic acid alkyl ester monomer (b1), a carboxyl group-containing (meth)acrylic monomer (b2), and a hydroxyl group-containing polymerizable monomer (b3). The radical initiator is at least one selected from the group consisting of a dihalogen radical initiator, an azo compound, and an organic peroxide, and the decane coupling agent (A) is bonded to the aforementioned (meth)acrylic acid alkyl group. The molar ratio (A/b1) of the ester monomer (b1) is 0.020 or less, and the content of the (meth)acrylic acid particles to the total amount of the composition is 15% by mass or more.
認為由於將本發明之組成物設為如此構成而獲得期望效果者。其理由尚不明確，但推測幾乎如下。 It is considered that the desired effect is obtained by setting the composition of the present invention as such. The reason is not clear, but it is estimated to be almost as follows.
一般水系底漆組成物如上述難以於短時間乾燥，為了展現高的密著性，有必要使底漆組成物充分乾燥。 Generally, the water-based primer composition is difficult to dry in a short time as described above, and in order to exhibit high adhesion, it is necessary to sufficiently dry the primer composition.
若於底漆組成物未充分乾燥之狀態於其上設置防水材，則上述組成物中之水氣化，或於防水材為胺基甲酸酯系時因水使異氰酸酯基分解而發生二氧化碳等之理由，會有於防水材與基底之間產生空洞之情況。若產生如此空洞，則防水材無法與底漆層形成結合，故密著性變低，此係本發明人等所推測。 When a water repellency material is provided on the primer composition in a state where the primer composition is not sufficiently dried, water in the above composition is vaporized, or when the water repellency material is an urethane type, carbonic acid is generated by decomposition of isocyanate groups by water. For this reason, there may be a void between the waterproof material and the substrate. When such a void occurs, the waterproof material cannot be combined with the primer layer, so that the adhesion is lowered, which is inferred by the inventors of the present invention.
依據本發明，即使本發明之組成物乾燥後於乾燥後之底漆組成物中殘留水分之狀態，由於組成物中含有之矽烷偶合劑(A)所具有之環氧丙基可與基底及防水材中之一者或兩者反應或相互作用，故認為基底與防水材之密著性優異。 According to the present invention, even if the composition of the present invention is dried, the moisture remains in the primer composition after drying, and the epoxy propyl group having the decane coupling agent (A) contained in the composition can be used with the substrate and waterproof. One of the materials or both react or interact, and it is considered that the adhesion between the substrate and the waterproof material is excellent.
以下，針對本發明組成物中含有之各成分加以說明。 Hereinafter, each component contained in the composition of the present invention will be described.
本發明之組成物中所含有之(甲基)丙烯酸系乳膠含有作為分散質之(甲基)丙烯酸粒子與分散介質，(甲基)丙烯酸粒子分散於分散介質中。又本發明之乳膠係包含懸浮液(於液相之分散介質中分散有固相的分散質之系統)及於液相的分散介質中分散有液相的分散質之系統之概念。 The (meth)acrylic latex contained in the composition of the present invention contains (meth)acrylic particles as a dispersoid and a dispersion medium, and the (meth)acrylic particles are dispersed in a dispersion medium. Further, the latex of the present invention is a system comprising a suspension (a system in which a dispersion of a solid phase is dispersed in a dispersion medium in a liquid phase) and a system in which a dispersion of a liquid phase is dispersed in a dispersion medium of a liquid phase.
分散介質若為水系溶劑則未特別限制。作為水系溶劑舉例為例如水；水中可溶之有機溶劑與水混合之混合溶劑。作為上述有機溶劑舉例為例如醇；如甲基乙基酮(MEK)之酮。 The dispersion medium is not particularly limited as long as it is an aqueous solvent. The aqueous solvent is exemplified by, for example, water; a mixed solvent of a water-soluble organic solvent mixed with water. The above organic solvent is exemplified by, for example, an alcohol; a ketone such as methyl ethyl ketone (MEK).
作為分散質之(甲基)丙烯酸粒子係在自由基起始劑的存在下使具有(甲基)丙烯醯基之聚合性單體(B)聚合所得的聚合物粒子。 The (meth)acrylic acid particles as a dispersoid are polymer particles obtained by polymerizing a polymerizable monomer (B) having a (meth) acrylonitrile group in the presence of a radical initiator.
(甲基)丙烯酸粒子之形狀若為粒狀則未特別限制。 The shape of the (meth)acrylic particles is not particularly limited as long as it is in the form of particles.
(甲基)丙烯酸粒子之平均粒徑可為例如0.01~0.6μm。(甲基)丙烯酸粒子之平均粒徑可使用粒度徑分佈測定機(Nanotrac UPA-EX150，日機裝公司製)測定。 The average particle diameter of the (meth)acrylic particles may be, for example, 0.01 to 0.6 μm. The average particle diameter of the (meth)acrylic acid particles can be measured using a particle size distribution measuring machine (Nanotrac UPA-EX150, manufactured by Nikkiso Co., Ltd.).
(甲基)丙烯酸粒子其表面可具有羧基。 The (meth)acrylic acid particles may have a carboxyl group on the surface.
製造(甲基)丙烯酸粒子時使用之具有(甲基)丙烯醯基之聚合性單體(B)較好含有(甲基)丙烯酸烷基酯單體(b1)、具有羧基之(甲基)丙烯酸系單體(b2)與具有羥基之含羥基的聚合性單體(b3)。 The polymerizable monomer (B) having a (meth)acrylonitrile group used for producing the (meth)acrylic acid particles preferably contains an alkyl (meth)acrylate monomer (b1) and a carboxyl group (methyl). An acrylic monomer (b2) and a hydroxyl group-containing polymerizable monomer (b3) having a hydroxyl group.
(甲基)丙烯酸烷基酯單體(b1)為(甲基)丙烯酸之烷基酯。 The alkyl (meth)acrylate monomer (b1) is an alkyl (meth)acrylate.
(甲基)丙烯酸烷基酯單體(b1)中，並未特別限制鍵結於酯鍵之烷基(脂肪族烴基)。可為直鏈狀、分支狀或環狀之任一者或該等之組合。 In the alkyl (meth)acrylate monomer (b1), an alkyl group (aliphatic hydrocarbon group) bonded to an ester bond is not particularly limited. It may be any of a linear chain, a branch or a ring or a combination of these.
作為(甲基)丙烯酸烷基酯單體(b1)之具體例舉例為例如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸己酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸丁基環己酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸辛酯、(甲基)丙烯酸壬酯。 Specific examples of the alkyl (meth)acrylate monomer (b1) are, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and butyl (meth)acrylate. Ester, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, butyl cyclohexyl (meth) acrylate, amyl (meth) acrylate, Octyl (meth)acrylate, decyl (meth)acrylate.
其中，較好為(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-乙基己酯，更好為(甲基)丙烯酸甲酯、(甲基)丙烯酸2-乙基己酯。 Among them, preferred is methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, more preferably (meth)acrylic acid Ester, 2-ethylhexyl (meth)acrylate.
(甲基)丙烯酸烷基酯單體(b1)可分別單 獨使用或組合2種以上使用。 Alkyl (meth) acrylate monomer (b1) can be separately It can be used alone or in combination of two or more.
(甲基)丙烯酸烷基酯單體(b1)之組合較好為(甲基)丙烯酸甲酯(MMA)與(甲基)丙烯酸2-乙基己酯(2HEA)之組合。 The combination of the alkyl (meth)acrylate monomer (b1) is preferably a combination of methyl (meth)acrylate (MMA) and 2-ethylhexyl (meth)acrylate (2HEA).
甲基丙烯酸甲酯對於丙烯酸2-乙基己酯的莫耳比(MMA/2HEA)較好為1.470~2.310，更好為1.650~2.030。 The molar ratio (MMA/2HEA) of methyl methacrylate to 2-ethylhexyl acrylate is preferably 1.470 to 2.310, more preferably 1.650 to 2.030.
又，(甲基)丙烯酸烷基酯單體(b1)舉例有不具有羧基或羥基作為較佳樣態。 Further, the (meth)acrylic acid alkyl ester monomer (b1) is exemplified by having no carboxyl group or hydroxyl group as a preferred aspect.
(甲基)丙烯酸系單體(b2)係具有(甲基)丙烯醯基與羧基之化合物。 The (meth)acrylic monomer (b2) is a compound having a (meth)acryl fluorenyl group and a carboxyl group.
(甲基)丙烯醯基之-CO-亦可形成羧基。 The (meth)acryloyl group -CO- can also form a carboxyl group.
又，(甲基)丙烯醯基與羧基可透過有機基鍵結。(甲基)丙烯醯基亦可為例如(甲基)丙烯醯氧基。 Further, the (meth)acrylonitrile group and the carboxyl group are permeable to the organic group. The (meth) acrylonitrile group may also be, for example, a (meth) propylene fluorenyloxy group.
作為(甲基)丙烯酸系單體(b2)舉例為例如(甲基)丙烯酸；如(甲基)丙烯酸羧基乙酯、(甲基)丙烯酸羧基戊酯之(甲基)丙烯酸羧基烷酯。 The (meth)acrylic monomer (b2) is exemplified by, for example, (meth)acrylic acid; a carboxyalkyl (meth)acrylate such as carboxyethyl (meth)acrylate or carboxypentyl (meth)acrylate.
(甲基)丙烯酸系單體(b2)可分別單獨使用或組合2種以上使用。 The (meth)acrylic monomer (b2) may be used alone or in combination of two or more.
(甲基)丙烯酸系單體(b2)對於(甲基)丙烯酸烷基酯單體(b1)的莫耳比(b2/b1)較好為0.038~0.075，更好為0.047~0.066。 The molar ratio (b2/b1) of the (meth)acrylic monomer (b2) to the alkyl (meth)acrylate monomer (b1) is preferably from 0.038 to 0.075, more preferably from 0.047 to 0.066.
具有羥基之含羥基之聚合性單體(b3)係具有羥基與作為聚合性官能基之(甲基)丙烯醯基之化合物。 The hydroxyl group-containing polymerizable monomer (b3) having a hydroxyl group is a compound having a hydroxyl group and a (meth)acrylonitrile group as a polymerizable functional group.
含羥基之聚合性單體(b3)1分子所具有之羥基可為1個或複數個。上述羥基較好為1個。 The hydroxyl group-containing polymerizable monomer (b3) may have one or a plurality of hydroxyl groups per molecule. The above hydroxyl group is preferably one.
含羥基之聚合性單體(b3)1分子所具有之(甲基)丙烯醯基亦可為例如(甲基)丙烯醯氧基。 The (meth) acrylonitrile group which one molecule of the hydroxyl group-containing polymerizable monomer (b3) has may be, for example, a (meth) propylene fluorenyloxy group.
列舉為較佳樣態之一係羥基與(甲基)丙烯醯基透過有機基(例如可具有雜原子之烴基)鍵結。並未特別限制有機基(雜原子、烴基)。 One of the preferred forms is a hydroxyl group bonded to a (meth)acryloyl group through an organic group (for example, a hydrocarbon group which may have a hetero atom). The organic group (hetero atom, hydrocarbon group) is not particularly limited.
含羥基之聚合性單體(b3)之具體例舉例為例如(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸2-羥基己酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸10-羥基癸酯、(甲基)丙烯酸12-羥基十二烷酯、丙烯酸(4-羥基甲基環己基)甲酯、N-羥甲基(甲基)丙烯醯胺、N-羥基(甲基)丙烯醯胺、乙烯醇、烯丙醇、2-羥基乙基乙烯醚、4-羥基丁基乙烯醚、二乙二醇單乙烯醚等。 Specific examples of the hydroxyl group-containing polymerizable monomer (b3) are, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, ( 2-hydroxyhexyl methacrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxy decyl (meth) acrylate, (meth) acrylate 12- Hydroxydodecyl ester, (4-hydroxymethylcyclohexyl)methyl acrylate, N-methylol (meth) acrylamide, N-hydroxy (meth) acrylamide, vinyl alcohol, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, and the like.
其中，較好為(甲基)丙烯酸2-羥基乙酯。 Among them, 2-hydroxyethyl (meth)acrylate is preferred.
含羥基之聚合性單體(b3)可分別單獨使用或組合2種以上使用。 The hydroxyl group-containing polymerizable monomer (b3) may be used alone or in combination of two or more.
具有羥基的含羥基聚合性單體(b3)對於 (甲基)丙烯酸烷基酯單體(b1)的莫耳比(b3/b1)較好為0.050~0.100，更好為0.069~0.100。 Hydroxyl-containing polymerizable monomer (b3) having a hydroxyl group for The molar ratio (b3/b1) of the alkyl (meth)acrylate monomer (b1) is preferably from 0.050 to 0.100, more preferably from 0.069 to 0.100.
製造(甲基)丙烯酸粒子時使用之單體除了上述(b1)~(b3)之單體以外，亦可進而使用具有乙烯性不飽和鍵之化合物。作為上述具有乙烯性不飽和鍵之化合物舉例為例如烯烴；如苯乙烯之乙烯性芳香族烴化合物；如巴豆酸、依康酸、馬來酸、富馬酸之羧酸化合物等。 The monomer used for producing the (meth)acrylic acid particles may further use a compound having an ethylenically unsaturated bond in addition to the monomers of the above (b1) to (b3). The compound having an ethylenically unsaturated bond is exemplified by, for example, an olefin; an ethylenic aromatic hydrocarbon compound such as styrene; a carboxylic acid compound such as crotonic acid, isaconic acid, maleic acid or fumaric acid.
製造(甲基)丙烯酸粒子時使用之自由基起始劑係選自由二鹵系自由基起始劑、偶氮化合物及有機過氧化物所成之群的至少一種。 The radical initiator used in the production of the (meth)acrylic acid particles is at least one selected from the group consisting of a dihalogen radical initiator, an azo compound, and an organic peroxide.
自由基起始劑可使聚合性單體(B)所具有之(甲基)丙烯醯基自由基化。 The radical initiator can radically catalyze the (meth) acryloyl group which the polymerizable monomer (B) has.
(二鹵系自由基起始劑) (dihalogen free radical initiator)
二鹵系自由基起始劑若為具有鹵素-鹵素鍵之物質(包含具有鹵素-鹵素鍵之化合物及鹵素分子)則未特別限制。未特別限制鹵素。 The dihalogen radical initiator is not particularly limited as long as it has a halogen-halogen bond (comprising a compound having a halogen-halogen bond and a halogen molecule). Halogen is not particularly limited.
(有機過氧化物) (organic peroxide)
作為有機過氧化物舉例為苯甲醯基過氧化物、第三丁基過氧化氫、異丙苯過氧化氫。 Examples of the organic peroxides are benzammonium peroxide, tert-butyl hydroperoxide, and cumene hydroperoxide.
(偶氮化合物) (azo compound)
自由基起始劑中，基於使本發明效果更優異之觀點，較好為偶氮化合物。 Among the radical initiators, an azo compound is preferred from the viewpoint of further improving the effects of the present invention.
偶氮化合物若為具有偶氮鍵之化合物則未特別限制。並未特別限制鍵結於偶氮鍵之有機基。 The azo compound is not particularly limited as long as it is a compound having an azo bond. The organic group bonded to the azo bond is not particularly limited.
作為偶氮化合物舉例為例如偶氮雙異丁腈、偶氮二碳醯胺、2,2’-偶氮雙-(2-脒基丙烷)二鹽酸鹽、2,2’-偶氮雙(異丁酸)二甲酯、偶氮雙-氰化戊酸、1,1’-偶氮雙-(2,4-二甲基戊腈)、偶氮雙甲基丁腈、2,2’-偶氮雙-(4-甲氧基-2,4-二甲基戊腈)。 Examples of the azo compound are, for example, azobisisobutyronitrile, azobiscarbamide, 2,2'-azobis-(2-amidinopropane) dihydrochloride, 2,2'-azobis (isobutyric acid) dimethyl ester, azobis-cyanide valeric acid, 1,1'-azobis-(2,4-dimethylvaleronitrile), azobismethylbutyronitrile, 2,2 '-Azobis-(4-methoxy-2,4-dimethylvaleronitrile).
自由基起始劑可分別單獨使用或可組合2種以上使用。 The radical initiators may be used alone or in combination of two or more.
本發明中，自由基起始劑之作為較佳樣態之一舉例為實質上不含過氧酸鹽。 In the present invention, one of the preferred embodiments of the radical initiator is exemplified by substantially no peroxyacid salt.
並未特別限制過硫酸鹽。舉例為例如過硫酸銨、過硫酸鉀、過硫酸鈉。 Persulfate is not particularly limited. Examples are, for example, ammonium persulfate, potassium persulfate, sodium persulfate.
所謂自由基起始劑實質上不含過硫酸鹽意指，過硫酸鹽之使用量相對於上述自由基起始劑，為0~0.1質量%。 The radical initiator is substantially free of persulfate, and the amount of persulfate used is 0 to 0.1% by mass based on the radical initiator.
本發明中，自由基起始劑之作為較佳樣態之一舉例為實質上不含氧化還原起始劑。 In the present invention, one of the preferred embodiments of the radical initiator is exemplified as being substantially free of a redox initiator.
並未特別限制氧化還原起始劑。舉例為例如如過硫酸鹽之氧化劑與如亞硫酸氫鈉之還原劑之組合。 The redox initiator is not particularly limited. For example, a combination of an oxidizing agent such as persulfate and a reducing agent such as sodium hydrogen sulfite.
所謂自由基起始劑實質上不含氧化還原起始劑意指， 氧化還原起始劑之使用量相對於上述自由基起始劑，為0~0.1質量%。 The free radical initiator is substantially free of redox initiators, The amount of the redox initiator to be used is 0 to 0.1% by mass based on the above-mentioned radical initiator.
自由基起始劑對於上述聚合性單體(B)總量之使用量(莫耳比)較好為0.0013~0.0100，更好為0.0026~0.0090。 The amount of the radical initiator to be used in the total amount of the above polymerizable monomer (B) (mol ratio) is preferably from 0.0013 to 0.0100, more preferably from 0.0026 to 0.0090.
(構成(甲基)丙烯酸粒子之聚合物之製造) (Manufacture of a polymer constituting (meth)acrylic particles)
構成(甲基)丙烯酸粒子之聚合物((甲基)丙烯酸系聚合物)可藉由在自由基起始劑存在下使上述聚合性單體(B)聚合而得。 The polymer ((meth)acrylic polymer) constituting the (meth)acrylic acid particles can be obtained by polymerizing the above polymerizable monomer (B) in the presence of a radical initiator.
上述聚合可在例如氮氣等惰性氣體氣流下，於60~80℃左右之溫度進行。 The above polymerization can be carried out at a temperature of about 60 to 80 ° C under an inert gas flow such as nitrogen.
又，上述(甲基)丙烯酸系聚合物之較佳樣態之一舉例為在水系溶劑或有機溶劑中製造。自由基起始劑、聚合性單體(B)、水系溶劑、有機溶劑與上述相同。 Further, one of the preferred aspects of the above (meth)acrylic polymer is exemplified by being produced in an aqueous solvent or an organic solvent. The radical initiator, the polymerizable monomer (B), the aqueous solvent, and the organic solvent are the same as described above.
於水系溶劑中進行上述聚合時，可將上述(甲基)丙烯酸系聚合物設為粒子狀，可設為含有(甲基)丙烯酸粒子之(甲基)丙烯酸系乳膠。 When the above polymerization is carried out in an aqueous solvent, the (meth)acrylic polymer may be in the form of particles, and may be a (meth)acrylic latex containing (meth)acrylic particles.
((甲基)丙烯酸系乳膠之製造方法) (Method for producing (meth)acrylic latex)
本發明之組成物中所含有之含有(甲基)丙烯酸粒子之(甲基)丙烯酸系乳膠之製造方法，舉例為例如在水系溶劑中，在自由基起始劑存在下使具有(甲基)丙烯醯基之聚合性單體(B)聚合之方法；如上述製造(甲基)丙 烯酸系聚合物(例如在有機溶劑中進行上述聚合之情況)，於上述聚合後，於反應系內添加水系溶劑並攪拌之方法。 The method for producing a (meth)acrylic latex containing (meth)acrylic acid particles contained in the composition of the present invention is, for example, an aqueous solvent having a (meth) group in the presence of a radical initiator a method for polymerizing a polymerizable monomer (B) of an acrylonitrile group; producing (meth) propyl as described above The olefinic polymer (for example, when the polymerization is carried out in an organic solvent), after the polymerization described above, a method of adding an aqueous solvent to the reaction system and stirring the mixture is carried out.
自由基起始劑、聚合性單體(B)、水系溶劑、有機溶劑與上述相同。 The radical initiator, the polymerizable monomer (B), the aqueous solvent, and the organic solvent are the same as described above.
(第三級胺(C)) (third grade amine (C))
本發明之組合物進而可含有第三級胺(C)。 The composition of the present invention may further contain a tertiary amine (C).
本發明中可用第三級胺(C)作為鹼。藉由使用第三級胺(C)，第三級胺(C)可使組成物中含有之(甲基)丙烯酸粒子所具有之羧基離子化，可使(甲基)丙烯酸粒子之分散良好。 The tertiary amine (C) can be used as a base in the present invention. By using the third-stage amine (C), the third-stage amine (C) can ionize the carboxyl group of the (meth)acrylic acid particles contained in the composition, and the dispersion of the (meth)acrylic acid particles can be made good.
第三級胺(C)較好為具有脂肪族烴基之第三級胺，更好鍵結於氮原子之烴基均為脂肪族烴基。 The third-stage amine (C) is preferably a tertiary amine having an aliphatic hydrocarbon group, and more preferably the hydrocarbon group bonded to the nitrogen atom is an aliphatic hydrocarbon group.
作為第三級胺(C)舉例為例如三乙胺、N,N-二甲基月桂胺、N,N-二甲基棕櫚胺。 As the tertiary amine (C), for example, triethylamine, N,N-dimethyllaurylamine, and N,N-dimethyl palmamine are exemplified.
第三級胺(C)分別可單獨使用或組合2種以上使用。 The third-stage amines (C) may be used singly or in combination of two or more.
第三級胺(C)對於(甲基)丙烯酸系單體(b2)的莫耳比(C/b2)較好為0.560~1.140，更好為0.760~0.940。 The molar ratio (C/b2) of the third-stage amine (C) to the (meth)acrylic monomer (b2) is preferably from 0.560 to 1.140, more preferably from 0.760 to 0.940.
(使用第三級胺(C)時之(甲基)丙烯酸系乳膠之製造方法) (Method for producing (meth)acrylic latex when third-stage amine (C) is used)
作為使用第三級胺(C)時之(甲基)丙烯酸系乳膠之製造方法，例如於如上述製造之(甲基)丙烯酸系乳膠中添加第三級胺(C)，將該等混合，可製造含有第三級胺(C)之(甲基)丙烯酸系乳膠。 As a method for producing the (meth)acrylic latex when the third-stage amine (C) is used, for example, a third-stage amine (C) is added to the (meth)acrylic latex produced as described above, and the mixture is mixed. A (meth)acrylic latex containing a third-order amine (C) can be produced.
作為與上述不同之方法，舉例為例如於水系溶劑中在自由基起始劑及第三級胺(C)存在下，使具有(甲基)丙烯醯基之聚合性單體(B)邊以攪拌機混合邊在60~90℃之條件下進行自由基聚合之方法。 As a method different from the above, for example, in the presence of a radical initiator and a third-stage amine (C) in an aqueous solvent, a polymerizable monomer (B) having a (meth) acrylonitrile group is used. The method of radical polymerization is carried out while mixing with a mixer at 60 to 90 °C.
又，作為與上述不同之方法，舉例為例如首先在自由基起始劑存在下，使具有(甲基)丙烯醯基之聚合性單體(B)聚合而製造(甲基)丙烯酸系聚合物，於製造後之反應系統內添加水(例如蒸餾水)及第三級胺(C)，將該等混合，製造含有第三級胺(C)之(甲基)丙烯酸系乳膠之方法。 Further, as a method different from the above, for example, first, a (meth)acrylic polymer is produced by polymerizing a polymerizable monomer (B) having a (meth)acrylinyl group in the presence of a radical initiator. A method of producing a (meth)acrylic latex containing a third-order amine (C) by adding water (for example, distilled water) and a third-stage amine (C) to the reaction system after the production.
在自由基起始劑存在下，使具有(甲基)丙烯醯基之聚合性單體(B)聚合時，使用上述有機溶劑時(具體為例如僅使用上述有機溶劑時)，亦可於聚合後反應系統內添加水(例如蒸餾水)及第三級胺(C)後，餾除上述有機溶劑。 When the polymerizable monomer (B) having a (meth)acryl fluorenyl group is polymerized in the presence of a radical initiator, when the above organic solvent is used (specifically, for example, when only the above organic solvent is used), polymerization may be carried out. After adding water (for example, distilled water) and the third-stage amine (C) to the post reaction system, the organic solvent is distilled off.
(甲基)丙烯酸系乳膠可分別單獨使用或組合2種以上使用。 The (meth)acrylic latex may be used alone or in combination of two or more.
(構成(甲基)丙烯酸粒子之聚合物) (polymer constituting (meth)acrylic particles)
本發明中，構成(甲基)丙烯酸系乳膠中所含之(甲 基)丙烯酸粒子之聚合物，舉例為較佳樣態之一係具有烷基與羥基與羧基且主骨架為聚(甲基)丙烯酸骨架之(甲基)丙烯酸系聚合物，矽烷偶合劑(A)對於具有烷基之重複單位之莫耳比為0.020以下。 In the present invention, it is composed of (meth)acrylic latex (A) The polymer of the acrylic acid particles is exemplified by a (meth)acrylic polymer having an alkyl group and a hydroxyl group and a carboxyl group, and the main skeleton is a poly(meth)acrylic acid skeleton, and a decane coupling agent (A). The molar ratio of the repeating unit having an alkyl group is 0.020 or less.
(烷基) (alkyl)
並未特別限制上述(甲基)丙烯酸系聚合物所具有之烷基。舉例為例如與上述(甲基)丙烯酸烷基酯單體(b1)之烷基酯所具有之烷基相同者。 The alkyl group of the above (meth)acrylic polymer is not particularly limited. For example, it is the same as the alkyl group which the alkyl ester of the alkyl (meth)acrylate monomer (b1) mentioned above has.
烷基可藉由上述(甲基)丙烯酸烷基酯單體(b1)導入(甲基)丙烯酸系聚合物中。 The alkyl group can be introduced into the (meth)acrylic polymer by the above alkyl (meth)acrylate monomer (b1).
(甲基)丙烯酸系聚合物較好含有由甲基丙烯酸甲酯(MMA)與丙烯酸2-乙基己酯(2HEA)形成之重複單位作為由(甲基)丙烯酸烷基酯單體(b1)形成之重複單位。 The (meth)acrylic polymer preferably contains a repeating unit formed of methyl methacrylate (MMA) and 2-ethylhexyl acrylate (2HEA) as the alkyl (meth)acrylate monomer (b1). The repeating unit formed.
(羧基) (carboxyl)
上述(甲基)丙烯酸系聚合物所具有之羧基可直接或透過有機基與主骨架鍵結。有機基與上述相同。 The carboxyl group of the above (meth)acrylic polymer may be bonded to the main skeleton directly or through an organic group. The organic group is the same as above.
羧基可藉由(甲基)丙烯酸系單體(b2)導入(甲基)丙烯酸系聚合物中。 The carboxyl group can be introduced into the (meth)acrylic polymer by the (meth)acrylic monomer (b2).
(甲基)丙烯酸系聚合物具有由(甲基)丙烯酸系單體(b2)形成之重複單位。 The (meth)acrylic polymer has a repeating unit formed of a (meth)acrylic monomer (b2).
羧基亦可藉由第三級胺(C)而離子化。 The carboxyl group can also be ionized by the tertiary amine (C).
(羥基) (hydroxyl)
上述(甲基)丙烯酸系聚合物所具有之羥基可直接或透過有機基與主骨架鍵結。有機基與上述相同。 The hydroxyl group of the above (meth)acrylic polymer may be bonded to the main skeleton directly or through an organic group. The organic group is the same as above.
羥基可藉由上述含羥基之聚合性單體(b3)導入(甲基)丙烯酸系聚合物中。 The hydroxyl group can be introduced into the (meth)acrylic polymer by the above hydroxyl group-containing polymerizable monomer (b3).
(甲基)丙烯酸系聚合物具有由含羥基之聚合性單體(b3)形成之重複單位。 The (meth)acrylic polymer has a repeating unit formed of a hydroxyl group-containing polymerizable monomer (b3).
(主骨架) (main skeleton)
上述(甲基)丙烯酸系聚合物之主骨架具有由具有(甲基)丙烯醯基之聚合性單體(B)形成之重複單位。(甲基)丙烯醯基亦可為(甲基)丙烯醯氧基。 The main skeleton of the above (meth)acrylic polymer has a repeating unit formed of a polymerizable monomer (B) having a (meth)acryl fluorenyl group. The (meth) acrylonitrile group may also be a (meth) propylene fluorenyl group.
(甲基)丙烯酸系聚合物之重量平均分子量(Mw)可為例如10,000~500,000。 The weight average molecular weight (Mw) of the (meth)acrylic polymer may be, for example, 10,000 to 500,000.
(甲基)丙烯酸系聚合物之重量平均分子量(Mw)可藉由以四氫呋喃為溶劑之凝膠滲透層析法(GPC)以聚苯乙烯換算表示之重量平均分子量。 The weight average molecular weight (Mw) of the (meth)acrylic polymer can be expressed by polystyrene conversion by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.
本發明之組成物中含有之矽烷偶合劑(A)具有環氧丙基與水解性矽烷基。 The decane coupling agent (A) contained in the composition of the present invention has a glycidyl group and a hydrolyzable decyl group.
作為水解性矽烷基舉例為例如烷氧基矽烷基。鍵結於1個矽原子之烷氧基數較好為2個或3個。 The hydrolyzable alkylene group is exemplified by, for example, an alkoxyalkyl group. The number of alkoxy groups bonded to one halogen atom is preferably two or three.
上述烷氧基之數為2個以下時，可鍵結於矽原子之烴基並未特別限制。舉例為例如烷基。 When the number of the alkoxy groups is two or less, the hydrocarbon group which may be bonded to the ruthenium atom is not particularly limited. For example, it is an alkyl group.
使環氧丙基與水解性矽烷基鍵結之有機基並未特別限制。舉例為例如可具有如氧原子、氮原子、硫原子之雜原子之烴基。 The organic group to which the epoxy propyl group is bonded to the hydrolyzable decyl group is not particularly limited. For example, a hydrocarbon group which may have a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom.
矽烷偶合劑(A)較好為環氧丙氧基烷基三烷氧基矽烷。作為環氧丙氧基烷基三烷氧基矽烷舉例為例如3-環氧丙氧基丙基三乙氧基矽烷、3-環氧丙氧基丙基三甲氧基矽烷。 The decane coupling agent (A) is preferably a glycidoxyalkyltrialkoxydecane. Examples of the glycidoxyalkyltrialkoxide are, for example, 3-glycidoxypropyltriethoxydecane and 3-glycidoxypropyltrimethoxydecane.
矽烷偶合劑(A)可分別單獨使用或組合2種以上使用。 The decane coupling agent (A) can be used alone or in combination of two or more.
矽烷偶合劑(A)對於前述(甲基)丙烯酸烷基酯單體(b1)的莫耳比(A/b1)為0.020以下。上述莫耳比(A/b1)，基於使本發明效果更優異、儲存安定性優異之觀點，更好為0.006~0.02，又更好為0.008~0.017。 The molar ratio (A/b1) of the decane coupling agent (A) to the alkyl (meth) acrylate monomer (b1) is 0.020 or less. The above molar ratio (A/b1) is more preferably from 0.006 to 0.02, more preferably from 0.008 to 0.017, from the viewpoint of further improving the effect of the present invention and excellent storage stability.
(除此之外之成分) (other ingredients)
本發明之組成物除了上述成分以外，可進而含有如調平劑、抗氧化劑、腐蝕防止劑、光安定劑、紫外線吸收劑、矽烷偶合劑(A)以外之矽烷偶合劑、填充劑之添加劑。 The composition of the present invention may further contain, in addition to the above components, an additive such as a leveling agent, an antioxidant, a corrosion inhibitor, a photostabilizer, an ultraviolet absorber, a decane coupling agent other than the decane coupling agent (A), and a filler.
本發明之組成物舉例較佳樣態之一係僅含有(甲基)丙烯酸系乳膠與矽烷偶合劑(A)。該情況下，(甲基)丙烯酸粒子所具有之羧基亦可經第三級胺(C)離子化。 One of the preferred embodiments of the composition of the present invention contains only a (meth)acrylic latex and a decane coupling agent (A). In this case, the carboxyl group of the (meth)acrylic acid particles may be ionized by the third-order amine (C).
本發明組成物其製造方法並未特別限制。舉例為例如使上述(甲基)丙烯酸系乳膠、矽烷偶合劑(A)及任意成分混合之方法。 The method for producing the composition of the present invention is not particularly limited. For example, a method of mixing the above (meth)acrylic latex, a decane coupling agent (A), and an optional component.
本發明之組成物含有(甲基)丙烯酸粒子作為固形分。 The composition of the present invention contains (meth)acrylic acid particles as a solid component.
(甲基)丙烯酸粒子(固形分)對於組成物總量之含量為15質量%以上，較好為15~60質量%，更好為15~40質量%。 The content of the (meth)acrylic acid particles (solid content) in the total amount of the composition is 15% by mass or more, preferably 15 to 60% by mass, more preferably 15 to 40% by mass.
本發明之組成物舉例作為較佳樣態之一係實質上不含有上述過硫酸鹽或氧化還原起始劑、或起因於該等之成分(以下將該等簡稱為過硫酸鹽)。 The composition of the present invention, as one of the preferred embodiments, is substantially free of the above-mentioned persulfate or redox initiator or components derived therefrom (hereinafter simply referred to as persulfate).
所謂本發明組成物實質上不含過硫酸鹽等意指過硫酸鹽等對於本發明組成物總量之含量為0~0.1質量%。 The composition of the present invention is substantially free of persulfate or the like, and means that the persulfate or the like is contained in an amount of from 0 to 0.1% by mass based on the total amount of the composition of the present invention.
本發明之組成物係用以使基底與防水材密著而使用。 The composition of the present invention is used to adhere the substrate to the waterproof material.
上述防水材並未特別限制。舉例為例如胺基甲酸酯防水材、聚矽氧系防水材、聚硫醚系防水材。其中，較好為胺基甲酸酯防水材。 The above waterproof material is not particularly limited. For example, a urethane waterproof material, a polyoxyl water-based material, or a polysulfide-based waterproof material. Among them, a urethane waterproof material is preferred.
防水材形態並未特別限制。舉例為例如液狀、薄片狀。 The form of the waterproof material is not particularly limited. For example, it is liquid or flake.
上述基底並未特別限制。舉例為例如無機系硬質材料，具體舉例為例如灰泥、玻璃、聚矽氧硬質塗層、陶瓷、水泥、瓷器、金屬。 The above substrate is not particularly limited. For example, an inorganic hard material is specifically exemplified by, for example, plaster, glass, polyoxyn hard coat, ceramic, cement, porcelain, metal.
使用本發明組成物使基底與防水材密著之方 法為例如首先將本發明組成物塗佈於基底上，於20~28℃之條件下乾燥。 Using the composition of the present invention to make the substrate and the waterproof material close together The method is, for example, first applying the composition of the present invention to a substrate and drying it at 20 to 28 °C.
自本發明之組成物形成之底漆層即使於其中殘留水，基底與防水材之密著性亦優異，故使用本發明之組成物時，可縮短其乾燥時間。 Since the primer layer formed from the composition of the present invention has excellent adhesion to the substrate and the water repellent material even if water remains therein, the drying time can be shortened when the composition of the present invention is used.
底漆之乾燥時間可為25~40分鐘。 The drying time of the primer can be 25 to 40 minutes.
其次，於乾燥後之基底上設置防水材。防水材為液狀時，將防水材流入上述乾燥後之基底上，防水材為薄片狀時將薄片鋪於上述乾燥後之基底上，隨後 Next, a waterproof material is placed on the dried substrate. When the waterproof material is in a liquid state, the waterproof material is poured into the dried substrate, and when the waterproof material is in the form of a sheet, the sheet is spread on the dried substrate, and then
藉由在25℃、45%RH之條件下養生3~5天，可使基底與防水材密著。 The substrate and the waterproof material can be adhered by curing at 25 ° C and 45% RH for 3 to 5 days.
以下顯示實施例具體說明本發明。惟本發明不限定於實施例。 The invention is specifically illustrated by the following examples. However, the invention is not limited to the examples.
將下述表1中之「調製(甲基)丙烯酸系乳膠時使用之成分/調配量」欄所示之各成分(調配量單位為mol，但第三級胺(C)1除外)於有機溶劑(MEK)中，邊以攪拌機混合邊在80℃之條件下進行自由基聚合，自反應開始後5小時後停止聚合，於所得反應液中添加水與下述表1所示之第三級胺(C)1(三乙胺)並攪拌乳化後，餾除上述有機溶劑(MEK)，調製(甲基)丙烯酸系乳膠。 Each component shown in the column "Components/mixing amount used in preparing a (meth)acrylic latex" in Table 1 (the amount of the compound is in the order of mol, but the tertiary amine (C) 1 is excluded) is organic. In the solvent (MEK), radical polymerization was carried out at 80 ° C while mixing with a stirrer, and polymerization was stopped 5 hours after the start of the reaction, and water was added to the obtained reaction liquid and the third stage shown in Table 1 below was added. After the amine (C) 1 (triethylamine) was stirred and emulsified, the organic solvent (MEK) was distilled off to prepare a (meth)acrylic latex.
如上述調製之(甲基)丙烯酸系乳膠均係於作為分散介質之水中，分散作為分散質之(甲基)丙烯酸粒子((甲基)丙烯酸系聚合物)。 The (meth)acrylic latex prepared as described above is dispersed in water as a dispersion medium, and dispersed as a (meth)acrylic particle ((meth)acrylic polymer).
構成(甲基)丙烯酸粒子之聚合物係具有烷基與羥基與羧基，且主骨架為聚(甲基)丙烯酸骨架的(甲基)丙烯酸系聚合物。矽烷偶合劑(A)對於(甲基)丙烯酸聚合物中具有烷基之重複單位的莫耳比為0.020以下。 The polymer constituting the (meth)acrylic acid particles is a (meth)acrylic polymer having an alkyl group and a hydroxyl group and a carboxyl group, and the main skeleton is a poly(meth)acrylic acid skeleton. The decane coupling agent (A) has a molar ratio of a repeating unit having an alkyl group in the (meth)acrylic polymer of 0.020 or less.
如上述調製之各(甲基)丙烯酸系乳膠直接使用於以下之組成物製造。 Each of the (meth)acrylic latexes prepared as described above was directly used in the following compositions.
下述表1中之「調製(甲基)丙烯酸系乳膠時使用之成分/調配量」欄所示之各成分詳情如以下。 The details of each component shown in the column "Components/mixing amount used in preparing a (meth)acrylic latex" in Table 1 below are as follows.
．(甲基)丙烯酸烷基酯單體(b1)-1(MMA)：甲基丙烯酸甲酯(分子量：100) . Alkyl (meth)acrylate monomer (b1)-1 (MMA): methyl methacrylate (molecular weight: 100)
．(甲基)丙烯酸烷基酯單體(b1)-2(2EH)：丙烯酸2-乙基己酯(分子量：184) . Alkyl (meth)acrylate monomer (b1)-2 (2EH): 2-ethylhexyl acrylate (molecular weight: 184)
．(甲基)丙烯酸系單體(b2)-1(MAA)：甲基丙烯酸(分子量：87) . (Meth)acrylic monomer (b2)-1 (MAA): methacrylic acid (molecular weight: 87)
．含羥基之聚合性單體(b3)-1(HEMA)：甲基丙烯酸2-羥基乙酯(分子量：130) . Hydroxy-containing polymerizable monomer (b3)-1 (HEMA): 2-hydroxyethyl methacrylate (molecular weight: 130)
．自由基起始劑1(比較)(APS)：過硫酸銨(分子量：228) . Free Radical Initiator 1 (Comparative) (APS): Ammonium Persulfate (Molecular Weight: 228)
．自由基起始劑2(AIBN)：2,2’-偶氮雙異丁腈(分子量：164) . Free radical initiator 2 (AIBN): 2,2'-azobisisobutyronitrile (molecular weight: 164)
．還原劑1(SBS)：亞硫酸氫鈉(分子量：104) . Reducing Agent 1 (SBS): sodium hydrogen sulfite (molecular weight: 104)
．第三級胺(C)1(TEA)：三乙胺 . Tertiary amine (C) 1 (TEA): triethylamine
將如上述調製之(甲基)丙烯酸系乳膠與下述表1中「使用組合物時使用之矽烷偶合劑A/調配量」欄所示之各矽烷偶合劑A(調配量單位為mol)以攪拌機混合，製造組成物。 The (meth)acrylic latex prepared as described above and each of the decane coupling agents A shown in the column of "the amount of the decane coupling agent A used in the use of the composition" in Table 1 (the amount of the compound is mol) The mixture was mixed to prepare a composition.
又，製造組成物時，係以使(甲基)丙烯酸粒子對於組成物總量之含量(質量%)成為表1之「固形分」欄所示之值(單位：質量%)之方式，於組成物中適當添加蒸餾水。上述固形分意指(甲基)丙烯酸粒子。 In the case of producing a composition, the content (% by mass) of the total amount of the (meth)acrylic acid particles in the composition is the value (unit: mass %) shown in the column of "solid content" in Table 1. Distilled water is appropriately added to the composition. The above solid fraction means (meth)acrylic acid particles.
下述表1之調製組合物時使用之矽烷偶合劑A細節如以下。 The details of the decane coupling agent A used in the preparation of the composition of the following Table 1 are as follows.
．矽烷偶合劑A1(比較)：3-甲基丙烯醯氧基丙基三乙氧基矽烷，KBM-503，信越化學工業公司製 . Decane coupling agent A1 (comparative): 3-methacryloxypropyltriethoxydecane, KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.
．矽烷偶合劑A2(比較)：3-巰基丙基三甲氧基矽烷，KBM-803，信越化學工業公司製 . Decane coupling agent A2 (comparative): 3-mercaptopropyltrimethoxydecane, KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.
．矽烷偶合劑A3(比較)：3-胺基丙基三乙氧基矽烷，KBM-903，信越化學工業公司製 . Decane coupling agent A3 (comparative): 3-aminopropyl triethoxy decane, KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.
．矽烷偶合劑A4：3-環氧丙氧基丙基三乙氧基矽烷，KBM-403，信越化學工業公司製 . Decane coupling agent A4: 3-glycidoxypropyl triethoxy decane, KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.
使用如上述製造之組成物進行以下之常態剝離試驗。 結果示於表1。 The following normal peel test was carried out using the composition manufactured as described above. The results are shown in Table 1.
．常態剝離試驗 . Normal peel test
(試驗體之製作) (production of test body)
首先將如上述製造之各組成物以刷毛塗佈於被密著體的灰泥(10cm×20cm，PALTEK公司製)上，於25℃之條件下短時間乾燥(30分鐘乾燥)。 First, each of the compositions produced as described above was applied to the adherend-formed plaster (10 cm × 20 cm, manufactured by PALTEK Co., Ltd.), and dried at 25 ° C for a short time (drying for 30 minutes).
其次，於上述乾燥後之灰泥上流入防水材(商品名HAMATITE URBAN ROOF U-8000，橫濱橡膠股份有限公司製，胺基甲酸酯防水材)。流入後之防水材層厚度為5mm。 Next, a water-repellent material (trade name: HAMATITE URBAN ROOF U-8000, manufactured by Yokohama Rubber Co., Ltd., urethane waterproof material) was introduced into the dried mortar. The thickness of the waterproof material layer after the inflow is 5 mm.
流入防水材後之灰泥在25℃、45%RH之條件下養生3天，製作試驗體。 The mortar which had flowed into the waterproof material was cured at 25 ° C and 45% RH for 3 days to prepare a test body.
(常態剝離試驗) (normal peel test)
自如上述製作之各試驗體於23℃之條件下以180℃之角度以手剝離防水材層。 Each of the test bodies prepared as described above was peeled off by hand at a temperature of 180 ° C under the conditions of 23 ° C.
(評價基準) (evaluation benchmark)
常態剝離試驗之評價基準如以下。 The evaluation criteria of the normal peeling test are as follows.
無法自灰泥拉離防水材層時，評價為基底與防水材之密著性優異，並將其以「A」表示。 When the waterproof material layer could not be pulled out from the plaster, it was evaluated that the adhesion between the base and the waterproof material was excellent, and it was represented by "A".
可自灰泥拉離防水材層時，評價為基底與防水材之密著性低，並將其以「B」表示。 When the waterproof material layer was pulled out from the plaster, it was evaluated that the adhesion between the base and the waterproof material was low, and it was represented by "B".
如表1所示，未使用特定自由基起始劑之比較例6或不含有特定矽烷偶合劑之比較例1~5，於使底漆組成物短時間乾燥時，可以手自基底剝離防水材層，基底與防水材之密著性低。 As shown in Table 1, Comparative Example 6 in which no specific radical initiator was used or Comparative Examples 1 to 5 which did not contain a specific decane coupling agent was used to peel the waterproof material from the substrate when the primer composition was dried for a short period of time. The layer, the substrate and the waterproof material have low adhesion.
矽烷偶合劑(A)/(甲基)丙烯酸烷基酯單體(b1)超過特定範圍之比較例7，於使底漆組成物短時間乾燥時，亦與上述比較例同樣，可以手自基底剝離防水材層，基底與防水材之密著性低。 Comparative Example 7 in which the decane coupling agent (A)/alkyl (meth) acrylate monomer (b1) exceeds a specific range, and when the primer composition is dried for a short period of time, it can be hand-held from the substrate as in the above comparative example. The waterproof material layer is peeled off, and the adhesion between the substrate and the waterproof material is low.
相對於此，實施例1即使乾燥時間短，基底 與防水材之密著性亦優異。 On the other hand, in Example 1, even if the drying time is short, the substrate It is also excellent in adhesion to waterproof materials.
又，雖未示於表1，但比較例7之組成物於25℃、45%RH條件下放置2週後，比較例7之組成物中水與固形分分離，儲存安定性差。 Further, although not shown in Table 1, the composition of Comparative Example 7 was allowed to stand under the conditions of 25 ° C and 45% RH for 2 weeks, and the water of the composition of Comparative Example 7 was separated from the solid fraction, and the storage stability was poor.
相對於此，實施例1之組成物與上述同樣儲存後組成物亦無變化，儲存安定性優異。 On the other hand, the composition of Example 1 did not change the composition after storage as described above, and was excellent in storage stability.
如此可判知本發明之組成物的儲存安定性亦優異。 Thus, it was found that the composition of the present invention is also excellent in storage stability.
Claims (11)
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| JP6536344B2 (en) * | 2015-10-13 | 2019-07-03 | 横浜ゴム株式会社 | Waterborne primer composition for sealing material |
| CN108137982B (en) * | 2015-10-13 | 2020-07-14 | 横滨橡胶株式会社 | Aqueous primer composition for sealing material |
| JP6864430B2 (en) * | 2015-10-13 | 2021-04-28 | 横浜ゴム株式会社 | Water-based primer composition for polyurethane-based sealant |
| JP6834599B2 (en) * | 2017-03-02 | 2021-02-24 | 横浜ゴム株式会社 | Primer composition |
| JP6972937B2 (en) * | 2017-11-07 | 2021-11-24 | 東洋製罐グループホールディングス株式会社 | Laminated film with excellent moisture barrier properties |
| JP7297188B2 (en) * | 2018-09-14 | 2023-06-26 | シーカ・ジャパン株式会社 | primer composition |
| EP3856702A1 (en) * | 2018-09-27 | 2021-08-04 | Dow Global Technologies LLC | Coating composition for controlling efflorescence |
| CN109337582A (en) * | 2018-11-16 | 2019-02-15 | 浙江中卓建设有限公司 | A kind of preparation method and its construction technology of environment-protecting and non-poisonous harmful waterproof paint |
| CN109666321A (en) * | 2018-12-25 | 2019-04-23 | 重庆纳斯美科技发展有限公司 | A kind of sheet metal roofing waterproof coating material and preparation method thereof |
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| JP4771716B2 (en) * | 2004-10-01 | 2011-09-14 | エスケー化研株式会社 | Aqueous primer composition and coating method thereof |
| EP2907856B1 (en) * | 2012-10-11 | 2019-05-01 | The Yokohama Rubber Co., Ltd. | Water-based primer composition |
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