JP2015151438A - Resin and resin aqueous dispersion - Google Patents
Resin and resin aqueous dispersion Download PDFInfo
- Publication number
- JP2015151438A JP2015151438A JP2014025260A JP2014025260A JP2015151438A JP 2015151438 A JP2015151438 A JP 2015151438A JP 2014025260 A JP2014025260 A JP 2014025260A JP 2014025260 A JP2014025260 A JP 2014025260A JP 2015151438 A JP2015151438 A JP 2015151438A
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- resin
- group
- olefin polymer
- acid anhydride
- 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.)
- Granted
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 85
- 239000011347 resin Substances 0.000 title claims abstract description 85
- 239000006185 dispersion Substances 0.000 title claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229920000098 polyolefin Polymers 0.000 claims abstract description 54
- 125000004018 acid anhydride group Chemical group 0.000 claims abstract description 44
- 229920001577 copolymer Polymers 0.000 claims abstract description 42
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 25
- 239000002253 acid Substances 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 230000003472 neutralizing effect Effects 0.000 claims description 7
- 239000004711 α-olefin Substances 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 229920001519 homopolymer Polymers 0.000 claims description 5
- 238000004581 coalescence Methods 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 239000002904 solvent Substances 0.000 abstract description 22
- 239000011248 coating agent Substances 0.000 abstract description 12
- 238000000576 coating method Methods 0.000 abstract description 12
- 239000000758 substrate Substances 0.000 abstract description 10
- 230000000704 physical effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 11
- WOLATMHLPFJRGC-UHFFFAOYSA-N furan-2,5-dione;styrene Chemical compound O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 WOLATMHLPFJRGC-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- -1 polypropylene Polymers 0.000 description 8
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 239000000976 ink Substances 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229920005672 polyolefin resin Polymers 0.000 description 5
- 239000013615 primer Substances 0.000 description 5
- 239000002987 primer (paints) Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000047 product Substances 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
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 2
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 2
- 229940011051 isopropyl acetate Drugs 0.000 description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- XMYQHJDBLRZMLW-UHFFFAOYSA-N methanolamine Chemical compound NCO XMYQHJDBLRZMLW-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000012462 polypropylene substrate Substances 0.000 description 2
- 238000012673 precipitation polymerization Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000004034 viscosity adjusting agent Substances 0.000 description 2
- KZVBBTZJMSWGTK-UHFFFAOYSA-N 1-[2-(2-butoxyethoxy)ethoxy]butane Chemical compound CCCCOCCOCCOCCCC KZVBBTZJMSWGTK-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- AVTLBBWTUPQRAY-UHFFFAOYSA-N 2-(2-cyanobutan-2-yldiazenyl)-2-methylbutanenitrile Chemical compound CCC(C)(C#N)N=NC(C)(CC)C#N AVTLBBWTUPQRAY-UHFFFAOYSA-N 0.000 description 1
- XYVAYAJYLWYJJN-UHFFFAOYSA-N 2-(2-propoxypropoxy)propan-1-ol Chemical compound CCCOC(C)COC(C)CO XYVAYAJYLWYJJN-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- OJPDDQSCZGTACX-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)anilino]ethanol Chemical compound OCCN(CCO)C1=CC=CC=C1 OJPDDQSCZGTACX-UHFFFAOYSA-N 0.000 description 1
- QHKGDMNPQAZMKD-UHFFFAOYSA-N 2-amino-2-methylbutan-1-ol Chemical compound CCC(C)(N)CO QHKGDMNPQAZMKD-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
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- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
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- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
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- 239000011591 potassium Substances 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Abstract
Description
本発明は、酸無水物基を有する共重合体に、オレフィン重合体をグラフト変性した樹脂、および、該樹脂と中和剤と水とを含む樹脂水分散体に関する。さらに詳しくは、オレフィン重合体部位で低極性のオレフィン系のフィルムに対して優れた塗膜物性（基材密着性、耐水性、耐溶剤性）を発現し、酸無水物基を有する共重合体部位で他樹脂との相溶性や水分散性にも優れる樹脂水分散体に関する。 The present invention relates to a resin obtained by graft-modifying an olefin polymer on a copolymer having an acid anhydride group, and a resin aqueous dispersion containing the resin, a neutralizing agent, and water. More specifically, a copolymer having an acid anhydride group that exhibits excellent coating film properties (base material adhesion, water resistance, solvent resistance) with respect to an olefin film having a low polarity at the olefin polymer site. The present invention relates to a resin water dispersion which is excellent in compatibility with other resins and water dispersibility at a site.
近年、加工性や機械物性に優れる上に安価であるポリプロピレン、ポリエチレン、ポリエステル等のポリオレフィン系のフィルムが、食品包装用を始めとする包装材料として広く使用されている。しかし、これらポリオレフィン系のフィルムは極性が低く、他樹脂との反応点となる官能基が少ないため、他樹脂との親和性が乏しいという問題がある。これらポリオレフィン系のフィルムとの親和性に優れる、低極性のポリオレフィン系樹脂がプライマー、塗料、インキ、粘着剤または接着剤として用いられている（特許文献１）。しかしこれらの樹脂はトルエン、キシレン等の芳香族系有機溶剤にしか溶解しないため、安全衛生、環境面から水性化の流れが大きくなっている。（特許文献２）では、ポリオレフィン系樹脂を塩素化して水に分散しているが、塩素化ポリオレフィン系樹脂は焼却時に塩素化合物が発生するため、環境保護の観点から好ましくない。（特許文献３）では非塩素系のポリオレフィン系樹脂を水に分散させる試みがなされているが、ポリオレフィン系樹脂を水に分散するために界面活性剤を用いており、塗膜の耐水性を悪化させる恐れがある。 In recent years, polyolefin films such as polypropylene, polyethylene, and polyester, which are excellent in processability and mechanical properties and are inexpensive, are widely used as packaging materials including food packaging. However, these polyolefin-based films have a problem that their polarity is low and there are few functional groups that are reactive points with other resins, so that their affinity with other resins is poor. A low-polarity polyolefin-based resin having excellent affinity with these polyolefin-based films is used as a primer, paint, ink, pressure-sensitive adhesive or adhesive (Patent Document 1). However, since these resins are only soluble in aromatic organic solvents such as toluene and xylene, the flow of water-based treatment is increasing from the viewpoint of safety and health and the environment. In (Patent Document 2), a polyolefin resin is chlorinated and dispersed in water, but a chlorinated polyolefin resin is not preferable from the viewpoint of environmental protection because a chlorine compound is generated during incineration. In (Patent Document 3), an attempt is made to disperse non-chlorinated polyolefin resin in water, but a surfactant is used to disperse the polyolefin resin in water, which deteriorates the water resistance of the coating film. There is a fear.
低極性のポリオレフィン系のフィルムに対して優れた塗膜物性（基材密着性、耐水性、耐溶剤性）を発現し、他樹脂との相溶性にも優れる樹脂、および該樹脂からなる樹脂水分散体の提供を目的とする。 Resin that exhibits excellent coating properties (base material adhesion, water resistance, solvent resistance) for low-polarity polyolefin-based films, and excellent compatibility with other resins, and resin water comprising the resin The purpose is to provide a dispersion.
すなわち、本発明は、一般式（１）で表される、構成単位Ｉ、構成単位ＩＩ、および構成単位ＩＩＩを含んでなる樹脂に関する。 That is, the present invention relates to a resin comprising the structural unit I, the structural unit II, and the structural unit III represented by the general formula (1).
一般式（１）
Ｒ1：オレフィン重合体残基、
Ｒ2：炭素数１〜１０の２価の炭化水素基、
Ｒ3、Ｒ4、Ｒ5、およびＲ6：各々水素原子、芳香族基またはメチル基、
ｘ、ｙおよびｚ：各々１以上の整数であり、ｘ＋ｙ＋ｚは２〜５０００の整数、を表す。］
General formula (1)
R 1 : Olefin polymer residue,
R 2 : a divalent hydrocarbon group having 1 to 10 carbon atoms,
R 3 , R 4 , R 5 and R 6 : each a hydrogen atom, an aromatic group or a methyl group,
x, y and z are each an integer of 1 or more, and x + y + z represents an integer of 2 to 5000. ]
また、本発明は、前記樹脂、中和剤、および水を含む樹脂水分散体に関する。 Moreover, this invention relates to the resin water dispersion containing the said resin, the neutralizing agent, and water.
また、本発明は、一般式（１）のＲ1におけるオレフィン重合体が、炭素数２〜１０のα−オレフィンの単独重合体または共重合体である、前記樹脂水分散体に関する。 Further, the present invention is an olefin polymer in R 1 in the general formula (1) is a homopolymer or copolymer of α- olefin having 2 to 10 carbon atoms, relates to the resin aqueous dispersion.
また、本発明は、一般式（１）のＲ1におけるオレフィン重合体の重量平均分子量が、５００〜３００００である、前記樹脂水分散体に関する。 Further, the present invention has a weight average molecular weight of the olefin polymer in R 1 of the general formula (1) is 500 to 30,000, relating to the resin aqueous dispersion.
また、本発明は、一般式（１）で表される樹脂の酸価が３０〜３００である、前記樹脂水分散体に関する。 Moreover, this invention relates to the said resin water dispersion whose acid value of resin represented by General formula (1) is 30-300.
さらに、本発明は、一般式（１）で表される樹脂が、
一般式（２）で表される１つの酸無水物基を有する変性オレフィン重合体（ａ）の酸無水物基１モルに対し、
一般式（３）で表される１つの１級アミノ基と１つの水酸基とを有する化合物（ｂ）の１級アミノ基を１モル反応させて、１つの水酸基を有するオレフィン重合体（Ａ）を得、
得られた１つの水酸基を有するオレフィン重合体（Ａ）の水酸基１モルに対し、一般式（４）で表される、構成単位ＩＶおよび構成単位Ｖを含んでなる酸無水物基を有する共重合体（ｃ）の酸無水物基１〜３０モルを反応させて得られる樹脂であることを特徴とする、前記樹脂水分散体に関する
Furthermore, in the present invention, the resin represented by the general formula (1)
For 1 mol of acid anhydride group of the modified olefin polymer (a) having one acid anhydride group represented by the general formula (2),
An olefin polymer (A) having one hydroxyl group is obtained by reacting 1 mol of the primary amino group of the compound (b) having one primary amino group and one hydroxyl group represented by the general formula (3). Get
Copolymer having an acid anhydride group comprising the structural unit IV and the structural unit V represented by the general formula (4) with respect to 1 mole of the hydroxyl group of the resulting olefin polymer (A) having one hydroxyl group. It is a resin obtained by reacting 1 to 30 mol of an acid anhydride group of the coalescence (c).
一般式（２）
一般式（３）
一般式（４）
ｘ、ｙおよびｚ：各々１以上の整数であり、ｘ＋ｙ＋ｚは２〜５０００の整数、を表す。］
General formula (4)
x, y and z are each an integer of 1 or more, and x + y + z represents an integer of 2 to 5000. ]
本発明により、低極性のポリオレフィン系のフィルムに対して優れた塗膜物性（基材密着性、耐水性、耐溶剤性）を発現し、他樹脂との相溶性にも優れる樹脂水分散体を提供できる。 According to the present invention, a resin aqueous dispersion that exhibits excellent coating properties (base material adhesion, water resistance, solvent resistance) for low-polarity polyolefin-based films and is excellent in compatibility with other resins. Can be provided.
本発明の樹脂水分散体は、オレフィン重合体が酸無水物基を有する共重合体にグラフト変性された構造を有することを特徴とする。オレフィン重合体部位により、極性の低いポリオレフィン系のフィルムに対する高い基材密着性が得られると同時に、耐水性、耐溶剤性といった塗膜物性にも優れる。また、酸無水物基を有する共重合体部位により安定した水分散性が得られると同時に、プライマー、塗料、インキとして用いた際に他樹脂との相溶性にも優れる。 The aqueous resin dispersion of the present invention is characterized in that the olefin polymer has a structure graft-modified to a copolymer having an acid anhydride group. Due to the olefin polymer site, high substrate adhesion to a polyolefin film having low polarity is obtained, and at the same time, coating film properties such as water resistance and solvent resistance are excellent. Further, stable water dispersibility can be obtained by the copolymer portion having an acid anhydride group, and at the same time, compatibility with other resins is excellent when used as a primer, paint or ink.
＜一般式（１）で表される樹脂＞
本発明の樹脂水分散体に含まれる、オレフィン重合体が酸無水物基を有する共重合体にグラフト変性された樹脂は、下記一般式（１）で表される、構成単位Ｉ、構成単位ＩＩ、および構成単位ＩＩＩを含んでなる樹脂である。構成単位Ｉは、オレフィン骨格由来の構造により非極性基材への密着性、耐水性、耐溶剤性を付与する。構成単位ＩＩは、水への分散性を付与する。また、構成単位ＩＩＩは、高分子量化による機能発現を付与する。
<Resin represented by general formula (1)>
Resins in which the olefin polymer is graft-modified to a copolymer having an acid anhydride group, contained in the aqueous resin dispersion of the present invention, are represented by structural unit I and structural unit II represented by the following general formula (1). And a resin comprising the structural unit III. The structural unit I imparts adhesion to a nonpolar substrate, water resistance, and solvent resistance due to the structure derived from the olefin skeleton. The structural unit II imparts dispersibility in water. In addition, the structural unit III imparts functional expression by increasing the molecular weight.
一般式（１）
［一般式（１）中、
Ｒ1：オレフィン重合体残基、
Ｒ2：炭素数１〜１０の２価の炭化水素基、
Ｒ3、Ｒ4、Ｒ5、およびＲ6：各々水素原子、芳香族基またはメチル基、
ｘ、ｙおよびｚ：各々１以上の整数であり、ｘ＋ｙ＋ｚは２〜５０００の整数、を表す。］
[In general formula (1),
R 1 : Olefin polymer residue,
R 2 : a divalent hydrocarbon group having 1 to 10 carbon atoms,
R 3 , R 4 , R 5 and R 6 : each a hydrogen atom, an aromatic group or a methyl group,
x, y and z are each an integer of 1 or more, and x + y + z represents an integer of 2 to 5000. ]
前記一般式（１）で表される樹脂は、一般式（２）で表される１つの酸無水物基を有する変性オレフィン重合体（ａ）の酸無水物基に対し、一般式（３）で表される１つの１級アミノ基と１つの水酸基とを有する化合物（ｂ）の１級アミノ基を反応させて、１つの水酸基を有するオレフィン重合体（Ａ）を得た後、得られた１つの水酸基を有するオレフィン重合体（Ａ）の水酸基に対し、一般式（４）で表される酸無水物基を有する共重合体（ｃ）の酸無水物基を反応させて得ることができる。 The resin represented by the general formula (1) is represented by the general formula (3) with respect to the acid anhydride group of the modified olefin polymer (a) having one acid anhydride group represented by the general formula (2). Obtained by reacting the primary amino group of the compound (b) having one primary amino group and one hydroxyl group represented by formula (b) to obtain an olefin polymer (A) having one hydroxyl group. It can be obtained by reacting the acid anhydride group of the copolymer (c) having an acid anhydride group represented by the general formula (4) with the hydroxyl group of the olefin polymer (A) having one hydroxyl group. .
一般式（２）
一般式（３）
一般式（４）
ｘ、ｙおよびｚ：各々１以上の整数であり、ｘ＋ｙ＋ｚは２〜５０００の整数、を表す。］
General formula (4)
x, y and z are each an integer of 1 or more, and x + y + z represents an integer of 2 to 5000. ]
本発明で使用する一般式（４）で表される、酸無水物基を有する共重合体（ｃ）は、構成単位ＩＶおよび構成単位Ｖを含んでなり、水への分散安定性に優れ、プライマー、塗料、インキとして用いた際に他樹脂との相溶性にも優れる。構成単位ＩＶは、水への分散性を付与する。構成単位ＩＶと共重合可能な構成単位Ｖは、高分子量化による機能発現を付与する。また、変性オレフィン重合体（ａ）は芳香族炭化水素系の溶剤への溶解性に特に優れるが、酸無水物基を有する共重合体（ｃ）はこれらの溶剤にも良好な溶解性を示す。 The copolymer (c) having an acid anhydride group represented by the general formula (4) used in the present invention comprises the structural unit IV and the structural unit V, and is excellent in dispersion stability in water. Excellent compatibility with other resins when used as a primer, paint or ink. The structural unit IV imparts dispersibility in water. The structural unit V copolymerizable with the structural unit IV imparts functional expression due to the increase in molecular weight. Further, the modified olefin polymer (a) is particularly excellent in solubility in an aromatic hydrocarbon solvent, but the copolymer (c) having an acid anhydride group exhibits good solubility in these solvents. .
（一般式（２）で表される１つの酸無水物基を有する変性オレフィン重合体（ａ））
本発明で使用する１つの酸無水物基を有する変性オレフィン重合体（ａ）は、極性の低いポリオレフィン系のフィルムに対する高い基材密着性を有すことに加え、片末端に１つの酸無水物基を有するために、ゲル化することなくグラフト化反応に用いることができる。
(Modified olefin polymer (a) having one acid anhydride group represented by the general formula (2))
The modified olefin polymer (a) having one acid anhydride group used in the present invention has high substrate adhesion to a polyolefin film having a low polarity, and one acid anhydride at one end. Since it has a group, it can be used in a grafting reaction without gelation.
本発明で使用する１つの酸無水物基を有する変性オレフィン重合体（ａ）は、オレフィン重合体の末端を酸で変性することによって得ることができる。オレフィン重合体は、常法に従って、例えば、バナジウム系触媒、マグネシウム触媒、チタン、ハロゲン等を成分とするチタン系触媒等を用いて製造することができる。オレフィン重合体としては、炭素数２〜４０のα−オレフィンの単独重合体および共重合体が挙げられる。 The modified olefin polymer (a) having one acid anhydride group used in the present invention can be obtained by modifying the terminal of the olefin polymer with an acid. The olefin polymer can be produced by a conventional method using, for example, a vanadium catalyst, a magnesium catalyst, a titanium catalyst containing titanium, halogen, or the like as a component. Examples of the olefin polymer include homopolymers and copolymers of α-olefins having 2 to 40 carbon atoms.
一般式（２）におけるＲ1は、炭素数２〜１０のα−オレフィンの単独重合および共重合体であることが好ましく、炭素数２または３のα−オレフィンの単独重合体または共重合体であることがより好ましい。炭素数が１０より大きいと、水への分散性が悪化する恐れがある。
本発明に用いられるα−オレフィンとしては、例えば、エチレン、１−ブテン、１−ペンテン、４−メチル−１−ペンテン、３−メチル−１−ペンテン、１−ヘキセン等が挙げられる。
R 1 in the general formula (2) is preferably a homopolymer or copolymer of an α-olefin having 2 to 10 carbon atoms, and is a homopolymer or copolymer of an α-olefin having 2 or 3 carbon atoms. More preferably. If the carbon number is greater than 10, the dispersibility in water may be deteriorated.
Examples of the α-olefin used in the present invention include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-hexene and the like.
また、一般式（２）中、Ｒ1の重量平均分子量は、５００〜３００００であることが好ましく、１０００〜２００００であることがより好ましい。Ｒ1の重量平均分子量が５００未満であると、オレフィン骨格由来の非極性基剤への密着性、耐水性、耐溶剤性が低下する恐れがある。３００００より大きいと、溶剤への溶解性、水への分散性、他樹脂との相溶性が低下する恐れがある。 Further, in the general formula (2), the weight average molecular weight of R 1 is preferably 500 to 30,000, more preferably 1,000 to 20,000. If the weight average molecular weight of R 1 is less than 500, adhesion to a nonpolar base derived from an olefin skeleton, water resistance, and solvent resistance may be reduced. When it is larger than 30000, the solubility in a solvent, the dispersibility in water, and the compatibility with other resins may be lowered.
１つの酸無水物基を有する変性オレフィン重合体（ａ）は、市販品を用いることもできる。市販品としては、例えば、ベーカー・ヒューズ社製のＸ−１００６５、Ｘ−１００８７、Ｘ−１００４４等が挙げられる。 As the modified olefin polymer (a) having one acid anhydride group, a commercially available product can be used. Examples of commercially available products include X-10065, X-10087, and X-10044 manufactured by Baker Hughes.
（一般式（３）で表される１つの１級アミノ基と１つの水酸基を有する化合物（ｂ））
本発明で使用する１つのアミノ基と１つの水酸基を有する化合物（ｂ）は、分子中に、酸無水物基と反応しかつ反応速度の異なる２つの官能基を有することで、ゲル化することなくアミノ基と一般式（２）で表される１つの酸無水物基を有する変性オレフィン重合体（ａ）中の酸無水物基とを反応させる第１反応を優先的に行うことができる。
(Compound (b) having one primary amino group and one hydroxyl group represented by the general formula (3))
The compound (b) having one amino group and one hydroxyl group used in the present invention is gelled by having two functional groups that react with an acid anhydride group and have different reaction rates in the molecule. The first reaction in which the amino group and the acid anhydride group in the modified olefin polymer (a) having one acid anhydride group represented by the general formula (2) are reacted can be performed preferentially.
一般式（３）におけるＲ2は、炭素数１〜１０の２価の炭化水素基であることが好ましく、炭素数１〜５の２価の炭化水素基であることがより好ましい。
化合物（ｂ）としては、例えば、アミノメタノール、２−アミノエタノール、３−アミノ−１−プロパノール、４−アミノ−１−ブタノール、５−アミノ−１−ペンタノール、６−アミノ−１−ヘキサノール等を用いることができ、アミノメタノール、２−アミノエタノール、３−アミノ−１−プロパノールが特に好ましい。
R 2 in the general formula (3) is preferably a divalent hydrocarbon group having 1 to 10 carbon atoms, and more preferably a divalent hydrocarbon group having 1 to 5 carbon atoms.
Examples of the compound (b) include aminomethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, and 6-amino-1-hexanol. Aminomethanol, 2-aminoethanol, and 3-amino-1-propanol are particularly preferable.
（一般式（４）で表される酸無水物基を有する共重合体（ｃ））
本発明で使用する酸無水物基を有する共重合体（ｃ）は、常法に従って製造することができる。例えば、無水マレイン酸と、無水マレイン酸と共重合可能な原料モノマーを反応容器に仕込み、溶媒中、ラジカル重合開始剤とともに溶液重合法や沈殿重合法により共重合させることによって製造することができる。
(Copolymer (c) having an acid anhydride group represented by formula (4))
The copolymer (c) having an acid anhydride group used in the present invention can be produced according to a conventional method. For example, it can be produced by charging maleic anhydride and a raw material monomer copolymerizable with maleic anhydride into a reaction vessel and copolymerizing them in a solvent together with a radical polymerization initiator by a solution polymerization method or a precipitation polymerization method.
無水マレイン酸と共重合可能な原料モノマーとしては、例えば、スチレン、α−メチルスチレン、ｐ−ヒドロキシスチレン、クロロメチルスチレン、ビニルトルエン、インデン等のスチレン類；エチレン、イソブチレン等のα−オレフィン類が挙げられる。 Examples of the raw material monomer copolymerizable with maleic anhydride include styrenes such as styrene, α-methylstyrene, p-hydroxystyrene, chloromethylstyrene, vinyltoluene, and indene; and α-olefins such as ethylene and isobutylene. Can be mentioned.
ラジカル重合開始剤としては、従来から使用されているものを特に制限なく使用することができ、例えば、ジ（ドデカノイル）パーオキサイド、ベンゾイルパーオキサイド、クメンハイドロパーオキサイド、ｔ−ブチルハイドロパーオキサイド等の有機過酸化物；２，２'−アゾビスイソブチロニトリル、２，２'−アゾビス（２−メチルブチロニトリル）、ジメチル−２，２'−アゾビスイソブチレート、α，α'−アゾ−α−エチルブチロニトリル等のアゾ化合物が挙げられる。 As the radical polymerization initiator, those conventionally used can be used without particular limitation, for example, di (dodecanoyl) peroxide, benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, etc. Organic peroxides; 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate, α, α′- Examples include azo compounds such as azo-α-ethylbutyronitrile.
また、重合反応に際して用いられる溶媒としては、ラジカル重合を阻害しない種々の溶媒、例えば、アセトン、メチルエチルケトン等のケトン類；ｎ−ヘキサン、ｎ−オクタン等の脂肪族炭化水素類；ベンゼン、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素類；酢酸エチル、酢酸イソプロピル等の脂肪酸エステル類；ジイソプロピルエーテル、ジオキサン、テトラヒドロフラン等のエーテル類；塩化メチレン、クロロホルム等の塩素化炭化水素類が挙げられる。これらの溶媒は単独で使用してもよいし、２種以上混合して使用してもよい。 Moreover, as a solvent used in the polymerization reaction, various solvents that do not inhibit radical polymerization, for example, ketones such as acetone and methyl ethyl ketone; aliphatic hydrocarbons such as n-hexane and n-octane; benzene, toluene, and xylene And aromatic hydrocarbons such as ethylbenzene; fatty acid esters such as ethyl acetate and isopropyl acetate; ethers such as diisopropyl ether, dioxane and tetrahydrofuran; and chlorinated hydrocarbons such as methylene chloride and chloroform. These solvents may be used alone or in combination of two or more.
重合温度は、使用する溶媒やラジカル重合開始剤等により異なるが、一般には０〜２００℃、好ましくは３０〜１５０℃の範囲である。また、重合時間は、一般に１〜５０時間、好ましくは２〜２０時間の範囲である。また、重合は常圧または加圧下に行うことができる。 The polymerization temperature varies depending on the solvent used, radical polymerization initiator, and the like, but is generally in the range of 0 to 200 ° C, preferably 30 to 150 ° C. The polymerization time is generally in the range of 1 to 50 hours, preferably 2 to 20 hours. The polymerization can be carried out at normal pressure or under pressure.
重合反応終了後、反応混合物からのアルカリ水溶性樹脂の分離取得は、常法に従って行うことができる。例えば、沈殿重合法を採用した場合は、沈殿した樹脂を濾過脱液し、次いで乾燥することにより酸無水物基を有する共重合体（ｃ）が得られ、また、溶液重合法を採用した場合には、溶媒を除去した後に乾燥することにより酸無水物基を有する共重合体（ｃ）が得られる。 After completion of the polymerization reaction, separation and acquisition of the alkaline water-soluble resin from the reaction mixture can be performed according to a conventional method. For example, when the precipitation polymerization method is employed, the copolymer (c) having an acid anhydride group is obtained by filtering and draining the precipitated resin and then drying, and when the solution polymerization method is employed. The copolymer (c) having an acid anhydride group can be obtained by drying after removing the solvent.
一般式（４）で表される酸無水物基を有する共重合体（ｃ）の酸価は、１００〜３５０であることが好ましい。１００未満では水への分散性が悪化するおそれがあり、３５０以上では低極性基材への密着性や耐水性が悪化する恐れがある。 The acid value of the copolymer (c) having an acid anhydride group represented by the general formula (4) is preferably 100 to 350. If it is less than 100, dispersibility in water may be deteriorated, and if it is 350 or more, adhesion to a low-polarity substrate and water resistance may be deteriorated.
一般式（４）で表される酸無水物基を有する共重合体（ｃ）は、市販品を用いることもできる。市販品としては、例えば、株式会社クラレ製のイソバン−６００、イソバン−０４、イソバン−０６、イソバン−１０、イソバン−１８、サートマー社製のＳＭＡ−１０００、ＳＭＡ−２０００、ＳＭＡ−３０００等が挙げられる。 A commercial item can also be used for the copolymer (c) which has an acid anhydride group represented by General formula (4). Examples of commercially available products include Kuraray Co., Ltd. Isoban-600, Isoban-04, Isoban-06, Isoban-10, Isoban-18, Sartomer SMA-1000, SMA-2000, SMA-3000, and the like. It is done.
＜一般式（１）で表される樹脂の製造条件＞
一般式（１）で表される樹脂は、前述のとおり、一般式（２）で表される１つの酸無水物基を有する変性オレフィン重合体（ａ）の酸無水物基に対し、一般式（３）で表される１つの１級アミノ基と１つの水酸基とを有する化合物（ｂ）の１級アミノ基を反応させて、１つの水酸基を有するオレフィン重合体（Ａ）を得る第１反応工程と、
得られた１つの水酸基を有するオレフィン重合体（Ａ）の水酸基に対し、一般式（４）で表される酸無水物基を有する共重合体（ｃ）の酸無水物基を反応させる第２反応工程により、得ることができる。
<Production conditions for the resin represented by the general formula (1)>
As described above, the resin represented by the general formula (1) has a general formula with respect to the acid anhydride group of the modified olefin polymer (a) having one acid anhydride group represented by the general formula (2). The first reaction for obtaining an olefin polymer (A) having one hydroxyl group by reacting the primary amino group of the compound (b) having one primary amino group and one hydroxyl group represented by (3) Process,
Second, the acid anhydride group of the copolymer (c) having an acid anhydride group represented by the general formula (4) is reacted with the hydroxyl group of the obtained olefin polymer (A) having one hydroxyl group. It can be obtained by a reaction step.
（第１反応工程）
第１反応工程では、変性オレフィン重合体（ａ）の酸無水物基１モルに対し、一般式（３）で表される１つの１級アミノ基と１つの水酸基とを有する化合物（ｂ）の１級アミノ基を１モル反応させて、１つの水酸基を有するオレフィン重合体（Ａ）を得ることが好ましい。
化合物（ｂ）の１級アミノ基が１モル未満では、続く第２反応において、共重合体（ｃ）と遊離の変性オレフィン重合体（ａ）が競合し、変性オレフィン重合体（ａ）同士が反応して水に不溶な副生成物が生じる恐れがある。化合物（ｂ）の１級アミノ基が１モルを超えると、第２反応において共重合体（ｃ）同士が反応してゲル化する恐れがある。
(First reaction step)
In the first reaction step, the compound (b) having one primary amino group and one hydroxyl group represented by the general formula (3) with respect to 1 mol of the acid anhydride group of the modified olefin polymer (a). It is preferable to react 1 mol of the primary amino group to obtain an olefin polymer (A) having one hydroxyl group.
When the primary amino group of the compound (b) is less than 1 mol, the copolymer (c) and the free modified olefin polymer (a) compete with each other in the subsequent second reaction, and the modified olefin polymers (a) are Reaction may produce by-products that are insoluble in water. When the primary amino group of the compound (b) exceeds 1 mol, the copolymers (c) may react with each other in the second reaction to cause gelation.
第１反応で使用できる溶剤としては、例えば、アセトン、メチルエチルケトン等のケトン類；ｎ−ヘキサン、ｎ−オクタン等の脂肪族炭化水素類；ベンゼン、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素類；酢酸エチル、酢酸イソプロピル等の脂肪酸エステル類；ジイソプロピルエーテル、ジオキサン、テトラヒドロフラン等のエーテル類；塩化メチレン、クロロホルム等の塩素化炭化水素類が挙げられる。これらの溶媒は単独で使用してもよいし、２種以上混合して使用してもよい。続く第２反応で用いられる一般式（２）で表される１つの酸無水物基を有する変性オレフィン重合体（ａ）の溶解性の観点から、ベンゼン、トルエン、キシレン、エチルベンゼン等の芳香族炭化水素類が好ましい。 Examples of the solvent that can be used in the first reaction include ketones such as acetone and methyl ethyl ketone; aliphatic hydrocarbons such as n-hexane and n-octane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; Examples include fatty acid esters such as ethyl acetate and isopropyl acetate; ethers such as diisopropyl ether, dioxane and tetrahydrofuran; and chlorinated hydrocarbons such as methylene chloride and chloroform. These solvents may be used alone or in combination of two or more. From the viewpoint of the solubility of the modified olefin polymer (a) having one acid anhydride group represented by the general formula (2) used in the subsequent second reaction, aromatic carbonization such as benzene, toluene, xylene, ethylbenzene and the like. Hydrogens are preferred.
第１反応における反応温度は、０〜６０℃、好ましくは２０〜４０℃の範囲である。また、反応時間は、１〜２０時間、好ましくは２〜１０時間の範囲である。 The reaction temperature in the first reaction is in the range of 0 to 60 ° C, preferably 20 to 40 ° C. The reaction time is in the range of 1 to 20 hours, preferably 2 to 10 hours.
反応の終点は、ＧＰＣによる重量平均分子量測定、ＩＲ測定による酸無水物基ピークの消失等により判断する。 The end point of the reaction is judged by weight average molecular weight measurement by GPC, disappearance of acid anhydride group peak by IR measurement, and the like.
（第２反応工程）
第２反応工程では、第１反応で得られた１つの水酸基を有するオレフィン重合体（Ａ）の水酸基１モルに対し、一般式（４）で表される酸無水物基を有する共重合体（ｃ）の酸無水物基１〜３０モルを反応させて、一般式（１）で表される樹脂を生成することが好ましい。好ましくは、３〜１５モルである。１モル未満では、水への分散力が低下する、あるいはプライマー、塗料、インキとして用いた際に他樹脂との相溶性が悪化する恐れがある。３０モルを超えると、ポリオレフィン系のフィルムに対する高い基材密着性が発現しない恐れがある。
(Second reaction step)
In the second reaction step, a copolymer having an acid anhydride group represented by the general formula (4) per 1 mol of the hydroxyl group of the olefin polymer (A) having one hydroxyl group obtained in the first reaction ( It is preferable to react 1-30 mol of acid anhydride groups of c) to produce a resin represented by the general formula (1). Preferably, it is 3-15 mol. If it is less than 1 mol, the dispersibility in water may be reduced, or the compatibility with other resins may deteriorate when used as a primer, paint or ink. When it exceeds 30 mol, there is a possibility that high substrate adhesion to a polyolefin-based film may not be exhibited.
本発明の第２反応では、上記の第１反応と同様の溶剤を用いることができる。 In the second reaction of the present invention, the same solvent as in the first reaction can be used.
第２反応における反応温度は、６０〜１１０℃、好ましくは７０〜１００℃の範囲である。また、反応時間は、１〜２０時間、好ましくは２〜１０時間の範囲である。 The reaction temperature in the second reaction is in the range of 60 to 110 ° C, preferably 70 to 100 ° C. The reaction time is in the range of 1 to 20 hours, preferably 2 to 10 hours.
反応の終点は、ＧＰＣによる重量平均分子量測定、ＩＲ測定による水酸基ピークの消失等により判断する。 The end point of the reaction is judged by the weight average molecular weight measurement by GPC, the disappearance of the hydroxyl peak by IR measurement, or the like.
＜樹脂水分散体＞
本発明の樹脂水分散体は、溶剤中で得られた一般式（１）で表される樹脂中のカルボン酸を中和剤で中和し、水を加えて溶剤を除去することにより水に分散することで得られる。
<Resin water dispersion>
The resin water dispersion of the present invention is obtained by neutralizing the carboxylic acid in the resin represented by the general formula (1) obtained in a solvent with a neutralizing agent, and adding water to remove the solvent. Obtained by dispersing.
一般式（１）で表される樹脂の酸価は３０〜３００であり、好ましくは１００〜２５０である。酸価が３０より低いと水への分散安定性が劣る恐れがある。３００より高いと、耐水性が劣る恐れがある。 The acid value of the resin represented by the general formula (1) is 30 to 300, preferably 100 to 250. If the acid value is lower than 30, dispersion stability in water may be inferior. If it is higher than 300, the water resistance may be poor.
（中和剤）
中和剤としては、例えば、アンモニア、エチルアミン、トリメチルアミン、トリエチルアミン、トリイソプロピルアミン、トリブチルアミン、トリエタノールアミン、Ｎ−メチルジエタノールアミン、Ｎ−フェニルジエタノールアミン、モノエタノールアミン、ジメチルエタノールアミン、ジエチルエタノールアミン、モルホリン、Ｎ−メチルモルホリン、２−アミノ−２−エチル−１−プロパノールなどの有機アミン類；リチウム、カリウム、ナトリウムなどのアルカリ金属；水酸化リチウム、水酸化ナトリウム、水酸化カリウムなどの無機アルカリ類等が挙げられる。ただし、乾燥性に効果が高いのは揮発性の高い塩基であり、好ましい塩基はアミノメチルプロパノール、アンモニアである。中和剤の添加量は、通常は、一般式（１）で表される樹脂のカルボキシル基に対して０．８〜１当量とすることが好ましい。
(Neutralizer)
Examples of the neutralizing agent include ammonia, ethylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, monoethanolamine, dimethylethanolamine, diethylethanolamine, morpholine. Organic amines such as N-methylmorpholine and 2-amino-2-ethyl-1-propanol; alkali metals such as lithium, potassium and sodium; inorganic alkalis such as lithium hydroxide, sodium hydroxide and potassium hydroxide Is mentioned. However, it is a highly volatile base that is highly effective in drying, and preferred bases are aminomethylpropanol and ammonia. Usually, the amount of the neutralizing agent added is preferably 0.8 to 1 equivalent with respect to the carboxyl group of the resin represented by the general formula (1).
（その他添加剤）
本発明の水性樹脂分散体には、本発明の効果を損なわない範囲で必要に応じて他の樹脂成分や、成膜助剤、酸化防止剤、紫外線吸収剤、塩酸吸収剤、脱塩酸防止剤、顔料、染料、充填剤、ブロッキング剤、帯電防止剤、スリップ防止剤、タッキファイヤ−樹脂、増粘剤、消泡剤、防腐剤、ｐＨ調整剤、レベリング剤、架橋剤、界面活性剤などを必要に応じて配合できる。
(Other additives)
In the aqueous resin dispersion of the present invention, other resin components, film forming aids, antioxidants, ultraviolet absorbers, hydrochloric acid absorbents, dehydrochlorinating inhibitors are added as necessary as long as the effects of the present invention are not impaired. Pigments, dyes, fillers, blocking agents, antistatic agents, anti-slip agents, tackifier resins, thickeners, antifoaming agents, preservatives, pH adjusters, leveling agents, crosslinking agents, surfactants, etc. Can be blended as needed.
成膜助剤は、塗膜の形成を助け、塗膜が形成された後においては比較的速やかに蒸発揮散して塗膜の強度を向上させる一時的な可塑化機能を担うものであり、沸点が１１０〜２００℃の溶媒が好適に用いられる。具体的には、プロピレングリコールモノブチルエーテル、エチレングリコールメチルエーテル、エチレングリコールエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールジエチルエーテル、ジプロピレングリコールモノプロピルエーテル、カルビトール、ブチルカルビトール、ジブチルカルビトール、ベンジルアルコールなどが挙げられる。これら成膜助剤は、樹脂水分散体組成物中に０．５〜１５重量％含まれることが好ましい。 The film-forming aid is responsible for the temporary plasticization function that helps the formation of the coating film and evaporates relatively quickly after the coating film is formed, thereby improving the strength of the coating film. Is preferably a solvent having a temperature of 110 to 200 ° C. Specifically, propylene glycol monobutyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol monobutyl ether, diethylene glycol diethyl ether, dipropylene glycol monopropyl ether, carbitol, butyl carbitol, dibutyl carbitol, benzyl alcohol, etc. Is mentioned. These film forming aids are preferably contained in the resin water dispersion composition in an amount of 0.5 to 15% by weight.
粘性調整剤は、樹脂水分散体１００重量部に対して１〜１００重量部用いてもよい。粘性調整剤としては、例えば、カルボキシメチルセルロース、メチルセルロース、ヒドロキシメチルセルロース、エチルセルロース、ポリビニルアルコール、ポリアクリル酸（及びその塩）、酸化スターチ、リン酸化スターチ、カゼインなどが挙げられる。 The viscosity modifier may be used in an amount of 1 to 100 parts by weight with respect to 100 parts by weight of the resin water dispersion. Examples of the viscosity modifier include carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, ethylcellulose, polyvinyl alcohol, polyacrylic acid (and its salt), oxidized starch, phosphorylated starch, and casein.
本発明の樹脂は、粘着剤、接着剤、塗料、インキ、プライマー等の用途に用いることができる。 The resin of the present invention can be used for applications such as pressure-sensitive adhesives, adhesives, paints, inks and primers.
以下に、実施例により本発明を更に具体的に説明するが、以下の実施例は本発明の権利範囲を何ら制限するものではない。なお、特に断りがない限り、「部」、「％」とは「重量部」、「重量％」を意味する。 EXAMPLES The present invention will be described more specifically with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. Unless otherwise specified, “parts” and “%” mean “parts by weight” and “% by weight”.
（ＩＲ測定条件）
ＦＴ−ＩＲ（Ｔｈｅｒｍｏ Ｆｉｓｈｅｒ Ｓｃｉｅｎｔｉｆｉｃ社製、ＮＩＣＯＬＥＴ６７００）を用いて、酸無水物基由来のピーク（１７９０ｃｍ-1付近）と水酸基由来のピーク（３３００ｃｍ-1付近）を測定した。
(IR measurement conditions)
Using FT-IR (manufactured by Thermo Fisher Scientific, NICOLET 6700), a peak derived from an acid anhydride group (near 1790 cm −1 ) and a peak derived from a hydroxyl group (near 3300 cm −1 ) were measured.
（酸価測定条件）
酸価とは、樹脂１ｇ中に含まれる酸性成分を中和するのに要する水酸化カリウムのミリグラム数である。乾燥させた樹脂について、ＪＩＳ Ｋ２５０１に記載の方法に従い、自動滴定装置（平沼産業社製、ＣＯＭ−１５００）を用いて、水酸化カリウム・エタノール溶液で電位差滴定を行い算出した。
(Acid value measurement conditions)
The acid value is the number of milligrams of potassium hydroxide required to neutralize the acidic component contained in 1 g of resin. The dried resin was calculated by potentiometric titration with a potassium hydroxide / ethanol solution using an automatic titrator (COM-1500, manufactured by Hiranuma Sangyo Co., Ltd.) according to the method described in JIS K2501.
（重量平均分子量）
重量平均分子量は、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）測定によるポリスチレン換算の値である。乾燥させた樹脂をテトラヒドロフランに溶解させ、０．１％の溶液を調製し、ＨＬＣ−８３２０−ＧＰＣ（東ソー社製、カラム番号Ｍ−００５３ 分子量測定範囲約２千〜約４００万）により重量平均分子量を測定した。
(Weight average molecular weight)
The weight average molecular weight is a value in terms of polystyrene as measured by GPC (gel permeation chromatography). The dried resin is dissolved in tetrahydrofuran to prepare a 0.1% solution, and the weight average molecular weight is measured by HLC-8320-GPC (manufactured by Tosoh Corporation, column number M-0053, molecular weight measurement range of about 2,000 to about 4,000,000). Was measured.
＜樹脂水分散体の作製＞
［実施例１］
（１）第１反応
滴下槽、コンデンサー、攪拌翼、および温度計を備え付けた反応槽に、変性ポリプロピレン／ヘキセン共重合体（ａ−１）（Ｘ−１００８７（ベーカー・ヒュージ社））１００．０部とトルエン１５９．６部とを仕込み３５℃に昇温して変性ポリプロピレン／ヘキセン共重合体（ａ−１）を溶解した。続いて、同じ温度で滴下槽からエタノールアミン６．４部を１５分かけて滴下し、その後７時間攪拌を続け、ＩＲで酸無水物基由来（１７９０ｃｍ-1付近）のピークが消失したことを確認し、樹脂溶液（Ｉ）を得た。
（２）第２反応
コンデンサー、攪拌翼、および温度計を備え付けた反応槽に、スチレン／無水マレイン酸共重合体（ｃ−１）（ＳＭＡ−３０００（サートマー社））２５０．０部とトルエン３７５．０部とを仕込み９０℃に昇温し、その後３時間同じ温度で攪拌を続けスチレン／無水マレイン酸共重合体（ｃ−１）を溶解した。そこへ、（１）で得られた樹脂溶液（Ｉ）を加え、その後７時間、同じ温度で攪拌を続け、樹脂溶液（ＩＩ）を得た。ＩＲで水酸基由来のピーク（３３００ｃｍ-1付近）が消失したことを確認し、温度を３０℃まで冷却した。
続いて、樹脂溶液（ＩＩ）に２５％アンモニア８６．４部と水５７５．６部とを添加して水に分散し、ストリッピングによりトルエンを除去した。その後、２５％アンモニア水でｐＨを８．５とし、更にイオン交換水で固形分を３５％に調整して樹脂水分散体を得た。なお、固形分は、１５０℃２０分焼き付け残分により求めた。
<Preparation of resin water dispersion>
[Example 1]
(1) First reaction A modified polypropylene / hexene copolymer (a-1) (X-10087 (Baker-Huge Company)) 100.0 was added to a reaction tank equipped with a dropping tank, a condenser, a stirring blade, and a thermometer. And 159.6 parts of toluene were charged and the temperature was raised to 35 ° C. to dissolve the modified polypropylene / hexene copolymer (a-1). Subsequently, 6.4 parts of ethanolamine was dropped from the dropping tank at the same temperature over 15 minutes, and then the stirring was continued for 7 hours. The peak derived from the acid anhydride group (near 1790 cm −1 ) disappeared by IR. As a result, a resin solution (I) was obtained.
(2) Second reaction In a reaction vessel equipped with a condenser, a stirring blade, and a thermometer, 250.0 parts of a styrene / maleic anhydride copolymer (c-1) (SMA-3000 (Sartomer)) and toluene 375 0.0 part was charged and the temperature was raised to 90 ° C., followed by stirring at the same temperature for 3 hours to dissolve the styrene / maleic anhydride copolymer (c-1). The resin solution (I) obtained in (1) was added thereto, and then stirring was continued at the same temperature for 7 hours to obtain a resin solution (II). It was confirmed by IR that the hydroxyl group-derived peak (near 3300 cm −1 ) disappeared, and the temperature was cooled to 30 ° C.
Subsequently, 86.4 parts of 25% ammonia and 575.6 parts of water were added to the resin solution (II) and dispersed in water, and toluene was removed by stripping. Thereafter, the pH was adjusted to 8.5 with 25% aqueous ammonia, and the solid content was adjusted to 35% with ion-exchanged water to obtain a resin water dispersion. In addition, solid content was calculated | required by 150 degreeC 20 minute baking residue.
［実施例２〜９］
表１に示す配合組成で、実施例１と同様の方法で反応させ、実施例２〜９の樹脂水分散体を得た。
[Examples 2 to 9]
With the compounding composition shown in Table 1, the reaction was conducted in the same manner as in Example 1 to obtain resin water dispersions of Examples 2-9.
（ａ−１）Ｒ１：プロピレン／ヘキセン共重合体（酸価１２５、重量平均分子量９５０）
（ａ−２）Ｒ１：デセン共重合体（酸価１３０、重量平均分子量９２０）
（ａ−３）Ｒ１：プロピレン／ヘキセン共重合体（酸価８、重量平均分子量１８０００）
（ａ−４）Ｒ１：プロピレン共重合体（酸価１７０、重量平均分子量７００）
（ｃ−１）スチレン／無水マレイン酸共重合体：スチレン／無水マレイン酸＝３／１（酸価２８５、重量平均分子量９５００）
（ｃ−２）スチレン／無水マレイン酸共重合体：スチレン／無水マレイン酸＝１０／１（酸価１０５、重量平均分子量８４００）
（ｃ−３）スチレン／無水マレイン酸共重合体：スチレン／無水マレイン酸＝４／９（酸価３４６、重量平均分子量９２００）
(A-1) R1: Propylene / hexene copolymer (acid value 125, weight average molecular weight 950)
(A-2) R1: Decene copolymer (acid value 130, weight average molecular weight 920)
(A-3) R1: Propylene / hexene copolymer (acid value 8, weight average molecular weight 18000)
(A-4) R1: Propylene copolymer (acid value 170, weight average molecular weight 700)
(C-1) Styrene / maleic anhydride copolymer: Styrene / maleic anhydride = 3/1 (acid value 285, weight average molecular weight 9500)
(C-2) Styrene / maleic anhydride copolymer: Styrene / maleic anhydride = 10/1 (acid value 105, weight average molecular weight 8400)
(C-3) Styrene / maleic anhydride copolymer: styrene / maleic anhydride = 4/9 (acid number 346, weight average molecular weight 9200)
［比較例１］
コンデンサー、攪拌翼、および温度計を備え付けた反応槽に、変性ポリプロピレン／ヘキセン共重合体（ａ−１）（Ｘ−１００８７（ベーカー・ヒュージ社））１００部に２５％アンモニア１５．２部と水１７０．５部とを仕込み９０℃に昇温し、その後７時間同じ温度で攪拌を続けＸ−１００８７を溶解した。
Ｘ−１００８７：片末端無水マレイン酸変性プロピレン／ヘキセン共重合体（酸価１２５、重量平均分子量９５０）
[Comparative Example 1]
In a reaction vessel equipped with a condenser, stirring blades, and thermometer, 100 parts of modified polypropylene / hexene copolymer (a-1) (X-10087 (Baker Huge)), 15.2 parts of 25% ammonia and water 170.5 parts was charged and the temperature was raised to 90 ° C., and then stirring was continued at the same temperature for 7 hours to dissolve X-10087.
X-10087: One-end maleic anhydride-modified propylene / hexene copolymer (acid value 125, weight average molecular weight 950)
［比較例２］
コンデンサー、攪拌翼、および温度計を備え付けた反応槽に、スチレン／無水マレイン酸共重合体（ｃ−１）（ＳＭＡ−３０００（サートマー社））１００部と２５％アンモニア３４．５部と水１５１．２部とを仕込み９０℃に昇温し、その後７時間同じ温度で攪拌を続けＳＭＡ−３０００を溶解した。
ＳＭＡ−３０００：スチレン／無水マレイン酸共重合体（酸価２８５、重量平均分子量９５００）
[Comparative Example 2]
In a reaction vessel equipped with a condenser, a stirring blade, and a thermometer, 100 parts of a styrene / maleic anhydride copolymer (c-1) (SMA-3000 (Sartomer)), 34.5 parts of 25% ammonia, and water 151 .2 parts were charged and the temperature was raised to 90 ° C., and then stirring was continued at the same temperature for 7 hours to dissolve SMA-3000.
SMA-3000: Styrene / maleic anhydride copolymer (acid value 285, weight average molecular weight 9500)
＜樹脂水分散体の評価＞
得られた樹脂水分散体について、密着性、分散安定性を評価した。評価結果を表２に示す。
<Evaluation of resin water dispersion>
About the obtained resin water dispersion, adhesiveness and dispersion stability were evaluated. The evaluation results are shown in Table 2.
（密着性：碁盤目剥離試験）
表面をイソプロピルアルコールで清拭したポリプロピレン基材に、得られた樹脂水分散体を噴霧塗布した。塗布後、試験片を乾燥機中で９０℃３０分間焼き付けし塗装板を得た。
塗装板を２３℃で２４時間放置した後、ＪＩＳ Ｋ ５４００に記載されている碁盤目付着試験の方法に準じて２ｍｍ間隔で１００マス（１０×１０）の碁盤目を付けた試験片を作製しセロハンテープを貼り付けた後、９０℃方向にはく離させ、１００マスの碁盤目のうちはく離されなかった碁盤目数にて評価した。評価としては、はく離されなかったマスの数が多い方を付着性が良好とした。評価基準を下記に示す。
○：剥離無し
△：わずかに剥離（実用上問題のないレベル）
×：完全に剥離
(Adhesion: cross-cut peel test)
The obtained resin water dispersion was spray-coated on a polypropylene substrate whose surface was wiped with isopropyl alcohol. After application, the test piece was baked in a dryer at 90 ° C. for 30 minutes to obtain a coated plate.
After leaving the painted plate at 23 ° C. for 24 hours, a test piece with a grid of 100 squares (10 × 10) is prepared at intervals of 2 mm in accordance with the grid adhesion test method described in JIS K 5400. After applying the cellophane tape, it was peeled in the direction of 90 ° C., and the number of grids that were not peeled out of the 100 square grids was evaluated. As an evaluation, the one having a larger number of cells that were not peeled was considered to have good adhesion. The evaluation criteria are shown below.
○: No peeling △: Slight peeling (practical level)
×: Completely peeled
（分散安定性）
樹脂水分散体を室温で２週間貯蔵した後、分散状態を目視で評価した。
○：良好
△：ややブツあり（実用上問題のないレベル）
×：分離、ゲル化
(Dispersion stability)
After the resin aqueous dispersion was stored at room temperature for 2 weeks, the dispersion state was visually evaluated.
○: Good △: Slightly bumpy (practical problem-free level)
×: Separation, gelation
（耐水性）
表面をイソプロピルアルコールで清拭したポリプロピレン基材に、得られた樹脂水分散体を噴霧塗布した。塗布後、試験片を乾燥機中で９０℃３０分間焼き付けし塗装板を得た。
水を綿棒に浸し、塗装板を５往復程ラビングした。評価基準は以下の通りである。
○：塗膜のとられなし
△：塗膜は一部とられるが、基材表面は見えない（実用上問題のないレベル）
×：塗膜がとられ、基材表面も見える
(water resistant)
The obtained resin water dispersion was spray-coated on a polypropylene substrate whose surface was wiped with isopropyl alcohol. After application, the test piece was baked in a dryer at 90 ° C. for 30 minutes to obtain a coated plate.
Water was dipped in a cotton swab and the coated plate was rubbed about 5 times. The evaluation criteria are as follows.
○: No coating film removed Δ: Part of the coating film is taken, but the surface of the substrate is not visible (a level that causes no practical problems)
X: The coating film is removed and the surface of the substrate is visible
表２に示すように、実施例１〜９で得た樹脂水分散体を用いた場合、ポリオレフィン基材への密着性、水への分散性、耐水性のバランスに優れる。中でも、実施例１および９で特に良好な結果となった。一方、比較例１、２で得た樹脂水分散体を用いた場合、ポリオレフィン基材への密着性、水への分散安定性、耐水性の低下が見られた。 As shown in Table 2, when the resin water dispersions obtained in Examples 1 to 9 are used, the balance between the adhesion to the polyolefin substrate, the dispersibility in water, and the water resistance is excellent. Among them, particularly good results were obtained in Examples 1 and 9. On the other hand, when the resin water dispersions obtained in Comparative Examples 1 and 2 were used, adhesion to the polyolefin substrate, dispersion stability in water, and water resistance were reduced.
Claims (6)
一般式（１）
Ｒ1：オレフィン重合体残基、
Ｒ2：炭素数１〜１０の２価の炭化水素基、
Ｒ3、Ｒ4、Ｒ5、およびＲ6：各々水素原子、芳香族基またはメチル基、
ｘ、ｙおよびｚ：各々１以上の整数であり、ｘ＋ｙ＋ｚは２〜５０００の整数、を表す。］ A resin comprising the structural unit I, the structural unit II, and the structural unit III represented by the general formula (1).
General formula (1)
R 1 : Olefin polymer residue,
R 2 : a divalent hydrocarbon group having 1 to 10 carbon atoms,
R 3 , R 4 , R 5 and R 6 : each a hydrogen atom, an aromatic group or a methyl group,
x, y and z are each an integer of 1 or more, and x + y + z represents an integer of 2 to 5000. ]
一般式（２）で表される１つの酸無水物基を有する変性オレフィン重合体（ａ）の酸無水物基１モルに対し、
一般式（３）で表される１つの１級アミノ基と１つの水酸基とを有する化合物（ｂ）の１級アミノ基を１モル反応させて、１つの水酸基を有するオレフィン重合体（Ａ）を得、
得られた１つの水酸基を有するオレフィン重合体（Ａ）の水酸基１モルに対し、一般式（４）で表される、構成単位ＩＶおよび構成単位Ｖを含んでなる酸無水物基を有する共重合体（ｃ）の酸無水物基１〜３０モルを反応させて得られる樹脂であることを特徴とする、請求項２〜５いずれか記載の樹脂水分散体。
一般式（２）
一般式（３）
一般式（４）
ｘ、ｙおよびｚ：各々１以上の整数であり、ｘ＋ｙ＋ｚは２〜５０００の整数、を表す。］ The resin represented by the general formula (1)
For 1 mol of acid anhydride group of the modified olefin polymer (a) having one acid anhydride group represented by the general formula (2),
An olefin polymer (A) having one hydroxyl group is obtained by reacting 1 mol of the primary amino group of the compound (b) having one primary amino group and one hydroxyl group represented by the general formula (3). Get
Copolymer having an acid anhydride group comprising the structural unit IV and the structural unit V represented by the general formula (4) with respect to 1 mole of the hydroxyl group of the resulting olefin polymer (A) having one hydroxyl group. The resin aqueous dispersion according to any one of claims 2 to 5, which is a resin obtained by reacting 1 to 30 mol of an acid anhydride group of the coalescence (c).
General formula (2)
General formula (3)
General formula (4)
x, y and z are each an integer of 1 or more, and x + y + z represents an integer of 2 to 5000. ]
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS598738A (en) * | 1982-07-08 | 1984-01-18 | Showa Denko Kk | Treatment of olefinic polymer |
| JPS60233131A (en) * | 1984-05-04 | 1985-11-19 | Toagosei Chem Ind Co Ltd | Modifier for polyolefinic resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS598738A (en) * | 1982-07-08 | 1984-01-18 | Showa Denko Kk | Treatment of olefinic polymer |
| JPS60233131A (en) * | 1984-05-04 | 1985-11-19 | Toagosei Chem Ind Co Ltd | Modifier for polyolefinic resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110832406A (en) * | 2017-06-26 | 2020-02-21 | 花王株式会社 | Binder resin composition for toner |
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