JP4581413B2 - Allylamine acid addition salt polymer, process for producing the same, and ink jet recording paper agent - Google Patents
Allylamine acid addition salt polymer, process for producing the same, and ink jet recording paper agent Download PDFInfo
- Publication number
- JP4581413B2 JP4581413B2 JP2004021995A JP2004021995A JP4581413B2 JP 4581413 B2 JP4581413 B2 JP 4581413B2 JP 2004021995 A JP2004021995 A JP 2004021995A JP 2004021995 A JP2004021995 A JP 2004021995A JP 4581413 B2 JP4581413 B2 JP 4581413B2
- Authority
- JP
- Japan
- Prior art keywords
- addition salt
- acid addition
- allylamine
- group
- acid
- 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 - Lifetime
Links
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 title claims description 175
- 150000003839 salts Chemical class 0.000 title claims description 90
- 239000002253 acid Substances 0.000 title claims description 79
- 229920000642 polymer Polymers 0.000 title claims description 72
- 239000003795 chemical substances by application Substances 0.000 title claims description 23
- 238000000034 method Methods 0.000 title claims description 15
- 239000000178 monomer Substances 0.000 claims description 45
- 239000007870 radical polymerization initiator Substances 0.000 claims description 27
- 238000004519 manufacturing process Methods 0.000 claims description 21
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- -1 diallylamine compound Chemical class 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 125000003277 amino group Chemical group 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000002798 polar solvent Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 238000004078 waterproofing Methods 0.000 claims description 7
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 5
- 239000003125 aqueous solvent Substances 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001408 amides Chemical class 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 37
- 238000006116 polymerization reaction Methods 0.000 description 36
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 25
- 229920001577 copolymer Polymers 0.000 description 25
- 239000007864 aqueous solution Substances 0.000 description 24
- 229910052757 nitrogen Inorganic materials 0.000 description 22
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 21
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 15
- 238000005227 gel permeation chromatography Methods 0.000 description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 10
- 239000000460 chlorine Substances 0.000 description 10
- 229910052801 chlorine Inorganic materials 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 7
- GBCKRQRXNXQQPW-UHFFFAOYSA-N n,n-dimethylprop-2-en-1-amine Chemical compound CN(C)CC=C GBCKRQRXNXQQPW-UHFFFAOYSA-N 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- IOXXVNYDGIXMIP-UHFFFAOYSA-N n-methylprop-2-en-1-amine Chemical compound CNCC=C IOXXVNYDGIXMIP-UHFFFAOYSA-N 0.000 description 6
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical compound NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 6
- 239000013053 water resistant agent Substances 0.000 description 6
- 229940045996 isethionic acid Drugs 0.000 description 5
- 229940098779 methanesulfonic acid Drugs 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 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 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 4
- WGESLFUSXZBFQF-UHFFFAOYSA-N n-methyl-n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCN(C)CC=C WGESLFUSXZBFQF-UHFFFAOYSA-N 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 0 CC(C)C(CC(C)(*)*)CN(C)* Chemical compound CC(C)C(CC(C)(*)*)CN(C)* 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229920003169 water-soluble polymer Polymers 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- QMYCJCOPYOPWTI-UHFFFAOYSA-N 2-[(1-amino-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidamide;hydron;chloride Chemical compound Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N QMYCJCOPYOPWTI-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 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
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- GNWBLLYJQXKPIP-ZOGIJGBBSA-N (1s,3as,3bs,5ar,9ar,9bs,11as)-n,n-diethyl-6,9a,11a-trimethyl-7-oxo-2,3,3a,3b,4,5,5a,8,9,9b,10,11-dodecahydro-1h-indeno[5,4-f]quinoline-1-carboxamide Chemical compound CN([C@@H]1CC2)C(=O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H](C(=O)N(CC)CC)[C@@]2(C)CC1 GNWBLLYJQXKPIP-ZOGIJGBBSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-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
- ATFXTFMLMZLRII-UHFFFAOYSA-N 2-(2-acetyloxybutan-2-yldiazenyl)butan-2-yl acetate Chemical compound CC(=O)OC(C)(CC)N=NC(C)(CC)OC(C)=O ATFXTFMLMZLRII-UHFFFAOYSA-N 0.000 description 1
- PZILQNGWHUGDLZ-UHFFFAOYSA-N 2-(2-acetyloxypropan-2-yldiazenyl)propan-2-yl acetate Chemical compound CC(=O)OC(C)(C)N=NC(C)(C)OC(C)=O PZILQNGWHUGDLZ-UHFFFAOYSA-N 0.000 description 1
- OXQGTIUCKGYOAA-UHFFFAOYSA-N 2-Ethylbutanoic acid Chemical compound CCC(CC)C(O)=O OXQGTIUCKGYOAA-UHFFFAOYSA-N 0.000 description 1
- LPMKLJSGINBUNE-UHFFFAOYSA-N 2-cyclohexyl-2-[[2-cyclohexyl-1-(hydroxyamino)-1-oxopropan-2-yl]diazenyl]-n-hydroxypropanamide Chemical compound C1CCCCC1C(C(=O)NO)(C)N=NC(C)(C(=O)NO)C1CCCCC1 LPMKLJSGINBUNE-UHFFFAOYSA-N 0.000 description 1
- WTRQSVQVTAXGDR-UHFFFAOYSA-N 2-cyclohexyl-N'-hydroxypropanimidamide Chemical compound C1(CCCCC1)C(C(N)=NO)C WTRQSVQVTAXGDR-UHFFFAOYSA-N 0.000 description 1
- ITUUDQHMMMKCCX-UHFFFAOYSA-N 2-ethylbutanehydrazide Chemical compound CCC(CC)C(=O)NN ITUUDQHMMMKCCX-UHFFFAOYSA-N 0.000 description 1
- QKRMFCXDTFLKKT-UHFFFAOYSA-N 2-hydroxyethanesulfonic acid Chemical compound OCCS(O)(=O)=O.OCCS(O)(=O)=O QKRMFCXDTFLKKT-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- XZHQUWDDJFKLND-UHFFFAOYSA-N 2-methylbutanehydrazide Chemical compound CCC(C)C(=O)NN XZHQUWDDJFKLND-UHFFFAOYSA-N 0.000 description 1
- PLNNJQXIITYYTN-UHFFFAOYSA-N 2-methylpropanehydrazide Chemical compound CC(C)C(=O)NN PLNNJQXIITYYTN-UHFFFAOYSA-N 0.000 description 1
- IJJCVGQRJQXQDH-UHFFFAOYSA-N 3-[[3-carboxy-1-(hydroxyamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-4-(hydroxyamino)-3-methyl-4-oxobutanoic acid Chemical compound OC(=O)CC(C)(C(=O)NO)N=NC(C)(CC(O)=O)C(=O)NO IJJCVGQRJQXQDH-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical group [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- XQKVFABGANYUJD-UHFFFAOYSA-N 4-[[4-carboxy-1-(hydroxyamino)-2-methyl-1-oxobutan-2-yl]diazenyl]-5-(hydroxyamino)-4-methyl-5-oxopentanoic acid Chemical compound OC(=O)CCC(C)(C(=O)NO)N=NC(C)(CCC(O)=O)C(=O)NO XQKVFABGANYUJD-UHFFFAOYSA-N 0.000 description 1
- OOQGEIDHPCFVDR-UHFFFAOYSA-N 4-amino-4-hydroxyimino-3-methylbutanoic acid Chemical compound C(=O)(O)CC(C(N)=NO)C OOQGEIDHPCFVDR-UHFFFAOYSA-N 0.000 description 1
- RHEUJUOLGVOBNU-UHFFFAOYSA-N 4-hydroxyhexanehydrazide Chemical compound CCC(O)CCC(=O)NN RHEUJUOLGVOBNU-UHFFFAOYSA-N 0.000 description 1
- LQVHERLFWFKPNY-UHFFFAOYSA-N 4-hydroxypentanehydrazide Chemical compound CC(O)CCC(=O)NN LQVHERLFWFKPNY-UHFFFAOYSA-N 0.000 description 1
- DXNSOGCOBGZUAZ-UHFFFAOYSA-N 5-amino-5-hydroxyimino-4-methylpentanoic acid Chemical compound C(=O)(O)CCC(C(N)=NO)C DXNSOGCOBGZUAZ-UHFFFAOYSA-N 0.000 description 1
- VQLUPYVJAAFBFP-UHFFFAOYSA-N 6-amino-6-hydroxyimino-4-methylhexanoic acid Chemical compound CC(CCC(O)=O)CC(N)=NO VQLUPYVJAAFBFP-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- UBVXAHLTIXYIAU-UHFFFAOYSA-N C(C)C(C#N)CCN(CC)CC Chemical compound C(C)C(C#N)CCN(CC)CC UBVXAHLTIXYIAU-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000283014 Dama Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- OCWLYWIFNDCWRZ-UHFFFAOYSA-N Methyl (S)-2-Methylbutanoate Chemical compound CCC(C)C(=O)OC OCWLYWIFNDCWRZ-UHFFFAOYSA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- FPXVYMJIOCACLZ-UHFFFAOYSA-N N'-hydroxy-2,2,4-trimethylpentanimidamide Chemical compound C(C(C)C)C(C(N)=NO)(C)C FPXVYMJIOCACLZ-UHFFFAOYSA-N 0.000 description 1
- SKLDZLWKWYXGFP-UHFFFAOYSA-N N'-hydroxy-2-methyl-3-phenylpropanimidamide Chemical compound C(C1=CC=CC=C1)C(C(N)=NO)C SKLDZLWKWYXGFP-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- DRVBDWGGQPJMIU-UHFFFAOYSA-N [1-[(1-formyloxycyclohexyl)diazenyl]cyclohexyl] formate Chemical compound C1CCCCC1(OC=O)N=NC1(OC=O)CCCCC1 DRVBDWGGQPJMIU-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 229920006322 acrylamide copolymer Polymers 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 125000005001 aminoaryl group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WYFGBFHRZGNGAU-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene;hydrochloride Chemical compound Cl.N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 WYFGBFHRZGNGAU-UHFFFAOYSA-N 0.000 description 1
- ZJZDQLCRNFFYFY-UHFFFAOYSA-N bis[2-(4,5-dihydro-1h-imidazol-2-yl)propan-2-yl]diazene;sulfuric acid Chemical compound OS(O)(=O)=O.N=1CCNC=1C(C)(C)N=NC(C)(C)C1=NCCN1 ZJZDQLCRNFFYFY-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920006319 cationized starch Polymers 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000004966 cyanoalkyl group Chemical group 0.000 description 1
- 125000002944 cyanoaryl group Chemical group 0.000 description 1
- JNSGIVNNHKGGRU-JYRVWZFOSA-N diethoxyphosphinothioyl (2z)-2-(2-amino-1,3-thiazol-4-yl)-2-methoxyiminoacetate Chemical compound CCOP(=S)(OCC)OC(=O)C(=N/OC)\C1=CSC(N)=N1 JNSGIVNNHKGGRU-JYRVWZFOSA-N 0.000 description 1
- YIOJGTBNHQAVBO-UHFFFAOYSA-N dimethyl-bis(prop-2-enyl)azanium Chemical compound C=CC[N+](C)(C)CC=C YIOJGTBNHQAVBO-UHFFFAOYSA-N 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- WDAXFOBOLVPGLV-UHFFFAOYSA-N ethyl isobutyrate Chemical compound CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 1
- SIVVHUQWDOGLJN-UHFFFAOYSA-N ethylsulfamic acid Chemical compound CCNS(O)(=O)=O SIVVHUQWDOGLJN-UHFFFAOYSA-N 0.000 description 1
- 238000002523 gelfiltration Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VUQUOGPMUUJORT-UHFFFAOYSA-N methyl 4-methylbenzenesulfonate Chemical compound COS(=O)(=O)C1=CC=C(C)C=C1 VUQUOGPMUUJORT-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- BHIWKHZACMWKOJ-UHFFFAOYSA-N methyl isobutyrate Chemical compound COC(=O)C(C)C BHIWKHZACMWKOJ-UHFFFAOYSA-N 0.000 description 1
- MYMDOKBFMTVEGE-UHFFFAOYSA-N methylsulfamic acid Chemical compound CNS(O)(=O)=O MYMDOKBFMTVEGE-UHFFFAOYSA-N 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- ZFGUAQSDWQIVMM-UHFFFAOYSA-N n'-hydroxy-2-methylbutanimidamide Chemical compound CCC(C)C(N)=NO ZFGUAQSDWQIVMM-UHFFFAOYSA-N 0.000 description 1
- JHRDEHLFNLLCQS-UHFFFAOYSA-N n'-hydroxy-2-methylpropanimidamide Chemical compound CC(C)C(N)=NO JHRDEHLFNLLCQS-UHFFFAOYSA-N 0.000 description 1
- KFRRAHGTTHZCNG-UHFFFAOYSA-N n'-hydroxy-2-phenylpropanimidamide Chemical compound ON=C(N)C(C)C1=CC=CC=C1 KFRRAHGTTHZCNG-UHFFFAOYSA-N 0.000 description 1
- JWAJUTZQGZBKFS-UHFFFAOYSA-N n,n-diethylprop-2-en-1-amine Chemical compound CCN(CC)CC=C JWAJUTZQGZBKFS-UHFFFAOYSA-N 0.000 description 1
- YXDIBARHIUGNEA-UHFFFAOYSA-N n-amino-n-cyclohexylformamide Chemical compound O=CN(N)C1CCCCC1 YXDIBARHIUGNEA-UHFFFAOYSA-N 0.000 description 1
- XXKFHYIDWHPLHG-UHFFFAOYSA-N n-butyl-n-prop-2-enylbutan-1-amine Chemical compound CCCCN(CC=C)CCCC XXKFHYIDWHPLHG-UHFFFAOYSA-N 0.000 description 1
- PUUULGNNRPBVBA-UHFFFAOYSA-N n-ethylprop-2-en-1-amine Chemical compound CCNCC=C PUUULGNNRPBVBA-UHFFFAOYSA-N 0.000 description 1
- UUTHZBDVSDGIIH-UHFFFAOYSA-N n-hydroxy-2-[[1-(hydroxyamino)-1-oxo-2-phenylpropan-2-yl]diazenyl]-2-phenylpropanamide Chemical compound C=1C=CC=CC=1C(C)(C(=O)NO)N=NC(C)(C(=O)NO)C1=CC=CC=C1 UUTHZBDVSDGIIH-UHFFFAOYSA-N 0.000 description 1
- JVAAYUYZJCNTQJ-UHFFFAOYSA-N n-hydroxy-2-[[1-(hydroxyamino)-2-methyl-1-oxo-3-phenylpropan-2-yl]diazenyl]-2-methyl-3-phenylpropanamide Chemical compound C=1C=CC=CC=1CC(C)(C(=O)NO)N=NC(C(=O)NO)(C)CC1=CC=CC=C1 JVAAYUYZJCNTQJ-UHFFFAOYSA-N 0.000 description 1
- HYYJPSNVZDDAJL-UHFFFAOYSA-N n-hydroxy-2-[[1-(hydroxyamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound ONC(=O)C(C)(C)N=NC(C)(C)C(=O)NO HYYJPSNVZDDAJL-UHFFFAOYSA-N 0.000 description 1
- SNAUETXKUXDMFB-UHFFFAOYSA-N n-prop-2-enylbutan-1-amine Chemical compound CCCCNCC=C SNAUETXKUXDMFB-UHFFFAOYSA-N 0.000 description 1
- HUEPADWXXGLLSW-UHFFFAOYSA-N n-prop-2-enylpropan-1-amine Chemical compound CCCNCC=C HUEPADWXXGLLSW-UHFFFAOYSA-N 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 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
- 239000000843 powder Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- FJWSMXKFXFFEPV-UHFFFAOYSA-N prop-2-enamide;hydrochloride Chemical compound Cl.NC(=O)C=C FJWSMXKFXFFEPV-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011780 sodium chloride Substances 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
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Images
Description
本発明は、アリルアミン類酸付加塩重合体、その製造方法、インクジェット記録紙用薬剤およびインクジェット記録用紙に関する。さらに詳しくは、本発明は、塩素を含まず、かつ水溶性に優れ、インクジェット記録紙用耐水化剤などとして好適なアリルアミン類酸付加塩重合体、このものを簡単なプロセスで効率よく製造する方法、前記アリルアミン類酸付加塩重合体を含むインクジェット記録紙用薬剤、および該薬剤を用いてなる耐水性を向上させたインクジェット記録用紙に関するものである。 The present invention relates to an allylamine acid addition salt polymer, a method for producing the same, a chemical for ink jet recording paper, and an ink jet recording paper. More specifically, the present invention relates to an allylamine acid addition salt polymer that does not contain chlorine, has excellent water solubility, and is suitable as a water-proofing agent for inkjet recording paper, and a method for efficiently producing the same by a simple process. The present invention relates to a chemical for an ink jet recording paper containing the allylamine acid addition salt polymer, and an ink jet recording paper having improved water resistance using the chemical.
一般の水溶性高分子化合物は、その分子量、イオン性等によって、ろ水性向上剤、歩留り向上剤、サイジング剤、紙力増強剤、紙塗工剤、紙加工剤をはじめとする製紙用薬剤として製紙分野で大量に用いられている。
一方、近年、コンピュータ利用技術の普及により、コンピュータにより作成した資料をプリンターなどを用いてプリントアウトすることが頻繁に行われるようになってきた。その際使用されるプリンターとしてはドットインパクトプリンター、レーザープリンター、サーマルプリンター、インクジェットプリンターなどが挙げられるが、プリントアウト時の機械的騒音がほとんどなく、かつプリントアウトに伴うランニングコストの低さから、インクジェットプリンターが多く用いられている。このインクジェットプリンターは、インクをジェット状に噴射して印刷するタイプのプリンターであり、それに用いられる用紙としては、通常、普通紙やコート紙が多く用いられている。
そして、インクジェット記録用紙として普通紙を用いた場合には、記録後水が付着した際、染料が滲み出るなどの問題が生じるので、一般に耐水化剤が使用される。この耐水化剤としては、例えばアリルアミン類酸付加塩重合体や、ジアリルジメチルアンモニウムクロリド−アクリルアミド共重合体（例えば、特許文献１参照）などが用いられている。
General water-soluble polymer compounds are used as paper making agents, including freeness improvers, yield improvers, sizing agents, paper strength enhancers, paper coating agents, and paper processing agents, depending on their molecular weight and ionicity. Used in large quantities in the papermaking field.
On the other hand, in recent years, with the spread of computer utilization technology, it has become frequent to print out materials created by a computer using a printer or the like. Printers used at that time include dot impact printers, laser printers, thermal printers, inkjet printers, etc., but there is almost no mechanical noise at the time of printout, and because of the low running cost associated with printout, inkjet Many printers are used. This ink jet printer is a type of printer that prints by jetting ink in the form of a jet. Usually, plain paper or coated paper is often used as paper used in the ink jet printer.
When plain paper is used as the ink jet recording paper, there is a problem that the dye oozes out when water adheres after recording. Therefore, a water-proofing agent is generally used. As this water-proofing agent, for example, an allylamine acid addition salt polymer, a diallyldimethylammonium chloride-acrylamide copolymer (for example, see Patent Document 1) and the like are used.
しかしながら、これらの耐水化剤を用いて製造されたインクジェット記録用紙は塩素を含むために、その用紙を廃棄し、焼却した場合に、量は少ないが、有害なダイオキシン化合物が発生する可能性がある。したがって、環境上の問題から、非塩素耐水化剤が求められている。
ところが、非塩素耐水化剤を得るために、塩酸付加塩以外のアリルアミン類酸付加塩、例えば硫酸塩やリン酸塩などを既知の方法で重合させた場合、得られるアリルアミン類酸付加塩重合体は、水溶性に劣るために実用的でなく、耐水化剤としての用途や、その他用途にも実際には使用されていないのが実状である。
一方、水溶性の高い非塩素アリルアミン類酸付加塩重合体として、例えばアリルアミン類酢酸付加塩重合体が知られている。しかしながら、このアリルアミン類酢酸付加塩重合体を簡単なプロセスで得るために、原料単量体としてアリルアミン類酢酸付加塩を用い、重合させようとしても、該酢酸付加塩では重合しないという問題があった。そのため、アリルアミン類酢酸付加塩重合体を得るには、まずアリルアミン類塩酸付加塩を重合させ、次いで得られるアリルアミン類塩酸付加塩重合体をアルカリで中和したのち、生成する塩を取り除き、遊離のアリルアミン類重合体を得、これに酢酸を加えてアリルアミン類酢酸付加塩重合体を製造するのが一般的であった。しかしながら、この場合、製造工程が煩雑であって生産性が悪く、コスト高になるのを免れないという問題が生じる。
However, when an allylamine acid addition salt other than a hydrochloric acid addition salt, for example, sulfate or phosphate is polymerized by a known method in order to obtain a chlorine-free water-resistant agent, the resulting allylamine acid addition salt polymer is obtained. Since it is inferior in water solubility, it is not practical, and is actually not used for water-proofing agents or other uses.
On the other hand, as non-chlorine allylamine acid addition salt polymers having high water solubility, for example, allylamine acetic acid addition salt polymers are known. However, in order to obtain this allylamine acetic acid addition salt polymer by a simple process, there is a problem that even if an allylamine acetic acid addition salt is used as a raw material monomer and polymerized, the acetic acid addition salt does not polymerize. . Therefore, to obtain an allylamine acetic acid addition salt polymer, first, the allylamine hydrochloride addition salt is polymerized, and then the resulting allylamine hydrochloride addition salt polymer is neutralized with an alkali. In general, an allylamine polymer was obtained, and acetic acid was added thereto to produce an allylamine acetic acid addition salt polymer. However, in this case, there is a problem that the manufacturing process is complicated, the productivity is poor, and the cost is unavoidable.
本発明は、このような事情のもとで、塩素を含まず、かつ水溶性に優れ、インクジェット記録紙用耐水化剤などとして好適なアリルアミン類酸付加塩重合体、このものを含むインクジェット記録紙用薬剤、および該薬剤を用いてなる耐水性を向上させたインクジェット記録用紙を提供することを目的とするものである。 Under such circumstances, the present invention is an allylamine acid addition salt polymer that does not contain chlorine, has excellent water solubility, and is suitable as a waterproofing agent for ink jet recording paper, and ink jet recording paper containing the same. It is an object of the present invention to provide a medical agent and an ink jet recording paper having improved water resistance using the chemical.
従来、極性溶媒中において、水溶性アゾ系ラジカル重合開始剤や過硫酸塩系ラジカル重合開始剤の存在下に、アリルアミン類付加塩を重合させる場合、酸付加塩として、塩酸塩、硫酸塩、リン酸塩などの鉱酸塩は重合できるが、酢酸塩などの有機酸塩では重合しないと思われていた。
本発明者らは、前記目的を達成するために鋭意研究を重ねた結果、意外にも、アリルアミン類の酸付加塩としてスルホン酸基を含む特定の有機酸塩を用いることにより、重合反応が進行し、塩素を含まず、かつ水溶性に優れる重合体が得られることを見出した。本発明は、かかる知見に基づいて完成したものである。
Conventionally, when an allylamine addition salt is polymerized in a polar solvent in the presence of a water-soluble azo radical polymerization initiator or a persulfate radical polymerization initiator, as an acid addition salt, hydrochloride, sulfate, phosphorus It was thought that mineral acid salts such as acid salts could be polymerized, but not organic acid salts such as acetates.
Surprisingly, the present inventors have conducted extensive research to achieve the above object, and surprisingly, the polymerization reaction proceeds by using a specific organic acid salt containing a sulfonic acid group as the acid addition salt of allylamines. And it discovered that the polymer which does not contain chlorine and was excellent in water solubility was obtained. The present invention has been completed based on such findings.
すなわち、本発明は、
（１）一般式（Ｉ）
That is, the present invention
(1) General formula (I)
（式中、Ｒ１およびＲ２は、それぞれ独立に水素原子またはヒドロキシル基を含んでいてもよい炭素数１〜４のアルキル基、Ｙ１はヒドロキシル基を含む炭素数１〜４のアルキル基または炭素数１〜４のアルキル基が置換されていてもよいアミノ基を示す。）
で表される構成単位、並びに一般式（ＩＩ−ａ）および一般式（ＩＩ−ｂ）
(Wherein, R 1 and R 2 are each independently a hydrogen atom or a hydroxyl group optionally containing an the alkyl group having 1 to 4 carbon atoms, Y 1 is an alkyl group having 1 to 4 carbon including carbon hydroxyl group Or an amino group which may be substituted with an alkyl group having 1 to 4 carbon atoms.)
As well as the general formula (II-a) and the general formula (II-b)
（式中、Ｒ３は水素原子またはヒドロキシル基を含んでいてもよい炭素数１〜４のアルキル基、Ｙ２はヒドロキシル基を含む炭素数１〜４のアルキル基または炭素数１〜４のアルキル基が置換されていてもよいアミノ基を示す。）
で表される構成単位の中から選ばれる少なくとも１種をからなることを特徴とするアリルアミン類酸付加塩重合体、
（２）一般式（Ｉ）におけるＹ１−ＳＯ３Ｈ、並びに一般式（ＩＩ−ａ）および（ＩＩ−ｂ）におけるＹ２−ＳＯ３Ｈが、それぞれ独立にイセチオン酸またはアミド硫酸である上記（１）項に記載のアリルアミン類酸付加塩重合体、
（３）極性溶媒中において、水溶性アゾ系ラジカル重合開始剤および／または過硫酸塩系ラジカル重合開始剤の存在下に、一般式（ＩＩＩ）
(Wherein, R 3 is a hydrogen atom or hydroxyl group which may contain an alkyl group having 1 to 4 carbon atoms, Y 2 is a hydroxyl group a including 1 to 4 carbon atoms alkyl or 1 to 4 carbon atoms (The amino group which the alkyl group may be substituted is shown.)
An allylamine acid addition salt polymer comprising at least one selected from the structural units represented by:
(2) In formula (I) in Y 1 -SO 3 H, and formula (II-a) and (II-b) in the Y 2 -SO 3 H are are each independently Lee Sechion acid or amide acid The allylamine acid addition salt polymer as described in (1) above,
(3) In a polar solvent, in the presence of a water-soluble azo radical polymerization initiator and / or a persulfate radical polymerization initiator, the compound represented by the general formula (III)
で表されるモノアリルアミン類酸付加塩、および／または一般式（ＩＶ）
And / or a monoallylamine acid addition salt represented by general formula (IV)
（式中、Ｒ３は水素原子またはヒドロキシル基を含んでいてもよい炭素数１〜４のアルキル基、Ｙ２はヒドロキシル基を含んでいてもよい炭素数１〜４のアルキル基または炭素数１〜４のアルキル基が置換されていてもよいアミノ基を示す。）
で表されるジアリルアミン類酸付加塩からなる単量体を重合させて、分子量が１０，９０ ０以上のアリルアミン類酸付加塩重合体を得ることを特徴とする、アリルアミン類酸付加塩重合体の製造方法、
（４）極性溶媒が水系溶媒である上記（３）項に記載の方法、
（５）上記（１）又は（２）項に記載のアリルアミン類酸付加塩重合体を含むことを特徴とするインクジェット記録紙用薬剤、および
（６）耐水化剤として用いられる上記（５）項に記載のインクジェット記録紙用薬剤
を提供するものである。
(In the formula, R 3 is a hydrogen atom or a C1-C4 alkyl group that may contain a hydroxyl group, Y 2 is a C1-C4 alkyl group that may contain a hydroxyl group, or C1 -4 represents an amino group on which the alkyl group may be substituted.)
A monomer consisting of diallylamine compound acid addition salt represented in by polymerizing, molecular weight and obtaining a 10,90 0 or more allylamines acid addition salt polymer, A Riruamin such acid addition salt polymer Manufacturing method,
(4) The method according to (3) above, wherein the polar solvent is an aqueous solvent,
(5) The ink for an ink jet recording paper comprising the allylamine acid acid addition salt polymer described in the above (1) or (2), and (6) the above (5) used as a water-resistant agent. The pharmaceutical for inkjet recording paper as described in 1 above is provided.
本発明によれば、塩素を含まず、かつ水溶性に優れ、インクジェット記録紙用耐水化剤などとして好適なアリルアミン類酸付加塩重合体、およびこのものを簡単なプロセスで効率よく製造する方法を提供することができる。
また、前記アリルアミン類酸付加塩重合体を含むインクジェット記録紙用薬剤、および該薬剤を用いてなる耐水性を向上させたインクジェット記録用紙を提供することができる。
According to the present invention, there is provided an allylamine acid addition salt polymer that does not contain chlorine, has excellent water solubility, and is suitable as a waterproofing agent for ink jet recording paper, and a method for efficiently producing the same by a simple process. Can be provided.
Further, it is possible to provide an ink jet recording paper agent containing the allylamine acid addition salt polymer, and an ink jet recording paper having improved water resistance using the agent.
本発明のアリルアミン類酸付加塩重合体は、構成単位として、一般式（Ｉ） The allylamine acid addition salt polymer of the present invention has a general formula (I) as a structural unit.
前記一般式（Ｉ）で表される構成単位におけるＲ１およびＲ２、並びに一般式（ＩＩ−ａ）、（ＩＩ−ｂ）で表される構成単位におけるＲ３は、それぞれ水素原子、水酸基を有していてもよい炭素数１〜４のアルキル基を示す。ここで、水酸基を有していてもよい炭素数１〜４のアルキル基は直鎖状、分岐状のいずれであってもよく、このようなものとしては、例えばメチル基、エチル基、ｎ−プロピル基、イソプロピル基、各種ブチル基、２−ヒドロキシエチル基、２−ヒドロキシプロピル基、３−ヒドロキシプロピル基などを好ましく挙げることができる。
前記一般式（Ｉ）におけるＲ１とＲ２は、たがいに同一であってもよいし、異なっていてもよい。また、一般式（Ｉ）、および一般式（ＩＩ−ａ）、（ＩＩ−ｂ）で表される構成単位において、それぞれ酸付加塩を形成するＹ１−ＳＯ３ＨおよびＹ２−ＳＯ３ＨにおけるＹ１およびＹ２は、それぞれヒドロキシル基を含んでいてもよい炭素数１〜４のアルキル基または炭素数１〜４のアルキル基が置換されていてもよいアミノ基を示す。
前記Ｙ１−ＳＯ３ＨおよびＹ２−ＳＯ３Ｈの具体例としては、それぞれメタンスルホン酸、エタンスルホン酸、イセチオン酸（２−ヒドロキシエタン−１−スルホン酸）、アミド硫酸、Ｎ−メチルアミド硫酸、Ｎ−エチルアミド硫酸など、好ましくはメタンスルホン酸、イセチオン酸およびアミド硫酸を挙げることができる。本発明のアリルアミン類酸付加塩重合体が共重合体である場合、該共重合体を構成する単量体単位における酸成分（Ｙ１−ＳＯ３Ｈ、Ｙ２−ＳＯ３Ｈ）は、同一であってもよいし、異なっていてもよい。
R 1 and R 2 in the structural unit represented by the general formula (I), and the general formula (II-a), the R 3 are each a hydrogen atom, a hydroxyl group in the structural unit represented by (II-b) The C1-C4 alkyl group which may have is shown. Here, the alkyl group having 1 to 4 carbon atoms which may have a hydroxyl group may be either linear or branched, and examples thereof include a methyl group, an ethyl group, and n- Preferable examples include propyl group, isopropyl group, various butyl groups, 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group and the like.
R 1 and R 2 in the general formula (I) may be the same or different. In the structural units represented by the general formula (I) and the general formulas (II-a) and (II-b), Y 1 -SO 3 H and Y 2 -SO 3 H which form acid addition salts, respectively. Y 1 and Y 2 in each represent an alkyl group having 1 to 4 carbon atoms which may contain a hydroxyl group or an amino group which may be substituted with an alkyl group having 1 to 4 carbon atoms.
Specific examples of Y 1 —SO 3 H and Y 2 —SO 3 H include methanesulfonic acid, ethanesulfonic acid, isethionic acid (2-hydroxyethane-1-sulfonic acid), amidosulfuric acid, and N-methylamidosulfuric acid, respectively. N-ethylamidosulfuric acid, preferably methanesulfonic acid, isethionic acid and amidosulfuric acid. When the allylamine acid addition salt polymer of the present invention is a copolymer, the acid components (Y 1 -SO 3 H, Y 2 -SO 3 H) in the monomer units constituting the copolymer are the same. It may be different or different.
本発明のアリルアミン類酸付加塩重合体の具体的な態様としては、
（１）モノアリルアミン酸付加塩重合体、
（２）Ｎ−アルキルモノアリルアミン酸付加塩重合体、
（３）Ｎ，Ｎ−ジアルキルモノアリルアミン酸付加塩重合体、
（４）ジアリルアミン酸付加塩重合体、
（５）Ｎ−アルキルジアリルアミン酸付加塩重合体、
（６）（Ａ）モノアリルアミン酸付加塩と、（Ｂ）Ｎ−アルキルモノアリルアミン酸付加塩、Ｎ，Ｎ−ジアルキルモノアリルアミン酸付加塩、ジアリルアミン酸付加塩およびＮ−アルキルジアリルアミン酸付加塩の中から選ばれる少なくとも１種のアリルアミン類酸付加塩との共重合体、
（７）（Ｃ）Ｎ−アルキルモノアリルアミン酸付加塩と、（Ｄ）Ｎ，Ｎ−ジアルキルモノアリルアミン酸付加塩、ジアリルアミン酸付加塩およびＮ−アルキルジアリルアミン酸付加塩の中から選ばれる少なくとも１種のアリルアミン類酸付加塩との共重合体、および
（８）（Ｅ）Ｎ，Ｎ−ジアルキルモノアリルアミン酸付加塩と（Ｆ）ジアリルアミン酸付加塩および／またはＮ−アルキルジアリルアミン酸付加塩との共重合体、
を挙げることができる。
As a specific aspect of the allylamine acid addition salt polymer of the present invention,
(1) Monoallylamine acid addition salt polymer,
(2) N-alkyl monoallylamine acid addition salt polymer,
(3) N, N-dialkylmonoallylamine acid addition salt polymer,
(4) diallylamic acid addition salt polymer,
(5) N-alkyldiallylamine acid addition salt polymer,
(6) Among (A) monoallylamine acid addition salt and (B) N-alkylmonoallylamine acid addition salt, N, N-dialkylmonoallylamine acid addition salt, diallylaminate addition salt and N-alkyldiallylaminate addition salt A copolymer with at least one allylamine acid addition salt selected from:
(7) (C) N-alkylmonoallylamine acid addition salt and (D) at least one selected from N, N-dialkylmonoallylamine acid addition salt, diallylaminate addition salt and N-alkyldiallylaminate addition salt Of (8) (E) N, N-dialkylmonoallylamine acid addition salt with (F) diallylamine acid addition salt and / or N-alkyldiallylamine acid addition salt. Polymer,
Can be mentioned.
前記（６）〜（８）において、（Ａ）成分の単量体と（Ｂ）成分の単量体、（Ｃ）成分の単量体と（Ｄ）成分の単量体、（Ｅ）成分の単量体と（Ｆ）成分の単量体の使用割合については特に制限はないが、通常モル比でそれぞれ９：１〜１：９の範囲が好ましい。
本発明のアリルアミン類酸付加塩重合体は、分子量が、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）法によるポリエチレングリコール換算の重量平均分子量で、５００〜５００，０００の範囲にあることが好ましく、より好ましくは８００〜１００，０００の範囲である。
このような構造を有する本発明のアリルアミン類酸付加塩重合体は、塩素を含まず、かつ水溶性に優れており、各種の用途、例えばインクジェット記録紙用薬剤など、特にインクジェット記録紙用耐水化剤として好適に用いられる。
In the above (6) to (8), the monomer (A) and the monomer (B), the monomer (C) and the monomer (D), (E) Although there is no restriction | limiting in particular about the usage-amount of the monomer of (F), and the monomer of (F), Usually, the range of 9: 1 to 1: 9 is respectively preferable by molar ratio.
The allylamine acid addition salt polymer of the present invention preferably has a molecular weight in the range of 500 to 500,000, more preferably a weight average molecular weight in terms of polyethylene glycol by gel permeation chromatography (GPC). It is in the range of 800 to 100,000.
The allylamine acid addition salt polymer of the present invention having such a structure does not contain chlorine, has excellent water solubility, and has various uses, for example, a chemical for ink jet recording paper, particularly water resistance for ink jet recording paper. It is suitably used as an agent.
次に、本発明のアリルアミン類酸付加塩重合体の製造方法について説明する。
本発明の製造方法においては、極性溶媒中において、水溶性アゾ系ラジカル重合開始剤および／または過硫酸塩系ラジカル重合開始剤の存在下に、一般式（ＩＩＩ）
Next, the manufacturing method of the allylamine acid addition salt polymer of this invention is demonstrated.
In the production method of the present invention, in the presence of a water-soluble azo radical polymerization initiator and / or a persulfate radical polymerization initiator in a polar solvent, the compound represented by the general formula (III)
で表されるモノアリルアミン類酸付加塩、および／または一般式（ＩＶ）
And / or a monoallylamine acid addition salt represented by general formula (IV)
で表されるジアリルアミン類酸付加塩を重合させることにより、前記一般式（Ｉ）で表される構成単位、並びに一般式（ＩＩ−ａ）および一般式（ＩＩ−ｂ）で表される構成単位の中から選ばれる少なくとも１種を有するアリルアミン類酸付加塩重合体を製造する。
And the structural unit represented by the general formula (II-a) and the general formula (II-b), by polymerizing the diallylamine acid addition salt represented by the general formula (I). An allylamine acid addition salt polymer having at least one selected from among the above is produced.
本発明においては、前記極性溶媒として、水系溶媒が好ましく用いられる。この水系溶媒としては、例えば８０重量％以上が水である水溶液からなる溶媒を指し、そして、この水系溶媒は水単独であることが、重合収率の向上や安全性の面から好ましい。水に混合できる極性溶媒としては、アルコール類として、メタノール、エタノール、プロパノール、エチレングリコール、ジエチレングリコール、１，２−プロパンジオール、１，３−ブタンジオールなど、アミド類として、ジメチルアセトアミド、ジメチルホルムアミドなどが例示できる。
また、重合触媒として用いられる水溶性アゾ系ラジカル重合開始剤は、分子内に−Ｎ＝Ｎ−基を有しているアゾ系ラジカル重合開始剤であって、水溶性のものであればよく、特に制限はない。ここで、水溶性とは、例えば大気圧下、重合温度において、水５０ｇに対し、１ｇ以上溶解可能であることを意味する。このようなアゾ系ラジカル重合開始剤としては、特公平２−１４３６４号公報、特公平２−５６３６１号公報、特公平２−５６３６２号公報、特公平２−５７０８２号公報、特公平２−５７０８３号公報に記載されているものが例示できる。
In the present invention, an aqueous solvent is preferably used as the polar solvent. As this aqueous solvent, for example, a solvent comprising an aqueous solution of 80% by weight or more is water, and it is preferable that the aqueous solvent is water alone from the viewpoint of improvement in polymerization yield and safety. Examples of polar solvents that can be mixed with water include alcohols such as methanol, ethanol, propanol, ethylene glycol, diethylene glycol, 1,2-propanediol, and 1,3-butanediol, and amides such as dimethylacetamide and dimethylformamide. It can be illustrated.
Further, the water-soluble azo radical polymerization initiator used as a polymerization catalyst is an azo radical polymerization initiator having a —N═N— group in the molecule, and may be water-soluble. There is no particular limitation. Here, water-soluble means that, for example, 1 g or more can be dissolved in 50 g of water at the polymerization temperature under atmospheric pressure. As such an azo radical polymerization initiator, JP-B-2-14364, JP-B-2-56361, JP-B-2-56362, JP-B-2-57082, JP-B-2-57083 What is described in the gazette can be illustrated.
これらのラジカル重合開始剤の中で、分子中にアゾ基とカチオン性窒素を有する化合物が好ましく、その中で、一般式（Ｖ）で示されるアゾ化合物の無機酸または有機酸塩が原料合成の容易さから実用に供せられる。 Among these radical polymerization initiators, compounds having an azo group and cationic nitrogen in the molecule are preferable, and among them, an inorganic acid or an organic acid salt of an azo compound represented by the general formula (V) is used for the raw material synthesis. It can be put to practical use because of its ease.
Ｒ４−Ｎ＝Ｎ−Ｒ５ …（Ｖ）
［式中のＲ４とＲ５の少なくとも一方、好ましくは両方がアミノアルキル、アミノアリール、アミジニルアルキル、アミジニルアリール、アミノアルカリール、アミノアラルキル、アミジニルアラルキル、アミジニルアルカリール、シアノアミノアルキルおよびシアノアミノアルカリールからなる群から選ばれるカチオン化し得る窒素原子を含む基であり、Ｒ４とＲ５の一方が上記カチオン化し得る窒素原子を含む基である場合には、残りのものが、アルキル、アリール、アルカリール、アラルキル、シアノアルキル、シアノアリール、シアノアルカリール、シアノアラルキルからなる群から選ばれた基であり、また、Ｒ４とＲ５は、これらが一緒になって一般式（ＶＩ）で示される単一のアルキレン基を形式してもよい。
R 4 −N = N−R 5 (V)
[At least one of R 4 and R 5 in the formula, preferably both are aminoalkyl, aminoaryl, amidinylalkyl, amidinylaryl, aminoalkaryl, aminoaralkyl, amidinylaralkyl, amidinylalkaryl. A cationizable nitrogen atom selected from the group consisting of cyanoaminoalkyl and cyanoaminoalkaryl, and when one of R 4 and R 5 is a group containing a cationizable nitrogen atom, the rest Are groups selected from the group consisting of alkyl, aryl, alkaryl, aralkyl, cyanoalkyl, cyanoaryl, cyanoalkaryl, cyanoaralkyl, and R 4 and R 5 are the same. A single alkylene group represented by the general formula (VI) may be formed.
これらのうち、一般式（Ｖ）で示されるアゾ系ラジカル重合開始剤が、アゾ基に隣接する第二又は第三炭素を有する化合物であることが特に好ましい。
Of these, the azo radical polymerization initiator represented by the general formula (V) is particularly preferably a compound having a second or third carbon adjacent to the azo group.
このアゾ系ラジカル重合開始剤の例としては、２，２´−ジアミジニル−２，２´−アゾプロパン・塩酸塩［別名として２，２´−アゾビス（２−アミジノプロパン）塩酸塩］、２，２´−ジアミジニル−２，２´−アゾブタン・塩酸塩、２，２´−ジアミジニル−２，２´−アゾペンタン・塩酸塩、２，２´−ビス（Ｎ−フェニルアミジニル）−２，２´−アゾプロパン・塩酸塩、２，２´−ビス（Ｎ−フェニルアミジニル）−２，２´−アゾブタン・塩酸塩、２，２´−ビス（Ｎ，Ｎ−ジメチルアミジニル）−２，２´−アゾプロパン・塩酸塩、２，２´−ビス（Ｎ，Ｎ−ジメチルアミジニル）−２，２´−アゾブタン・塩酸塩、２，２´−ビス（Ｎ，Ｎ−ジエチルアミジニル）−２，２´−アゾプロパン・塩酸塩、２，２´−ビス（Ｎ，Ｎ−ジエチルアミジニル）−２，２´−アゾブタン・塩酸塩、２，２´−ビス（Ｎ，Ｎ−ジｎ−ブチルアミジニル）−２，２´−アゾプロパン・塩酸塩、２，２´−ビス（Ｎ，Ｎ−ジｎ−ブチルアミジニル）−２，２´−アゾブタン・塩酸塩、３，３´−ビス（Ｎ，Ｎ−ジｎ−ブチルアミジニル）−３，３´−アゾペンタン・塩酸塩、アゾ−ビス−Ｎ，Ｎ´−ジメチレンイソブチルアミジン・塩酸塩などが挙げられる。これらの塩酸塩は、二塩酸塩であることが好ましい。 Examples of the azo radical polymerization initiator include 2,2′-diamidinyl-2,2′-azopropane hydrochloride (also known as 2,2′-azobis (2-amidinopropane) hydrochloride), 2,2 '-Diamidinyl-2,2'-azobutane hydrochloride, 2,2'-diamidinyl-2,2'-azopentane hydrochloride, 2,2'-bis (N-phenylamidinyl) -2,2' -Azopropane hydrochloride, 2,2'-bis (N-phenylamidinyl) -2,2'-azobutane hydrochloride, 2,2'-bis (N, N-dimethylamidinyl) -2, 2'-azopropane hydrochloride, 2,2'-bis (N, N-dimethylamidinyl) -2,2'-azobutane hydrochloride, 2,2'-bis (N, N-diethylamidinyl) ) -2,2'-azopropane hydrochloride, 2,2'-bis (N, N-die) Amidinyl) -2,2'-azobutane hydrochloride, 2,2'-bis (N, N-di-n-butylamidinyl) -2,2'-azopropane hydrochloride, 2,2'-bis (N, N -Di-n-butylamidinyl) -2,2'-azobutane hydrochloride, 3,3'-bis (N, N-din-butylamidinyl) -3,3'-azopentane hydrochloride, azo-bis-N, N'-dimethylene isobutylamidine hydrochloride etc. are mentioned. These hydrochlorides are preferably dihydrochlorides.
また、アゾ系ラジカル重合開始剤の別の例として、２，２´−アゾビス［２−（２−イミダゾリン−２−イル）プロパン］塩酸塩、２，２´−アゾ−ビス（２−メチル−４−ジエチルアミノ）−ブチロニトリル・塩酸塩、２，２´−アゾ−ビス（２−メチル−４−ジメチルアミノ）−ブチロニトリル・塩酸塩、２，２´−アゾ−ビス（２−メチル−４−ジエチルアミノ）−ブチロニトリル・塩酸塩、２，２´−アゾ−ビス（２−エチル−４−ジエチルアミノ）−ブチロニトリルまたは２，２´−アゾ−ビス（２−メチル−４−ジメチルアミノ）−ブチロニトリルを、ジメチル硫酸またはｐ−トルエンスルホン酸メチルなどで四級化して得た第４アンモニウム塩型アゾニトリル； ３，５−ジアミジニル−１，２−ジアゾ−１−シクロペンテン・塩酸塩、３−メチル−３，４−ジアミジニル−１，２−ジアゾ−１−シクロペンテン・塩酸塩、３−エチル−３，５−ジアミジニル−１，２−ジアゾ−１−シクロペンテン・塩酸塩、３，５−ジメチル−３，５−ジアミジニル−１，２−ジアゾ−１−シクロペンテン・塩酸塩、３、６−ジアミジニル−１，２−ジアゾ−１−シクロヘキセン・塩酸塩、３−フェニル−３，５−ジアミジニル−１，２−ジアゾ−１−シクロペンテン・塩酸塩、３，５−ジフェニル−３，５−ジアミジニル−１，２−ジアゾ−１−シクロペンテン・塩酸塩； ２，２´−アゾビス−（２−メチル−プロピオアミドキシム）、２，２´−アゾビス−（２−メチル−プロピオン−ヒドロキサム酸）、２，２´−アゾビス−（２−メチル−ブチロアミドキシム）、２，２´−アゾビス−（２−メチル−ブチルヒドロキサム酸）、２，２´−アゾビス−（２−イソブチル−２−メチル−プロピオアミドキシム）、２，２´−アゾビス−（２−イソブチル−２−メチル−プロピオン−ヒドロキサム酸）、２，２´−アゾビス−（２−シクロヘキシル−プロピオアミドキシム）、２，２´−アゾビス−（２−シクロヘキシル−プロピオン−ヒドロキサム酸）、２，２´−アゾビス−（２−フェニル−プロピオアミドキシム）、２，２´−アゾビス−（２−フェニル−プロピオン−ヒドロキサム酸）、２，２´−アゾビス−（２−ベンジル−プロピオアミドキシム）、２，２´−アゾビス−（２−ベンジル−プロピオン−ヒドロキサム酸）、１，１´−アゾビス−（シクロヘキシル−カルボアミドキシム、１，１´−アゾビス−（シクロヘキシル−カルボヒドロキサム酸）； ２，２´−アゾビス−（２−カルボキシメチル−プロピオアミドキシム）、２，２´−アゾビス−（２−カルボキシエチル−プロピオアミドキシム）、３，３´−アゾビス−（３−カルボキシエチル−ブチロアミドキシム）、２，２´−アゾビス−（２−カルボキシメチル−プロピオンヒドロキサム酸）、２，２´−アゾビス−（２−カルボキシエチル−プロピオンヒドロキサム酸）、３，３´−アゾビス−（３−カルボキシエチル−ブチルヒドロキサム酸）； ２，２´−アゾビス−（２−メチルプロピオン酸メチルエステル）、２，２´−アゾビス−（２−メチルプロピオン酸エチルエステル）、２，２´−アゾビス−（２−エチルプロピオン酸メチルエステル）、２，２´−アゾビス−（２−エチル酪酸メチルエステル）、２，２´−アゾビス−（２−アセトキシ−プロパン）、２，２´−アゾビス−（２−アセトキシ−ブタン）、１，１´−アゾビス（１−ホルムオキシ−シクロヘキサン）； ２，２´−アゾビス−（２−メチルプロピオン酸ヒドラジド）、２，２´−アゾビス−（２−メチル酪酸ヒドラジド）、２，２´−アゾビス−（２−エチル酪酸ヒドラジド）、１，１´−アゾビス−（１−シクロヘキシルカルボン酸ヒドラジド）、４，４´−アゾビス−（４−ヒドロキシ吉草酸ヒドラジド）、４，４´−アゾビス−（４−ヒドロキシカプロン酸ヒドラジド）などが挙げられる。
これらのアゾ系ラジカル重合開始剤は単独で用いてもよいし、２種以上を組み合わせて用いてもよい。
一方、過硫酸塩系ラジカル重合開始剤としては、例えば過硫酸アンモニウム、過硫酸ナトリウム、過硫酸カリウムなどが挙げられ、これらは単独で用いてもよいし、２種以上を組み合わせて用いてもよい。また、前記アゾ系ラジカル重合開始剤と併用することもできる。
As another example of the azo radical polymerization initiator, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] hydrochloride, 2,2′-azo-bis (2-methyl-) 4-diethylamino) -butyronitrile hydrochloride, 2,2'-azo-bis (2-methyl-4-dimethylamino) -butyronitrile hydrochloride, 2,2'-azo-bis (2-methyl-4-diethylamino) ) -Butyronitrile hydrochloride, 2,2'-azo-bis (2-ethyl-4-diethylamino) -butyronitrile or 2,2'-azo-bis (2-methyl-4-dimethylamino) -butyronitrile Quaternary ammonium salt type azonitrile obtained by quaternization with sulfuric acid or methyl p-toluenesulfonate; 3,5-diamidinyl-1,2-diazo-1-cyclopentene / hydrochloric acid Salt, 3-methyl-3,4-diamidinyl-1,2-diazo-1-cyclopentene hydrochloride, 3-ethyl-3,5-diamidinyl-1,2-diazo-1-cyclopentene hydrochloride, 3, 5-dimethyl-3,5-diamidinyl-1,2-diazo-1-cyclopentene hydrochloride, 3,6-diamidinyl-1,2-diazo-1-cyclohexene hydrochloride, 3-phenyl-3,5- Diamidinyl-1,2-diazo-1-cyclopentene hydrochloride, 3,5-diphenyl-3,5-diamidinyl-1,2-diazo-1-cyclopentene hydrochloride; 2,2′-azobis- (2- Methyl-propioamidoxime), 2,2'-azobis- (2-methyl-propion-hydroxamic acid), 2,2'-azobis- (2-methyl-butyroamidoxime), 2,2'-azo Su- (2-methyl-butylhydroxamic acid), 2,2'-azobis- (2-isobutyl-2-methyl-propioamidoxime), 2,2'-azobis- (2-isobutyl-2-methyl-propion) -Hydroxamic acid), 2,2'-azobis- (2-cyclohexyl-propioamidoxime), 2,2'-azobis- (2-cyclohexyl-propion-hydroxamic acid), 2,2'-azobis- (2- Phenyl-propioamidoxime), 2,2'-azobis- (2-phenyl-propion-hydroxamic acid), 2,2'-azobis- (2-benzyl-propioamidoxime), 2,2'-azobis- ( 2-benzyl-propion-hydroxamic acid), 1,1'-azobis- (cyclohexyl-carboamidoxime, 1,1'-azobis- (cyclo Hexyl-carbohydroxamic acid); 2,2'-azobis- (2-carboxymethyl-propioamidoxime), 2,2'-azobis- (2-carboxyethyl-propioamidoxime), 3,3'-azobis- (3-carboxyethyl-butyroamidoxime), 2,2'-azobis- (2-carboxymethyl-propion hydroxamic acid), 2,2'-azobis- (2-carboxyethyl-propion hydroxamic acid), 3,3 '-Azobis- (3-carboxyethyl-butylhydroxamic acid); 2,2'-azobis- (2-methylpropionic acid methyl ester), 2,2'-azobis- (2-methylpropionic acid ethyl ester), 2 , 2'-azobis- (2-ethylpropionic acid methyl ester), 2,2'-azobis- (2-ethylbutyric acid Chill ester), 2,2'-azobis- (2-acetoxy-propane), 2,2'-azobis- (2-acetoxy-butane), 1,1'-azobis (1-formoxy-cyclohexane); '-Azobis- (2-methylpropionic acid hydrazide), 2,2'-azobis- (2-methylbutyric acid hydrazide), 2,2'-azobis- (2-ethylbutyric acid hydrazide), 1,1'-azobis- (1-cyclohexylcarboxylic acid hydrazide), 4,4′-azobis- (4-hydroxyvaleric acid hydrazide), 4,4′-azobis- (4-hydroxycaproic acid hydrazide), and the like.
These azo radical polymerization initiators may be used alone or in combination of two or more.
On the other hand, examples of the persulfate-based radical polymerization initiator include ammonium persulfate, sodium persulfate, and potassium persulfate. These may be used alone or in combination of two or more. It can also be used in combination with the azo radical polymerization initiator.
本発明の方法において、原料単量体として用いられる前記一般式（ＩＩＩ）で表されるモノアリルアミン類酸付加塩としては、例えばモノアリルアミン、Ｎ−メチルアリルアミン、Ｎ−エチルアリルアミン、Ｎ−プロピルアリルアミン、Ｎ−ブチルアリルアミン、Ｎ，Ｎ−ジメチルアリルアミン、Ｎ−メチル−Ｎ−エチルアリルアミン、Ｎ，Ｎ−ジエチルアリルアミン、Ｎ，Ｎ−ジプロピルアリルアミン、Ｎ，Ｎ−ジブチルアリルアミンなどのモノアリルアミン類のメタンスルホン酸付加塩、イセチオン酸付加塩、アミド硫酸付加塩などを好ましく挙げることができる。
一方、原料単量体として用いられる前記一般式（ＩＶ）で表されるジアリルアミン類酸付加塩としては、例えばジアリルアミン、Ｎ−メチルジアリルアミン、Ｎ−エチルジアリルアミン、Ｎ−プロピルジアリルアミン、Ｎ−（２−ヒドロキシエチル）ジアリルアミン、Ｎ−（２−ヒドロキシプロピル）ジアリルアミン、Ｎ−（３−ヒドロキシプロピル）ジアリルアミンなどのジアリルアミン類のメタンスルホン酸付加塩、イセチオン酸付加塩、アミド硫酸付加塩などを好ましく挙げることができる。
本発明の方法において、アリルアミン類酸付加塩重合体、具体的には前述の（１）〜（８）で示した態様の重合体を製造するに際し、単量体としてＮ，Ｎ−ジアルキルモノアリルアミン酸付加塩を用いないで、アリルアミン類酸付加塩重合体を製造する場合、前記ラジカル重合開始剤の使用量は、一般的にはアリルアミン類酸付加塩の全量に対して、０．１モル％以上、好ましくは０．２〜１５モル％、より好ましくは０．５〜１０モル％である。一方、単量体として、Ｎ，Ｎ−ジアルキルモノアリルアミン酸付加塩を含むものを用い、アリルアミン類酸付加塩重合体を製造する場合、１モル％以上、好ましくは２〜５０モル％、より好ましくは３〜４０モル％、特に好ましくは４〜２０モル％である。
Examples of the monoallylamine acid addition salt represented by the general formula (III) used as a raw material monomer in the method of the present invention include monoallylamine, N-methylallylamine, N-ethylallylamine, and N-propylallylamine. Methane of monoallylamines such as N-butylallylamine, N, N-dimethylallylamine, N-methyl-N-ethylallylamine, N, N-diethylallylamine, N, N-dipropylallylamine, N, N-dibutylallylamine Preferred examples include sulfonic acid addition salts, isethionic acid addition salts, amidosulfuric acid addition salts, and the like.
On the other hand, examples of the diallylamine acid addition salt represented by the general formula (IV) used as a raw material monomer include diallylamine, N-methyldiallylamine, N-ethyldiallylamine, N-propyldiallylamine, N- (2- Preferred examples include methanesulfonic acid addition salts, isethionic acid addition salts, amidosulfuric acid addition salts of diallylamines such as hydroxyethyl) diallylamine, N- (2-hydroxypropyl) diallylamine, and N- (3-hydroxypropyl) diallylamine. it can.
In the method of the present invention, an N, N-dialkylmonoallylamine is used as a monomer in producing an allylamine acid addition salt polymer, specifically, the polymer having the above-described embodiments (1) to (8). When an allylamine acid addition salt polymer is produced without using an acid addition salt, the amount of the radical polymerization initiator used is generally 0.1 mol% based on the total amount of allylamine acid addition salt. As mentioned above, Preferably it is 0.2-15 mol%, More preferably, it is 0.5-10 mol%. On the other hand, when an allylamine acid addition salt polymer is produced using a monomer containing an N, N-dialkylmonoallylamine acid addition salt as the monomer, it is 1 mol% or more, preferably 2 to 50 mol%, more preferably. Is 3 to 40 mol%, particularly preferably 4 to 20 mol%.
重合温度は、通常、２０℃〜還流温度、好ましくは３０〜１００℃、さらに好ましくは４０〜８０℃である。重合時間は、重合温度およびラジカル重合開始剤の種類と量などに左右され一概には定めることができないが、通常３００時間以内で十分である。
また、出発単量体の濃度はその溶解度の範囲内で高いほうが好ましく、この場合、重合収率と重合度は高くなりやすい。出発単量体の濃度は通常１５重量％以上、好ましくは２０〜９０重量％である。
このようにして、前記一般式（Ｉ）で表される構成単位、並びに一般式（ＩＩ−ａ）および一般式（ＩＩ−ｂ）で表される構成単位の中から選ばれる少なくとも１種を有するアリルアミン類酸付加塩重合体を含む水溶液が得られる。
このアリルアミン類酸付加塩重合体の水溶液は、そのまままたは濃度調整して、インクジェット記録紙用薬剤などの各種用途に用いることができる。あるいは、所望により、アリルアミン類酸付加塩重合体の形で取り出し、精製して、各種用途に用いてもよい。
The polymerization temperature is usually 20 ° C. to reflux temperature, preferably 30 to 100 ° C., more preferably 40 to 80 ° C. The polymerization time depends on the polymerization temperature and the type and amount of the radical polymerization initiator, and cannot be determined unconditionally, but is usually sufficient within 300 hours.
Further, the concentration of the starting monomer is preferably higher within the solubility range, and in this case, the polymerization yield and the polymerization degree are likely to be high. The concentration of the starting monomer is usually 15% by weight or more, preferably 20 to 90% by weight.
Thus, it has at least 1 sort (s) chosen from the structural unit represented by the said general formula (I), and the structural unit represented by general formula (II-a) and general formula (II-b). An aqueous solution containing an allylamine acid addition salt polymer is obtained.
The aqueous solution of this allylamine acid addition salt polymer can be used as it is or after adjusting its concentration for various uses such as a drug for ink jet recording paper. Alternatively, if desired, it may be taken out in the form of an allylamine acid addition salt polymer, purified and used in various applications.
本発明のアリルアミン類酸付加塩重合体は、塩素を含まず、かつ水溶性に優れており、インクジェット記録紙用薬剤、特に耐水化剤として好適に用いられる。
本発明はまた、前記アリルアミン類酸付加塩重合体を含むインクジェット記録紙用薬剤をも提供する。
この薬剤は、インクジェット記録用紙における基紙の内部に含有させてもよく、基紙表面に形成させる塗工層に用いてもよいが、特に塗工層に用いるのが好ましい。該薬剤を塗工層に用いる場合には、例えば当該アリルアミン類酸付加塩重合体の水溶液に必要に応じ、表面サイズ剤としての水溶性高分子化合物、無機顔料、有機顔料、顔料分散剤、増粘剤、消泡剤、紫外線吸収剤、酸化防止剤、防腐剤、極性有機溶剤などを加えることによって、塗工液を調製することができる。
ここで、水溶性高分子化合物としては、例えば酸化澱粉、カチオン化澱粉又は各種変性澱粉、ポリエチレンオキシド、ポリアクリルアミド、ポリアクリル酸ナトリウム、ヒドロキシメチルセルロース、ポリビニルアルコールなどを挙げることができる。無機顔料としては、例えば軽質炭酸カルシウム、重質炭酸カルシウム、カオリン（白土）、タルク、硫酸カルシウム、硫酸バリウム、酸化チタン、酸化亜鉛、硫酸亜鉛、炭酸亜鉛、サチンホワイト、珪酸アルミニウム、ケイソウ土、珪酸カルシウム、合成シリカ、水酸化アルミニウム、アルミナなどを挙げることができる。有機顔料としては、例えば、スチレン系プラスチックピグメント、アクリル系プラスチックピグメント、尿素樹脂顔料などを挙げることができる。
基紙への塗工方法としては、例えばサイズプレス、ゲートロールコーター、ブレードメタリングサイズプレス、ロッドコーター、エアーナイフコーター、カーテンコーターなどの各種塗工方法を用いることができる。
塗工量は、当該アリルアミン類酸付加塩重合体として、通常０．１〜１０．０ｇ／ｍ２、好ましくは０．２〜５．０ｇ／ｍ２の範囲で選定される。
このようにして、得られたインクジェット記録用紙は、耐水性に優れると共に、耐光性及び発色性が良好である。
The allylamine acid addition salt polymer of the present invention does not contain chlorine, is excellent in water solubility, and is suitably used as a chemical for ink jet recording paper, particularly as a water-resistant agent.
The present invention also provides an ink jet recording paper agent comprising the allylamine acid addition salt polymer.
This agent may be contained in the base paper of the ink jet recording paper, and may be used in a coating layer formed on the surface of the base paper, but is particularly preferably used in the coating layer. When the agent is used for the coating layer, for example, an aqueous solution of the allylamine acid addition salt polymer, if necessary, a water-soluble polymer compound as a surface sizing agent, an inorganic pigment, an organic pigment, a pigment dispersant, an increase agent. A coating liquid can be prepared by adding a sticky agent, an antifoaming agent, an ultraviolet absorber, an antioxidant, a preservative, a polar organic solvent, and the like.
Here, examples of the water-soluble polymer compound include oxidized starch, cationized starch or various modified starches, polyethylene oxide, polyacrylamide, sodium polyacrylate, hydroxymethylcellulose, polyvinyl alcohol and the like. Examples of inorganic pigments include light calcium carbonate, heavy calcium carbonate, kaolin (white clay), talc, calcium sulfate, barium sulfate, titanium oxide, zinc oxide, zinc sulfate, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, and silicic acid. Calcium, synthetic silica, aluminum hydroxide, alumina and the like can be mentioned. Examples of organic pigments include styrene plastic pigments, acrylic plastic pigments, urea resin pigments, and the like.
As a coating method for the base paper, various coating methods such as a size press, a gate roll coater, a blade metering size press, a rod coater, an air knife coater, and a curtain coater can be used.
The coating amount as the allylamines acid addition salt polymer, usually 0.1~10.0g / m 2, is selected preferably in the range of 0.2~5.0g / m 2.
Thus, the obtained inkjet recording paper is excellent in water resistance and light resistance and color developability.
次に、本発明を実施例により、さらに詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。
なお、ポリマーの重量平均分子量および重合収率は、下記の方法に従って測定した。
重合体の重量平均分子量（Ｍｗ）は、日立Ｌ−６０００型高速液体クロマトグラフを使用し、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ法）によって測定した。溶離液流路ポンプは日立Ｌ−６０００、検出器はショーデックスＲＩ ＳＥ−６１示差屈折率検出器、カラムはアサヒパックの水系ゲル濾過タイプのＧＳ−２２０ＨＱ（排除限界分子量３，０００）とＧＳ−６２０ＨＱ（排除限界分子量２００万）とをダブルに接続したものを用いた。サンプルは溶離液で０．５ｇ／１００ｍｌの濃度に調整し、２０μｌを用いた。溶離液には、０．４ｍｏｌ／Ｌの塩化ナトリウム水溶液を使用した。カラム温度は３０℃で、流速は１．０ｍｌ／分で実施した。標準サンプルとして分子量１０６、１９４、４４０、６００、１４７０、４１００、７１００、１０３００、１２６００、２３０００などのポリエチレングリコールを用いて較正曲線を求め、その較正曲線を基に重合体のＭｗを求めた
重合体の重合収率は、ＧＰＣピークの面積比より求めた。
また、各略号の意味を、以下に示す。
ＧＰＣ：ゲル・パーミエーション・クロマトグラフィー
ＡＢＡＰ：２，２’−アゾビス（２−アミジノプロパン）塩酸塩
ＶＡ−０４６Ｂ：２，２’−アゾビス［２−（イミダゾリン−２−イル）プロパン］硫酸塩
ＡＰＳ：過硫酸アンモニウム
ＩＲスペクトル：赤外吸収スペクトル
ＡＡ：アリルアミン（モノアリルアミン）
ＭＡＡ：Ｎ−メチルアリルアミン
ＤＭＡＡ：Ｎ，Ｎ−ジメチルアリルアミン
ＤＡＡ：ジアリルアミン
ＤＡＭＡ：Ｎ−メチルジアリルアミン
実施例１
アリルアミン・メタンスルホン酸塩とジアリルアミン・メタンスルホン酸塩との共重合体の製造（仕込モル比 ４：１）
攪拌機、温度計、ジムロート式還流冷却管を備えた１リットルの４つ口丸底セパラブルフラスコに水 ３２２．４ｇ、メタンスルホン酸 ２８８．３ｇ（３．０モル）を仕込み、冷却攪拌下でアリルアミン（モノアリルアミン） １３７．０ｇ（２．４モル）、ジアリルアミン ５８．３ｇ（０．６モル）を徐々に滴下してアリルアミン・メタンスルホン酸塩とジアリルアミン・メタンスルホン酸塩の混合モノマー水溶液を調製した。モノマー濃度６０重量％の混合モノマー水溶液を５０℃に保ち、それにラジカル重合開始剤としてＡＢＡＰ ４．０７ｇ（モノマーに対して ０．５モル％）添加した。さらに重合反応を開始してから２４時間経過した後にもＡＢＡＰ ４．０７ｇ添加した。重合反応は５０℃で合計７２時間行った。
得られた標記重合体の水溶液は、淡黄褐色透明の粘性溶液となった。重合収率は９５％であった。重量平均分子量は、１９９００であった。その溶液の一部をイソプロパノール中に投入して再沈殿させ、濾別後に５０℃で４８時間の真空乾燥することにより、白色粉体状のアリルアミン・メタンスルホン酸塩とジアリルアミン・メタンスルホン酸塩の共重合体を得た。得られた共重合体のＩＲスペクトルは、１１８０ｃｍ−１と１０５０ｃｍ−１にスルホン酸塩のＳ＝Ｏ伸縮に由来する吸収を示し、アリルアミン・メタンスルホン酸塩とジアリルアミン・メタンスルホン酸塩の共重合体であることを支持している。図１および図２に、それぞれ、ＩＲスペクトル、ＧＰＣ測定の結果を記載する。
実施例２
アリルアミン・メタンスルホン酸塩重合体の製造
攪拌機、温度計、ジムロート式還流冷却管を備えた１リットルの４つ口丸底セパラブルフラスコに水 ３０６．３ｇ、メタンスルホン酸 ２８８．３ｇ（３．０モル）を仕込み、冷却攪拌下でアリルアミン（モノアリルアミン） １７１．３ｇ（３．０モル）を徐々に滴下してアリルアミン・メタンスルホン酸塩モノマー水溶液を調製した。モノマー濃度６０重量％のアリルアミン・メタンスルホン酸塩水溶液を５０℃に保ち、それにラジカル重合開始剤としてＡＢＡＰ ８．１４ｇ（モノマーに対して １．０モル％）添加した。さらに重合反応を開始してから２４時間経過した後にもＡＢＡＰ ８．１４ｇ添加した。重合反応は５０℃で合計７２時間行った。
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
The polymer weight average molecular weight and polymerization yield were measured according to the following methods.
The weight average molecular weight (Mw) of the polymer was measured by gel permeation chromatography (GPC method) using a Hitachi L-6000 type high performance liquid chromatograph. The eluent flow path pump is Hitachi L-6000, the detector is Shodex RI SE-61 differential refractive index detector, the column is Asahi Pack's water-based gel filtration type GS-220HQ (exclusion limit molecular weight 3,000) and GS- 620HQ (exclusion limit molecular weight 2 million) and a double connection were used. The sample was adjusted to a concentration of 0.5 g / 100 ml with an eluent, and 20 μl was used. A 0.4 mol / L sodium chloride aqueous solution was used as an eluent. The column temperature was 30 ° C. and the flow rate was 1.0 ml / min. A calibration curve was obtained using polyethylene glycol having a molecular weight of 106, 194, 440, 600, 1470, 4100, 7100, 10300, 12600, 23000, etc. as a standard sample, and the Mw of the polymer was obtained based on the calibration curve. The polymerization yield was determined from the area ratio of the GPC peak.
Moreover, the meaning of each abbreviation is shown below.
GPC: gel permeation chromatography ABAP: 2,2′-azobis (2-amidinopropane) hydrochloride VA-046B: 2,2′-azobis [2- (imidazolin-2-yl) propane] sulfate APS : Ammonium persulfate IR spectrum: Infrared absorption spectrum AA: Allylamine (monoallylamine)
MAA: N-methylallylamine DMAA: N, N-dimethylallylamine DAA: diallylamine DAMA: N-methyldiallylamine Example 1
Production of copolymers of allylamine methanesulfonate and diallylamine methanesulfonate (feeding molar ratio 4: 1)
A 1 liter four-necked round bottom separable flask equipped with a stirrer, thermometer, and Jimroth reflux condenser was charged with 322.4 g of water and 288.3 g (3.0 mol) of methanesulfonic acid, and allylamine was stirred under cooling. (Monallylamine) 137.0 g (2.4 mol) and diallylamine 58.3 g (0.6 mol) were gradually added dropwise to prepare a mixed monomer aqueous solution of allylamine / methanesulfonate and diallylamine / methanesulfonate. . A mixed monomer aqueous solution having a monomer concentration of 60% by weight was kept at 50 ° C., and 4.07 g of ABAP (0.5 mol% based on the monomer) was added thereto as a radical polymerization initiator. Further, 4.07 g of ABAP was added even after 24 hours had elapsed from the start of the polymerization reaction. The polymerization reaction was carried out at 50 ° C. for a total of 72 hours.
The obtained aqueous solution of the title polymer was a pale yellowish brown transparent viscous solution. The polymerization yield was 95%. The weight average molecular weight was 19,900. A part of the solution was poured into isopropanol for reprecipitation, and after filtration, vacuum drying was performed at 50 ° C. for 48 hours, whereby white powdery allylamine methanesulfonate and diallylamine methanesulfonate were mixed. A copolymer was obtained. The obtained IR spectrum of the copolymer showed an absorption derived from S = O stretching of sulfonate to 1180 cm -1 and 1050 cm -1, the copolymerization of allylamine methanesulfonate and diallylamine methanesulfonate Supports being united. 1 and 2 show the results of IR spectrum and GPC measurement, respectively.
Example 2
Production of allylamine / methanesulfonate polymer A 1-liter four-necked round bottom separable flask equipped with a stirrer, thermometer, and Dimroth reflux condenser was used with 306.3 g of water and 288.3 g of methanesulfonic acid (3.0 Mol) was added dropwise, and 171.3 g (3.0 mol) of allylamine (monoallylamine) was gradually added dropwise under cooling and stirring to prepare an aqueous solution of allylamine / methanesulfonate monomer. An allylamine / methanesulfonate aqueous solution having a monomer concentration of 60% by weight was kept at 50 ° C., and 8.14 g of ABAP (1.0 mol% based on the monomer) was added thereto as a radical polymerization initiator. Further, 8.14 g of ABAP was also added after 24 hours had elapsed from the start of the polymerization reaction. The polymerization reaction was carried out at 50 ° C. for a total of 72 hours.
得られた標記重合体の水溶液は、淡黄褐色透明の粘性溶液であった。重合収率は９７％、重量平均分子量は、１２５００であった。水溶液の一部をイソプロパノール中に投入して再沈殿させ、濾別後に５０℃で４８時間の真空乾燥することにより、白色粉状態のモノアリルアミン・メタンスルホン酸塩重合体を得た。結果を表１に示す。
実施例３〜４
アリルアミン・メタンスルホン酸塩重合体の製造
ラジカル重合開始剤をＡＰＳまたはＶＡ−０４６Ｂに変えて分割添加による重合反応を実施した以外は、実施例２と同様に操作し、アリルアミン・メタンスルホン酸塩重合体を得た。その結果を表１に示す。
実施例５〜７
アリルアミン・メタンスルホン酸塩とジアリルアミン・メタンスルホン酸塩類との共重合体の製造
モノマーの仕込組成比等を変えた以外は、実施例１と同様に操作し、標記の共重合体を得た。その結果を表１に示す。
実施例８
Ｎ−メチルアリルアミン・メタンスルホン酸塩重合体の製造
モノマーをＮ−メチルアリルアミンに変えて開始剤を分割添加による重合反応を実施した以外は、実施例２と同様に操作し、Ｎ−メチルアリルアミン・メタンスルホン酸塩重合体を得た。その結果を表１に示す。
実施例９
Ｎ，Ｎ−ジメチルアリルアミン・メタンスルホン酸塩重合体の製造
モノマーをＮ，Ｎ−ジメチルアリルアミンに変え、さらに、開始剤量を多くし、分割添加による重合反応を実施した以外は、実施例２と同様に操作し、Ｎ，Ｎ−ジメチルアリルアミン・メタンスルホン酸塩重合体を得た。その結果を表１に示す。
実施例１０
アリルアミン・メタンスルホン酸塩とＮ−メチルアリルアミン・メタンスルホン酸塩との共重合体の製造
モノマーの仕込組成比を変えて、ジアリルアミンの代わりにＮ−メチルアリルアミンを用いて重合反応を実施した以外は、実施例１と同様に操作し、標記の共重合体を得た。その結果を表１に示す。
実施例１１
アリルアミン・メタンスルホン酸塩とＮ，Ｎ−ジメチルアリルアミン・メタンスルホン酸塩との共重合体の製造
モノマーの仕込組成比を変えて、ジアリルアミンの代わりにＮ，Ｎ−ジメチルアリルアミンを用いて重合反応を実施した以外は、実施例１と同様に操作し、標記の共重合体を得た。その結果を表１に示す。
The obtained aqueous solution of the title polymer was a pale yellowish brown transparent viscous solution. The polymerization yield was 97% and the weight average molecular weight was 12,500. A part of the aqueous solution was poured into isopropanol for reprecipitation, followed by filtration and vacuum drying at 50 ° C. for 48 hours to obtain a monoallylamine / methanesulfonate polymer in a white powder state. The results are shown in Table 1.
Examples 3-4
Production of allylamine / methanesulfonate polymer The same procedure as in Example 2 was carried out except that the radical polymerization initiator was changed to APS or VA-046B and a polymerization reaction was carried out by split addition. Coalescence was obtained. The results are shown in Table 1.
Examples 5-7
Production of Copolymer of Allylamine / Methanesulfonate and Diallylamine / Methanesulfonate The procedure described in Example 1 was followed except that the monomer composition ratio was changed to obtain the title copolymer. The results are shown in Table 1.
Example 8
Production of N-methylallylamine / methanesulfonate polymer The monomer was changed to N-methylallylamine and the polymerization reaction was carried out by split addition of the initiator. A methanesulfonate polymer was obtained. The results are shown in Table 1.
Example 9
The production monomer of the N, N -dimethylallylamine / methanesulfonate polymer was changed to N, N-dimethylallylamine, and the amount of the initiator was increased. By operating in the same manner, an N, N-dimethylallylamine / methanesulfonate polymer was obtained. The results are shown in Table 1.
Example 10
The production composition of the copolymer of allylamine / methanesulfonate and N-methylallylamine / methanesulfonate was changed except that the polymerization composition was changed by using N-methylallylamine instead of diallylamine. The title copolymer was obtained in the same manner as in Example 1. The results are shown in Table 1.
Example 11
Production of copolymer of allylamine methanesulfonate and N, N-dimethylallylamine methanesulfonate The composition ratio of monomers was changed, and N, N-dimethylallylamine was used instead of diallylamine to conduct polymerization reaction. The title copolymer was obtained in the same manner as in Example 1 except for carrying out. The results are shown in Table 1.
実施例１２
アリルアミン・イセチオン酸塩重合体の製造
攪拌機、温度計、ジムロート式還流冷却管を備えた１リットルの４つ口丸底セパラブルフラスコに水 ２１．１ｇ、７０重量％イセチオン酸水溶液 ５４０．０ｇ（３．０モル）を仕込み、冷却攪拌下でアリルアミン（モノアリルアミン） １７１．３ｇ（３．０モル）を徐々に滴下してアリルアミン・イセチオン酸塩モノマー水溶液を調製した。モノマー濃度７５重量％のアリルアミン・イセチオン酸塩水溶液を５５℃に保ち、それにラジカル重合開始剤としてＡＢＡＰ １２．２０ｇ（モノマーに対して １．５モル％）添加した。さらに重合反応を開始してから２４時間経過した後にもＡＢＡＰ １２．２０ ｇ添加した。重合反応は５５℃で合計７２時間行った。
得られた標記重合体の溶液は、無色透明の弱粘性溶液となった。重合収率は９５％であり、重量平均分子量は、３２００であった。図３にＧＰＣ測定結果を示す。
実施例１３
アリルアミン・イセチオン酸塩とジアリルアミン・イセチオン酸塩との共重合体の製造（仕込モル比 ４：１）
攪拌機、温度計、ジムロート式還流冷却管を備えた１リットルの４つ口丸底セパラブルフラスコに水 ８３．７ｇ、７０重量％イセチオン酸 ５４０．０ｇ（３．０モル）を仕込み、冷却攪拌下でアリルアミン（モノアリルアミン） １３７．０ｇ（２．４モル）、ジアリルアミン ５８．３ｇ（０．６モル）を徐々に滴下してアリルアミン・イセチオン酸塩とジアリルアミン・イセチオン酸塩の混合モノマー水溶液を調製した。モノマー濃度７０重量％の混合モノマー水溶液を５５℃に保ち、それにラジカル重合開始剤としてＡＢＡＰ １２．２０ｇ（モノマーに対して １．５モル％）添加した。さらに重合反応を開始してから２４時間経過した後にもＡＢＡＰ ８．１４ｇ添加した。重合反応は５５℃で合計７２時間行った。得られた標記共重合体の水溶液は、淡黄褐色透明の粘性溶液であった。重合収率は９５％であり、重量平均分子量は、４４００であった。
実施例１４〜１６
アリルアミン・イセチオン酸塩とジアリルアミン類・イセチオン酸塩との共重合体の製造
モノマーの仕込組成比を変えて、もしくはジアリルアミンの代わりにＮ−メチルジアリルアミンを用いて重合反応を実施した以外は、実施例１３と同様に操作し、標記の共重合体を得た。その結果を表２に示す。
Example 12
Production of allylamine / isethionate polymer 21.1 g of water and 540.0 g of a 70 wt% aqueous solution of isethionic acid were added to a 1 liter four-necked round bottom separable flask equipped with a stirrer, thermometer and Dimroth reflux condenser. 1.0 mol) was added, and 171.3 g (3.0 mol) of allylamine (monoallylamine) was gradually added dropwise under cooling and stirring to prepare an aqueous solution of an allylamine and isethionate monomer. An aqueous solution of allylamine and isethionate having a monomer concentration of 75% by weight was kept at 55 ° C., and 12.20 g of ABAP (1.5 mol% based on the monomer) was added thereto as a radical polymerization initiator. Furthermore, 12.20 g of ABAP was also added after 24 hours had elapsed from the start of the polymerization reaction. The polymerization reaction was carried out at 55 ° C. for a total of 72 hours.
The obtained solution of the title polymer became a colorless transparent weak viscous solution. The polymerization yield was 95% and the weight average molecular weight was 3200. FIG. 3 shows the GPC measurement results.
Example 13
Production of a copolymer of allylamine and isethionate and diallylamine and isethionate (feeding molar ratio 4: 1)
A 1 liter four-necked round bottom separable flask equipped with a stirrer, thermometer, and Jimroth reflux condenser was charged with 83.7 g of water and 540.0 g (3.0 mol) of 70% by weight isethionic acid under cooling and stirring. Allylamine (monoallylamine) 137.0 g (2.4 mol) and diallylamine 58.3 g (0.6 mol) were gradually added dropwise to prepare a mixed monomer aqueous solution of allylamine / isethionate and diallylamine / isethionate. . A mixed monomer aqueous solution having a monomer concentration of 70% by weight was kept at 55 ° C., and 12.20 g of ABAP (1.5 mol% based on the monomer) was added thereto as a radical polymerization initiator. Further, 8.14 g of ABAP was also added after 24 hours had elapsed from the start of the polymerization reaction. The polymerization reaction was carried out at 55 ° C. for a total of 72 hours. The obtained aqueous solution of the title copolymer was a light yellowish brown transparent viscous solution. The polymerization yield was 95% and the weight average molecular weight was 4400.
Examples 14-16
Example of production except that the polymerization reaction was carried out using N-methyldiallylamine instead of diallylamine or by changing the composition ratio of the monomers for producing the copolymer of allylamine / isethionate and diallylamine / isethionate In the same manner as in Example 13, the title copolymer was obtained. The results are shown in Table 2.
実施例１７
アリルアミン・アミド硫酸塩重合体の製造
攪拌機、温度計、ジムロート式還流冷却管を備えた１リットルの４つ口丸底セパラブルフラスコに水 ３０８．４ｇ、アミド硫酸２９１．３ｇ（３．０モル）を仕込み、冷却攪拌下でアリルアミン（モノアリルアミン） １７１．３ｇ（３．０モル）を徐々に滴下してアリルアミン・アミド硫酸塩モノマー水溶液を調製した。モノマー濃度６０重量％のアリルアミン・アミド硫酸塩水溶液を５０℃に保ち、それにラジカル重合開始剤としてＡＢＡＰ ８．１４ｇ（モノマーに対して １．０モル％）添加した。さらに重合反応を開始してから２４時間経過した後にもＡＢＡＰ ８．１４ｇ添加した。重合反応は５０℃で合計７２時間行った。
得られた標記重合体の水溶液は、黄色透明の粘性溶液となった。重合収率は ９６％、重量平均分子量は、１３２００であった。
実施例１８
アリルアミン・アミド硫酸塩重合体の製造
モノマー濃度を変えて重合反応を実施した以外は、実施例１７と同様に操作し、アリルアミン・アミド硫酸塩重合体を得た。その結果を表３に示す。
実施例１９〜２２
アリルアミン・アミド硫酸塩とジアリルアミン類・アミド硫酸塩との共重合体の製造
付加塩としてアミド硫酸を用いてモノマーの仕込組成比を変えて、もしくはジアリルアミンの代わりにＮ−メチルジアリルアミンを用いて重合反応を実施した以外は、実施例１３と同様に操作し、標記の共重合体を得た。その結果を表３に示す。図４に、実施例１９で得られた重合体のＧＰＣ測定結果を示す。
Example 17
Production of allylamine / amide sulfate polymer 308.4 g of water and 291.3 g (3.0 mol) of amidosulfuric acid in a 1 liter four-necked round bottom separable flask equipped with a stirrer, thermometer and Dimroth reflux condenser. Then, 171.3 g (3.0 mol) of allylamine (monoallylamine) was gradually added dropwise under cooling and stirring to prepare an allylamine / amide sulfate monomer aqueous solution. An allylamine / amidosulfate aqueous solution having a monomer concentration of 60% by weight was kept at 50 ° C., and 8.14 g of ABAP (1.0 mol% based on the monomer) was added thereto as a radical polymerization initiator. Further, 8.14 g of ABAP was also added after 24 hours had elapsed from the start of the polymerization reaction. The polymerization reaction was carried out at 50 ° C. for a total of 72 hours.
The obtained aqueous solution of the title polymer became a yellow transparent viscous solution. The polymerization yield was 96%, and the weight average molecular weight was 13,200.
Example 18
Production of allylamine / amidosulfate polymer An allylamine / amidosulfate polymer was obtained in the same manner as in Example 17 except that the polymerization reaction was carried out by changing the monomer concentration. The results are shown in Table 3.
Examples 19-22
Production of copolymer of allylamine / amidosulfate and diallylamines / amidosulfate Polymerization reaction using amidosulfuric acid as addition salt, changing monomer charge composition ratio, or using N-methyldiallylamine instead of diallylamine The title copolymer was obtained in the same manner as in Example 13 except that The results are shown in Table 3. In FIG. 4, the GPC measurement result of the polymer obtained in Example 19 is shown.
比較例１
重合媒体として水を用いたアリルアミン・酢酸塩とジアリルアミン・酢酸塩との共重合体の製造（仕込モル比 ４：１）
攪拌機、温度計、ジムロート式還流冷却管を備えた１リットルの４つ口丸底セパラブルフラスコに水 １６０．９ｇ、酢酸 １８０．２ｇ（３．０モル）を仕込み、冷却攪拌下でアリルアミン（モノアリルアミン） １３７．０ｇ（２．４モル）、ジアリルアミン ５８．３ｇ（０．６モル）を徐々に滴下してアリルアミン・酢酸塩とジアリルアミン・酢酸塩の混合モノマー水溶液を調製した。モノマー濃度７０重量％の混合モノマー水溶液を５５℃に保ち、それにラジカル重合開始剤としてＡＢＡＰ １２．２０ ｇ（モノマーに対して １．５モル％）添加した。さらに重合反応を開始してから２４時間経過した後にもＡＢＡＰ １２．２０ｇ添加した。重合反応は５５℃で合計７２時間行った。得られた水溶液は、黄色透明で低粘性の溶液となった。ＧＰＣを測定しても重合反応を示唆するような重合体のピークは観察されなかった。
Comparative Example 1
Production of a copolymer of allylamine / acetate and diallylamine / acetate using water as the polymerization medium (feeding molar ratio 4: 1)
A 1 liter four-necked round bottom separable flask equipped with a stirrer, thermometer and Dimroth reflux condenser was charged with 160.9 g of water and 180.2 g (3.0 mol) of acetic acid, and allylamine (mono) under cooling and stirring. Allylamine) 137.0 g (2.4 mol) and diallylamine 58.3 g (0.6 mol) were gradually added dropwise to prepare a mixed monomer aqueous solution of allylamine / acetate and diallylamine / acetate. A mixed monomer aqueous solution having a monomer concentration of 70% by weight was kept at 55 ° C., and 12.20 g of ABAP (1.5 mol% based on the monomer) was added thereto as a radical polymerization initiator. Furthermore, 12.24 g of ABAP was also added after 24 hours had elapsed from the start of the polymerization reaction. The polymerization reaction was carried out at 55 ° C. for a total of 72 hours. The obtained aqueous solution became a yellow transparent and low-viscosity solution. Even when the GPC was measured, no polymer peak indicating a polymerization reaction was observed.
本発明のアリルアミン類酸付加塩重合体は、塩素を含まず、かつ水溶性に優れ、インクジェット記録紙用薬剤、特に耐水化剤として好適に用いられる。 The allylamine acid addition salt polymer of the present invention does not contain chlorine, is excellent in water solubility, and is suitably used as a chemical for ink jet recording paper, particularly as a water-resistant agent.
Claims (6)
（式中、Ｒ１およびＲ２は、それぞれ独立に水素原子またはヒドロキシル基を含んでいてもよい炭素数１〜４のアルキル基、Ｙ１はヒドロキシル基を含む炭素数１〜４のアルキル基または炭素数１〜４のアルキル基が置換されていてもよいアミノ基を示す。）
で表される構成単位、並びに一般式（ＩＩ−ａ）および一般式（ＩＩ−ｂ）
（式中、Ｒ３は水素原子またはヒドロキシル基を含んでいてもよい炭素数１〜４のアルキル基、Ｙ２はヒドロキシル基を含む炭素数１〜４のアルキル基または炭素数１〜４のアルキル基が置換されていてもよいアミノ基を示す。）
で表される構成単位の中から選ばれる少なくとも１種からなることを特徴とするアリルアミン類酸付加塩重合体。Formula (I)
(Wherein, R 1 and R 2 are each independently a hydrogen atom or a hydroxyl group optionally containing an the alkyl group having 1 to 4 carbon atoms, Y 1 is an alkyl group having 1 to 4 carbon including carbon hydroxyl group Or an amino group which may be substituted with an alkyl group having 1 to 4 carbon atoms.)
As well as the general formula (II-a) and the general formula (II-b)
(Wherein, R 3 is a hydrogen atom or hydroxyl group which may contain an alkyl group having 1 to 4 carbon atoms, Y 2 is a hydroxyl group a including 1 to 4 carbon atoms alkyl or 1 to 4 carbon atoms (The amino group which the alkyl group may be substituted is shown.)
An allylamine acid addition salt polymer comprising at least one selected from the structural units represented by:
（式中、Ｒ１およびＲ２は、それぞれ独立に水素原子またはヒドロキシル基を含んでいてもよい炭素数１〜４のアルキル基、Ｙ１はヒドロキシル基を含んでいてもよい炭素数１〜４のアルキル基または炭素数１〜４のアルキル基が置換されていてもよいアミノ基を示す。）
で表されるモノアリルアミン類酸付加塩、および／または一般式（ＩＶ）
（式中、Ｒ３は水素原子またはヒドロキシル基を含んでいてもよい炭素数１〜４のアルキル基、Ｙ２はヒドロキシル基を含んでいてもよい炭素数１〜４のアルキル基または炭素数１〜４のアルキル基が置換されていてもよいアミノ基を示す。）
で表されるジアリルアミン類酸付加塩からなる単量体を重合させて、分子量が１０，９０ ０以上のアリルアミン類酸付加塩重合体を得ることを特徴とする、アリルアミン類酸付加塩重合体の製造方法。In a polar solvent, in the presence of a water-soluble azo radical polymerization initiator and / or a persulfate radical polymerization initiator, the compound represented by the general formula (III)
(In the formula, R 1 and R 2 each independently represent a hydrogen atom or a hydroxyl group that may contain a hydroxyl group, and Y 1 may contain a hydroxyl group. Or an amino group which may be substituted with an alkyl group of 1 to 4 carbon atoms.)
And / or a monoallylamine acid addition salt represented by general formula (IV)
(In the formula, R 3 is a hydrogen atom or a C1-C4 alkyl group that may contain a hydroxyl group, Y 2 is a C1-C4 alkyl group that may contain a hydroxyl group, or C1 -4 represents an amino group on which the alkyl group may be substituted.)
A monomer consisting of diallylamine compound acid addition salt represented in by polymerizing, molecular weight and obtaining a 10,90 0 or more allylamines acid addition salt polymer, A Riruamin such acid addition salt polymer Manufacturing method.
The chemical | medical agent for inkjet recording paper of Claim 5 used as a waterproofing agent.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6160703A (en) * | 1984-09-01 | 1986-03-28 | Nitto Boseki Co Ltd | Production of polymer of monoallylamine or its salt |
| JPH09291493A (en) * | 1996-04-22 | 1997-11-11 | Asahi Denka Kogyo Kk | Agent for making recording paper waterproof |
| JP2000063435A (en) * | 1998-04-17 | 2000-02-29 | Nitto Boseki Co Ltd | Preparation of allylamine polymer |
| JP2002293842A (en) * | 2001-03-30 | 2002-10-09 | Nitto Boseki Co Ltd | Allylamine-allylsulfonic acid-based copolymer, its production method and use |
| JP2002316475A (en) * | 2000-10-27 | 2002-10-29 | Oji Paper Co Ltd | Ink jet recording sheet |
| JP2005059448A (en) * | 2003-08-15 | 2005-03-10 | Oji Paper Co Ltd | Inkjet recording sheet |
-
2004
- 2004-01-29 JP JP2004021995A patent/JP4581413B2/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6160703A (en) * | 1984-09-01 | 1986-03-28 | Nitto Boseki Co Ltd | Production of polymer of monoallylamine or its salt |
| JPH09291493A (en) * | 1996-04-22 | 1997-11-11 | Asahi Denka Kogyo Kk | Agent for making recording paper waterproof |
| JP2000063435A (en) * | 1998-04-17 | 2000-02-29 | Nitto Boseki Co Ltd | Preparation of allylamine polymer |
| JP2002316475A (en) * | 2000-10-27 | 2002-10-29 | Oji Paper Co Ltd | Ink jet recording sheet |
| JP2002293842A (en) * | 2001-03-30 | 2002-10-09 | Nitto Boseki Co Ltd | Allylamine-allylsulfonic acid-based copolymer, its production method and use |
| JP2005059448A (en) * | 2003-08-15 | 2005-03-10 | Oji Paper Co Ltd | Inkjet recording sheet |
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| Publication number | Publication date |
|---|---|
| JP2005213372A (en) | 2005-08-11 |
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