JP2001329124A - Water-based composition and antistatic film using the same - Google Patents
Water-based composition and antistatic film using the sameInfo
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- JP2001329124A JP2001329124A JP2000154520A JP2000154520A JP2001329124A JP 2001329124 A JP2001329124 A JP 2001329124A JP 2000154520 A JP2000154520 A JP 2000154520A JP 2000154520 A JP2000154520 A JP 2000154520A JP 2001329124 A JP2001329124 A JP 2001329124A
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- water
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- 239000000203 mixture Substances 0.000 title claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title abstract description 43
- 229920001577 copolymer Polymers 0.000 claims abstract description 26
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 9
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000005977 Ethylene Substances 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 125000002723 alicyclic group Chemical group 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 abstract description 7
- 238000000034 method Methods 0.000 description 22
- 238000000576 coating method Methods 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 17
- 239000006185 dispersion Substances 0.000 description 10
- -1 polyethylene terephthalate Polymers 0.000 description 10
- 239000000178 monomer Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- 239000002216 antistatic agent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000001875 compounds Chemical group 0.000 description 4
- 230000001804 emulsifying effect Effects 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-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
- 239000003093 cationic surfactant Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 239000005871 repellent Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- RRZIJNVZMJUGTK-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical compound FC(F)=C(F)OC(F)=C(F)F RRZIJNVZMJUGTK-UHFFFAOYSA-N 0.000 description 1
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 description 1
- JAIXJKPOHMMBKS-UHFFFAOYSA-N 2-chloro-1,1,3,4,4,5,6,6,6-nonafluoro-5-(trifluoromethyl)hex-1-ene Chemical compound FC(C(C(F)(F)F)(C(C(C(=C(F)F)Cl)F)(F)F)F)(F)F JAIXJKPOHMMBKS-UHFFFAOYSA-N 0.000 description 1
- 125000006181 4-methyl benzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])C([H])([H])* 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000001680 brushing effect Effects 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 229920006228 ethylene acrylate copolymer Polymers 0.000 description 1
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、水性組成物および
これを用いた撥水性の帯電防止膜に関するものである。TECHNICAL FIELD The present invention relates to an aqueous composition and a water-repellent antistatic film using the same.
【０００２】[0002]
【従来の技術】プラスチックは軽量性、成形性、外観が
優れるため、成型体やフィルム・シートとして、家電・
オフィス機器の筐体、自動車部品、各種包装用材料、雑
貨品等に幅広く使用されている。しかしながら、プラス
チックは材料自身の電気抵抗が高いため、摩擦や剥離に
よって生じた静電気が漏洩することなく蓄積し、このた
め外観的には埃付着による商品価値の低下、電子機器な
どでは放電による誤動作などの問題点を有している。2. Description of the Related Art Plastics are excellent in lightness, moldability, and appearance.
Widely used for housing of office equipment, automobile parts, various packaging materials, miscellaneous goods, etc. However, plastics have high electrical resistance, so the static electricity generated by friction and peeling accumulates without leaking, which reduces the product value due to dust adhesion and malfunctions due to electric discharge in electronic devices. Problem.
【０００３】このような静電気障害に対しては、帯電防
止剤を使用することがその対処手段として公知である。
即ち、アニオン界面活性剤、カチオン界面活性剤、両性
界面活性剤、ノニオン界面活性剤等からなる帯電防止剤
をプラスチックに練り込む（内部添加）か、またはプラ
スチック表面に塗布する（外部塗布）ことが一般的に行
われている。[0003] The use of an antistatic agent is known as a countermeasure against such electrostatic damage.
That is, an antistatic agent composed of an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, or the like can be kneaded into a plastic (internal addition) or applied to the plastic surface (external application). Generally done.
【０００４】内部添加の場合は、帯電防止効果の耐久性
は比較的良好なものの、プラスチック材料の全体に添加
する必要があるため、添加量を多く必要とし、そのた
め、コストが大きくなる傾向がある。[0004] In the case of internal addition, although the durability of the antistatic effect is relatively good, it is necessary to add it to the entire plastic material, so that a large amount of addition is required, which tends to increase the cost. .
【０００５】外部塗布の場合は、帯電防止効果を必要と
する表面のみに適用するのでコストは小さいが、表面摩
擦や洗浄により帯電防止剤が容易に脱落し、その効果が
失われ易いという欠点を持っている。[0005] In the case of external coating, the cost is small because it is applied only to the surface requiring an antistatic effect, but the disadvantage is that the antistatic agent easily falls off due to surface friction or washing, and the effect is easily lost. have.
【０００６】また一方で、野外で使用する衣類、自動車
などの外装・電気部品などは水の浸透を避けるために撥
水処理が必要である。[0006] On the other hand, clothes and exterior / electric parts such as automobiles used outdoors require a water-repellent treatment to avoid water penetration.
【０００７】[0007]
【発明が解決しようとする課題】かかる問題点に対し、
特開平４−１９８３０９号公報には、第４級アンモニウ
ム塩を含有するポリアクリルアミド系共重合体の水性組
成物をプラスチック表面に塗布することによって摩擦耐
久性のある帯電防止性の塗膜を形成する方法が提案され
ている。しかしながら、この方法であっても、更なる耐
久性が要求される場面、例えば湿潤条件下での摩擦耐久
性や高温での水洗に対する耐久性の点ではまだ改良の必
要がある。また、ポリエチレンテレフタレートフィルム
等の基材に対する密着性という点でも改良の余地があ
る。SUMMARY OF THE INVENTION
JP-A-4-198309 discloses that an aqueous composition of a polyacrylamide copolymer containing a quaternary ammonium salt is applied to the surface of a plastic to form an antistatic coating film having friction durability. A method has been proposed. However, even with this method, there is still a need for improvement in situations where further durability is required, for example, friction durability under wet conditions and durability against water washing at high temperatures. Further, there is room for improvement in terms of adhesion to a substrate such as a polyethylene terephthalate film.
【０００８】一方、帯電防止性の塗膜を得る別の手段と
しては、例えば特開平２−１２０３７０号公報や特開平
３−１２６７６９号公報に見られるように、過塩素酸や
チオシアン酸塩等の導電性塩を遊離基重合性単量体に含
有させて放射線を照射し、帯電防止性の硬化塗膜を得る
方法が知られている。しかしながら、この方法にあって
は、導電化のために用いる材料が低分子量で、しかも本
質的に水溶性であるため、耐水性の点で不満足な水準に
ある。On the other hand, as another means for obtaining an antistatic coating film, for example, as disclosed in JP-A-2-120370 and JP-A-3-126679, there are known methods such as perchloric acid and thiocyanate. There is known a method in which a conductive salt is contained in a free-radical polymerizable monomer and irradiated with radiation to obtain a cured antistatic cured coating film. However, in this method, the material used for conductivity is low in molecular weight and essentially water-soluble, so that it is at an unsatisfactory level in terms of water resistance.
【０００９】同様に、第４級アンモニウム塩型界面活性
剤、例えばトリエチルアルキルエーテルアンモニウムサ
ルフェートを導電化剤として用いる方法が、特開昭６０
−２２１４１４号公報に提案されているが、水溶性低分
子量化合物である点で前記と同様の欠点を有している。Similarly, a method of using a quaternary ammonium salt type surfactant, for example, triethylalkyl ether ammonium sulfate as a conductive agent is disclosed in Japanese Patent Application Laid-Open No. 60-1985.
Although it is proposed in JP-A-221414, it has the same drawbacks as described above in that it is a water-soluble low molecular weight compound.
【００１０】また、一方繊維に撥水性を持たせるために
は、フッ素樹脂エマルジョンをコーティングする方法が
用いられているが、衣類などに代表される防水・撥水加
工は強力な疎水性の発現であり、水の弾きは良好である
が、静電気を蓄積する傾向がある。On the other hand, in order to impart water repellency to the fiber, a method of coating with a fluororesin emulsion is used. However, waterproofing and water repellent treatment represented by clothing and the like is characterized by strong hydrophobicity. Yes, water repellency is good, but tends to accumulate static electricity.
【００１１】したがって、親水性を付与することにより
得られる帯電防止特性と疎水性を付与することにより得
られる撥水性は相反する特性となり、両立しがたいもの
であった。Therefore, the antistatic property obtained by imparting hydrophilicity and the water repellency obtained by imparting hydrophobicity are contradictory properties and are incompatible.
【００１２】本発明は、このような従来の問題点に鑑み
てなされたものであり、その目的とするところは、水洗
に対する耐久性など優れた耐久性と、撥水性とを有する
帯電防止性塗膜を形成する水性組成物を提供することに
ある。The present invention has been made in view of such conventional problems, and an object of the present invention is to provide an antistatic coating having excellent durability such as durability against water washing and water repellency. It is to provide an aqueous composition for forming a film.
【００１３】[0013]
【課題を解決するための手段】本発明の水性組成物は、
下記Ａ成分とＢ成分を含有してなる水性組成物であっ
て、Ａ成分とＢ成分の合計量に対するＡ成分の重量比が
０．０５〜０．５０である水性組成物である。Means for Solving the Problems The aqueous composition of the present invention comprises:
An aqueous composition containing the following components A and B, wherein the weight ratio of the component A to the total amount of the components A and B is 0.05 to 0.50.
【００１４】Ａ成分は、下記式（１）で表されるエチレ
ン構造単位７０〜９９モル％と、下記一般式（２）で表
されるアクリレート構造単位０〜１５モル％と、下記一
般式（３）で表されるアクリルアミド構造単位１〜３０
モル％とを含有し、重量平均分子量が１,０００〜８０,
０００であるカチオン変性共重合体である。The component A comprises 70 to 99 mol% of an ethylene structural unit represented by the following formula (1), 0 to 15 mol% of an acrylate structural unit represented by the following general formula (2), and Acrylamide structural unit 1 to 30 represented by 3)
Mol%, and a weight average molecular weight of 1,000 to 80,
000, which is a cation-modified copolymer.
【００１５】[0015]
【化２】 Embedded image
【００１６】上記式中、Ｒ１は水素原子又は炭素数１〜
４のアルキル基を示し、Ｒ２は炭素数２〜８のアルキレ
ン基を示し、Ｒ３、Ｒ４、Ｒ５はそれぞれ独立に炭素数
１〜１２のアルキル基、炭素数７〜１２のアリールアル
キル基又は炭素数６〜１２の脂環アルキル基を示し、Ｘ
はハロゲン原子、ＣＨ３ＯＳＯ３、Ｃ２Ｈ５ＯＳＯ３又
はＲ６ＳＯ３を示し、ここで、Ｒ６は炭素数１〜１２の
アルキル基、炭素数７〜１２のアリールアルキル基又は
炭素数６〜１２の脂環アルキル基を示す。In the above formula, R1 is a hydrogen atom or a compound having 1 to 1 carbon atoms.
R2 represents an alkylene group having 2 to 8 carbon atoms; R3, R4, and R5 each independently represent an alkyl group having 1 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, or a carbon atom having 7 to 12 carbon atoms; An alicyclic alkyl group of 6 to 12;
Represents a halogen atom, CH3OSO3, C2H5OSO3 or R6SO3, wherein R6 represents an alkyl group having 1 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, or an alicyclic alkyl group having 6 to 12 carbon atoms.
【００１７】Ｂ成分は、フッ素原子を重量分率で２５％
以上含む重合体又は共重合体である。The component B contains 25% by weight of fluorine atoms.
A polymer or copolymer containing the above.
【００１８】[0018]
【発明の実施の形態】以下に本発明の実施に関連する事
項について詳細に説明する。 （１）Ａ成分 Ａ成分として使用するカチオン変性共重合体は、上記し
たように、式（１）で表されるエチレン構造単位と、一
般式（２）で表されるアクリレート構造単位と、一般式
（３）で表されるアクリルアミド構造単位とを含有して
なる線状に不規則に配列したアクリルアミド系共重合体
である。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The matters relating to the implementation of the present invention will be described below in detail. (1) Component A As described above, the cation-modified copolymer used as the component A includes an ethylene structural unit represented by the formula (1), an acrylate structural unit represented by the general formula (2), It is an acrylamide-based copolymer linearly and irregularly arranged containing the acrylamide structural unit represented by the formula (3).
【００１９】式（１）で表されるエチレン構造単位は、
分子内に７０〜９９モル％含有されている。この含有割
合が７０モル％未満の場合は塗膜の水洗時の耐久性が悪
化し、９９モル％を越える場合は帯電防止効果が劣る。
好ましい範囲は８０〜９７モル％である。The ethylene structural unit represented by the formula (1) is
70-99 mol% is contained in the molecule. When the content is less than 70 mol%, the durability of the coating film at the time of washing is deteriorated, and when it exceeds 99 mol%, the antistatic effect is poor.
The preferred range is 80-97 mol%.
【００２０】一般式（２）で表されるアクリレート構造
単位は、分子内に０〜１５モル％含有されている。この
含有割合が１５モル％を越えると塗膜にベタツキが生じ
てしまう。該アクリレート構造単位は、本発明では必ず
しも必須ではないが、存在することによりＢ成分との混
和性および接着性が良好となり、透明な硬化塗膜が得ら
れやすいので好ましい。アクリレート構造単位の含有割
合の好ましい範囲は１〜１０モル％である。The acrylate structural unit represented by the general formula (2) is contained in the molecule in an amount of 0 to 15 mol%. If the content exceeds 15 mol%, the coating film becomes sticky. The acrylate structural unit is not essential in the present invention, but is preferable because the presence of the acrylate structural unit improves the miscibility with the component B and the adhesiveness, and makes it easy to obtain a transparent cured coating film. The preferred range of the content ratio of the acrylate structural unit is 1 to 10 mol%.
【００２１】このアクリレート構造単位において、Ｒ１
は水素原子又は炭素数１〜４のアルキル基である。炭素
数４を越えると、塗膜が柔らかくなり過ぎ、ベタツキの
原因となる。Ｒ１の具体例としては、水素原子、メチル
基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−
ブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基等が挙げら
れ、これらの基は１分子中に混在していてもよい。これ
らの中ではメチル基およびエチル基が特に好ましい。In this acrylate structural unit, R1
Is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. When the number of carbon atoms exceeds 4, the coating film becomes too soft and causes stickiness. Specific examples of R1 include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-
Examples thereof include a butyl group, a sec-butyl group and a t-butyl group, and these groups may be present in one molecule. Of these, a methyl group and an ethyl group are particularly preferred.
【００２２】一般式（３）で示されるアクリルアミド構
造単位は、分子内に１〜３０モル％含有されている。こ
の含有割合が１モル％未満の場合は帯電防止性が不足
し、３０モル％を越える場合は塗膜の高温耐水性が悪化
する。好ましい範囲は２〜１０モル％である。The acrylamide structural unit represented by the general formula (3) is contained in the molecule in an amount of 1 to 30 mol%. When the content is less than 1 mol%, the antistatic property is insufficient, and when it exceeds 30 mol%, the high temperature water resistance of the coating film is deteriorated. A preferred range is 2 to 10 mol%.
【００２３】このアクリルアミド構造単位において、Ｒ
２は炭素数２〜８のアルキレン基である。具体例として
は、エチレン基、プロピレン基、ヘキサメチレン基、ネ
オペンチレン基等が挙げられ、これらの基は１分子中に
混在していてもよい。これらの中では、製造の容易性お
よび経済性の面からエチレン基とプロピレン基が特に好
ましい。In this acrylamide structural unit, R
2 is an alkylene group having 2 to 8 carbon atoms. Specific examples include an ethylene group, a propylene group, a hexamethylene group, a neopentylene group, and the like, and these groups may be present in one molecule. Among these, an ethylene group and a propylene group are particularly preferable from the viewpoint of ease of production and economy.
【００２４】また、Ｒ３、Ｒ４、Ｒ５は、それぞれ独立
に、炭素数１〜１２のアルキル基、炭素数７〜１２のア
リールアルキル基、又は、炭素数６〜１２の脂環アルキ
ル基である。具体例としては、メチル基、エチル基、ｎ
−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｓｅｃ
−ブチル基、ｎ−オクチル基、ｎ−ラウリル基等のアル
キル基；ベンジル基、４−メチルベンジル基等のアリー
ルアルキル基；シクロヘキシル基、メチルシクロヘキシ
ル基等の脂環アルキル基が挙げられ、これらの基は１分
子中に混在していてもよい。これらの中ではメチル基、
エチル基が特に好ましい。R3, R4 and R5 are each independently an alkyl group having 1 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, or an alicyclic alkyl group having 6 to 12 carbon atoms. Specific examples include a methyl group, an ethyl group, n
-Propyl group, i-propyl group, n-butyl group, sec
Alkyl groups such as -butyl group, n-octyl group and n-lauryl group; arylalkyl groups such as benzyl group and 4-methylbenzyl group; alicyclic alkyl groups such as cyclohexyl group and methylcyclohexyl group; The groups may be mixed in one molecule. In these, methyl group,
Ethyl groups are particularly preferred.
【００２５】また、４級アンモニウム塩の対イオンであ
るＸは、Ｃｌ、Ｂｒ、Ｉなどのハロゲン原子、ＣＨ３Ｏ
ＳＯ３、Ｃ２Ｈ５ＯＳＯ３等のアルキルサルフェート、
又は、Ｒ６ＳＯ３であり、これらは１分子中に混在して
いてもよい。ここで、Ｒ６ＳＯ３の具体例としては、メ
タンスルホン酸、エタンスルホン酸、プロパンスルホン
酸、ドデカンスルホン酸、パラトルエンスルホン酸、メ
タキシレンスルホン酸などが挙げられる。Ｘは、帯電防
止性能の点から、Ｃｌ、ＣＨ３ＯＳＯ３、Ｃ２Ｈ５ＯＳ
Ｏ３、メタンスルホン酸、エタンスルホン酸、パラトル
エンスルホン酸が好ましい。X, which is a counter ion of a quaternary ammonium salt, is a halogen atom such as Cl, Br, I, etc .;
Alkyl sulfates such as SO3, C2H5OSO3,
Alternatively, R6SO3, which may be present in one molecule. Here, specific examples of R6SO3 include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, dodecanesulfonic acid, paratoluenesulfonic acid, and metaxylenesulfonic acid. X represents Cl, CH3OSO3, C2H5OS from the viewpoint of antistatic performance.
O3, methanesulfonic acid, ethanesulfonic acid, and paratoluenesulfonic acid are preferred.
【００２６】以上の構造単位よりなるＡ成分のカチオン
変性共重合体は、本発明の効果を損なわない範囲で、少
量の他の構造単位、例えば、アクリル酸、メタクリル
酸、アクリロニトリル、グリシジルメタクリレート、ス
チレン等の構造単位を含有してもよい。The cation-modified copolymer of the component A comprising the above structural unit may contain a small amount of other structural units such as acrylic acid, methacrylic acid, acrylonitrile, glycidyl methacrylate, and styrene as long as the effects of the present invention are not impaired. And the like.
【００２７】このカチオン変性共重合体の重量平均分子
量は１，０００〜８０，０００である。重量平均分子量
が１，０００未満の場合には塗膜の物性が著しく低下
し、８０，０００を越える場合には水に対する分散性が
低下する。特に好ましい重量平均分子量は３，０００〜
５０，０００である。ここで、重量平均分子量とは、ゲ
ルパーミュエーションクロマトグラフィー（ＧＰＣ）で
測定した単分散のポリスチレン換算の重量平均分子量を
いい、超高温ＧＰＣ法（絹川等、高分子論文集４４巻２
号、１３９〜１４１頁、１９８７）に準じて測定でき
る。The cation-modified copolymer has a weight average molecular weight of 1,000 to 80,000. When the weight average molecular weight is less than 1,000, the physical properties of the coating film are remarkably reduced, and when it exceeds 80,000, the dispersibility in water is reduced. Particularly preferred weight average molecular weight is 3,000-
50,000. Here, the weight-average molecular weight means a monodisperse polystyrene-equivalent weight-average molecular weight measured by gel permeation chromatography (GPC).
No. 139-141, 1987).
【００２８】このカチオン変性共重合体の製造方法は、
特に限定されるものではない。たとえば特開平４−１９
８３０９号公報に記載されているように、エチレンとア
クリル酸エステルを高圧重合法により共重合させて得ら
れるエチレン−アクリル酸エステル共重合体をたとえば
特開昭６０−７９００８号公報に記載の方法により加水
分解と同時に熱減成して所望の分子量とし、得られたエ
チレン−アクリル酸エステル−アクリル酸共重合体を
Ｎ，Ｎ−ジアルキルアミノアルキルアミンでアミド化し
たのち、４級化剤でカチオン変性することにより、Ａ成
分の共重合体が得られる。The method for producing this cation-modified copolymer is as follows:
There is no particular limitation. For example, JP-A-4-19
As described in JP-A-8309, an ethylene-acrylate copolymer obtained by copolymerizing ethylene and an acrylate by a high-pressure polymerization method is produced, for example, by the method described in JP-A-60-79008. The resulting ethylene-acrylic acid ester-acrylic acid copolymer is amidated with N, N-dialkylaminoalkylamine, and then cationically modified with a quaternizing agent. By doing so, a copolymer of the component A is obtained.
【００２９】このＡ成分の共重合体を水に分散、乳化ま
たは可溶化させる方法についても、特に限定されるもの
ではない。たとえば、特開平４−１９８３０９号公報に
記載されているように、該共重合体、水および必要であ
れば界面活性剤をオートクレーブ等の撹拌装置を備えた
高圧容器中に仕込み、撹拌しながら加熱する高圧乳化法
により、均一な水分散体とすることができる。The method for dispersing, emulsifying or solubilizing the copolymer of the component A in water is not particularly limited. For example, as described in JP-A-4-198309, the copolymer, water and, if necessary, a surfactant are charged into a high-pressure vessel equipped with a stirrer such as an autoclave and heated while stirring. By the high-pressure emulsification method described above, a uniform aqueous dispersion can be obtained.
【００３０】ここで、前記界面活性剤としては、ノニオ
ン性およびカチオン性のものが好ましく、また、その使
用量は、通常、カチオン変性共重合体１００重量部に対
して２５重量部以下、好ましくは２０重量部以下であ
る。なお、本カチオン変性共重合体は、それ自体が乳化
力を有するものであるので、界面活性剤は必ずしも要し
ない。The surfactant is preferably a nonionic or cationic surfactant. The amount of the surfactant is usually 25 parts by weight or less, preferably 25 parts by weight or less, based on 100 parts by weight of the cation-modified copolymer. 20 parts by weight or less. In addition, since the present cation-modified copolymer itself has emulsifying power, a surfactant is not necessarily required.
【００３１】また、上記高圧容器での加熱温度は、通
常、カチオン変性共重合体が溶融する温度よりも５〜２
０℃高い温度、すなわち６０〜２００℃が好ましい。ま
た、加熱時間は、加熱温度によって異なるが、１０分間
〜１時間程度で充分である。The heating temperature in the high-pressure vessel is usually 5 to 2 times higher than the temperature at which the cation-modified copolymer melts.
A temperature 0 ° C. higher, that is, 60 to 200 ° C. is preferred. The heating time varies depending on the heating temperature, but about 10 minutes to 1 hour is sufficient.
【００３２】（２）Ｂ成分 本発明のＢ成分として使用する重合体は、フッ素原子を
重量分率で２５%以上含む重合体または共重合体であ
る。フッ素原子の重量分率が３０％〜８０％が好まし
く、２５％未満では、良好な撥水性が発現されない。本
発明に使用されるフッ素原子を２５%以上含む重合体
（共重合体）としては特に限定されるものではないが、
テトラフルオロエチレン、パーフルオロビニルエーテ
ル、ヘキサフルオロプロピレン、クロロトリフルオロエ
チレン、ビニリデンフルオライド、フルオロアルキルア
クリレート、フルオロアルキルメタクリレート、フルオ
ロアルキルシロキサンの一種以上の重合体または共重合
体が挙げられる。また、水中への分散性を高めるため
に、共重合可能なモノマーと共重合してもよい。さらに
安定性を向上させるために、有機溶剤を使用してもよ
い。ただし、共重合可能なモノマーおよび有機溶剤は必
ずしも必須成分ではない。本重合体を、水中に分散また
は乳化する方法については特に限定されるものでない
が、前記重合体（共重合体）の微粉末を界面活性剤を用
いて水中に分散する方法、または、前記フッ素原子含有
モノマーまたは、前記フッ素原子含有モノマーと共重合
可能なモノマーを乳化重合することにより得ることがで
きる。共重合可能なモノマーとしては特に限定されるも
のではないが、アクリル酸エステル類、メタクリル酸エ
ステル類、脂肪族カルボン酸ビニルエステル、芳香族カ
ルボン酸ビニルエステル、アクリル酸（塩）、メタクリ
ル酸（塩）、などがあげられ、単独もしくは複数で使用
できる。安定性向上のために使用される溶剤としては、
アセトン、メチルエチルケトン、炭素数1〜4のアルコー
ル、ジメチルスルホキシド、ジメチルホルムアミドなど
水に対して溶解性を持つ溶剤が好ましい。この溶剤は0
〜25％の範囲で使用される。(2) Component B The polymer used as the component B of the present invention is a polymer or copolymer containing 25% or more by weight of fluorine atoms. The weight fraction of fluorine atoms is preferably 30% to 80%, and if it is less than 25%, good water repellency is not exhibited. The polymer (copolymer) containing 25% or more of fluorine atoms used in the present invention is not particularly limited,
Examples include one or more polymers or copolymers of tetrafluoroethylene, perfluorovinyl ether, hexafluoropropylene, chlorotrifluoroethylene, vinylidene fluoride, fluoroalkyl acrylate, fluoroalkyl methacrylate, and fluoroalkyl siloxane. Further, in order to enhance dispersibility in water, it may be copolymerized with a copolymerizable monomer. In order to further improve the stability, an organic solvent may be used. However, the copolymerizable monomer and the organic solvent are not necessarily essential components. The method of dispersing or emulsifying the present polymer in water is not particularly limited, but the method of dispersing the polymer (copolymer) fine powder in water using a surfactant, or the method of dispersing or emulsifying the fluorine in the water, It can be obtained by emulsion polymerization of an atom-containing monomer or a monomer copolymerizable with the fluorine atom-containing monomer. The copolymerizable monomer is not particularly limited, but may be acrylic acid ester, methacrylic acid ester, aliphatic carboxylic acid vinyl ester, aromatic carboxylic acid vinyl ester, acrylic acid (salt), methacrylic acid (salt). ), Etc., and can be used alone or in combination. As a solvent used for improving stability,
Solvents having solubility in water, such as acetone, methyl ethyl ketone, alcohols having 1 to 4 carbon atoms, dimethyl sulfoxide and dimethylformamide, are preferred. This solvent is 0
Used in the range of ~ 25%.
【００３３】水中への分散において使用される界面活性
剤は特に限定されないが、非イオン系および／またはカ
チオン系活性剤が好ましい。The surfactant used for dispersion in water is not particularly limited, but nonionic and / or cationic surfactants are preferred.
【００３４】（３）水性組成物 本発明の水性組成物は、上記Ａ成分のカチオン変性共重
合体とＢ成分のフッ素原子含有重合体が均一に水又は水
を主成分とする水系媒体に分散されたものである。ここ
でいう分散とは、これら成分を水に分散させたもの、乳
化させたもの、可溶化させたもの等、巨視的に均一な系
を包含する概念である。(3) Aqueous Composition In the aqueous composition of the present invention, the cation-modified copolymer of the component A and the fluorine atom-containing polymer of the component B are uniformly dispersed in water or an aqueous medium containing water as a main component. It was done. The term “dispersion” as used herein is a concept that encompasses macroscopically uniform systems such as those in which these components are dispersed in water, emulsified, and solubilized.
【００３５】この水性組成物の調製方法としては、上記
Ａ成分とＢ成分とを水分散体同士で混合すること、Ａ成
分の水分散体にＢ成分を分散すること、Ｂ成分の水分散
体にＡ成分を分散することのいずれでもよい。この内、
Ａ成分、Ｂ成分それぞれの水分散体を調整し、混合する
方法がもっとも簡便である。The aqueous composition may be prepared by mixing the above-mentioned A component and the B component with each other in an aqueous dispersion, dispersing the B component in the aqueous dispersion of the A component, and dispersing the aqueous dispersion of the B component. May be dispersed. Of these,
The simplest method is to prepare and mix the aqueous dispersions of the component A and the component B, respectively.
【００３６】水性組成物中に含まれる両成分の濃度（固
形分濃度）は、Ａ成分が２〜４０重量％、Ｂ成分が５〜
４０重量％であることが好ましい。上記濃度を上回ると
分離、粘度上昇のため塗布が困難となる。また、上記濃
度を下回ると有効成分濃度が小さくなり、塗布膜もムラ
が生じ易くなる。The concentration (solid content) of both components contained in the aqueous composition is 2 to 40% by weight for the component A and 5 to 5% for the component B.
Preferably it is 40% by weight. If the concentration exceeds the above range, application becomes difficult due to separation and increase in viscosity. On the other hand, when the concentration is lower than the above-mentioned concentration, the concentration of the active ingredient becomes small, and the coating film is apt to be uneven.
【００３７】また、Ａ成分とＢ成分の合計に対するＡ成
分の重量比は０．０５〜０．５０である。Ａ成分の重量
比が０．０５未満であると、表面抵抗値が高くなり、良
好な帯電防止効果が得られない。また、Ａ成分の重量比
が０．５０より大きいと塗膜の撥水性が著しく低下す
る。The weight ratio of the component A to the total of the components A and B is 0.05 to 0.50. If the weight ratio of the component A is less than 0.05, the surface resistance increases, and a good antistatic effect cannot be obtained. When the weight ratio of the component A is more than 0.50, the water repellency of the coating film is remarkably reduced.
【００３８】本発明の水性組成物は、第３の成分として
架橋剤を含有してもよい。架橋剤としては、ポリエポキ
シ化合物、メラミン化合物、ジブチル錫ジラウレート等
の有機スズ化合物、水溶性または水分散性のポリイソシ
アネート化合物等が挙げられる。本発明の水性組成物に
おいて、架橋剤は必ずしも必要でないが、架橋剤を配合
すると、塗膜の強度が上昇し、耐水性も増加する。The aqueous composition of the present invention may contain a crosslinking agent as a third component. Examples of the crosslinking agent include polyepoxy compounds, melamine compounds, organotin compounds such as dibutyltin dilaurate, and water-soluble or water-dispersible polyisocyanate compounds. In the aqueous composition of the present invention, a cross-linking agent is not always necessary. However, when a cross-linking agent is blended, the strength of the coating film increases and the water resistance also increases.
【００３９】また、本発明の水性組成物においては、着
色のために一般的な体質顔料等を配合したり、耐熱性付
与を目的とした酸化防止剤の配合、接着性を調整する際
の各種分散剤、皮張り防止剤、レベリング剤、消泡剤、
増粘剤、造膜助剤、離型剤等の各種添加剤を性能が低下
しない範囲以内で配合することも可能である。In the aqueous composition of the present invention, a general extender pigment or the like may be blended for coloring, an antioxidant may be blended for the purpose of imparting heat resistance, and various kinds of additives may be used for adjusting the adhesiveness. Dispersants, anti-skinning agents, leveling agents, defoamers,
Various additives such as a thickener, a film-forming aid, and a release agent can be blended within a range where the performance is not reduced.
【００４０】本発明の水性組成物は、プラスチックなど
の各種基材の表面に塗布する帯電防止剤として使用する
ことができる。基材の種類、塗布方法、塗布量は特に限
定されない。塗布方法としては、例えば、スプレー処
理、刷毛処理、ロールコータ処理、浸漬処理等が挙げら
れる。塗布後、適宜の条件で乾燥させることにより、耐
温水性、撥水性に優れる帯電防止性の塗膜が造膜され、
基材表面の帯電防止性及び撥水性を改善することができ
る。The aqueous composition of the present invention can be used as an antistatic agent applied to the surface of various substrates such as plastics. The type of the base material, the coating method, and the coating amount are not particularly limited. Examples of the application method include a spraying process, a brushing process, a roll coater process, and a dipping process. After application, by drying under appropriate conditions, warm water resistance, an antistatic coating film excellent in water repellency is formed,
The antistatic property and the water repellency of the substrate surface can be improved.
【００４１】[0041]
【実施例】以下に、本発明の実施例について説明する
が、本発明はこれらの実施例に限定されるものではな
い。合成例１（Ａ１〜Ａ４の合成） Ａ成分のカチオン変性共重合体として、表１に示す４種
類の構成の共重合体Ａ１〜Ａ４を特開平４−１９８３０
９号公報に記載の方法に準じて製造し、さらに、高圧乳
化法により各共重合体Ａ１〜Ａ４の水分散体を調製し
た。EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples. Synthesis Example 1 (Synthesis of A1 to A4) As the cation-modified copolymer of the component A, copolymers A1 to A4 having four kinds of constitutions shown in Table 1 were disclosed in JP-A-4-19830.
The aqueous dispersion of each of the copolymers A1 to A4 was prepared by a high-pressure emulsification method according to the method described in JP-A No. 9-No.
【００４２】[0042]
【表１】 [Table 1]
【００４３】合成例２（B１〜B４の合成） 攪拌装置,加熱装置、滴下ロート、温度計、還流冷却装
置、窒素導入管を備えた１０００ｍｌのフラスコに表２
に記載した組成のモノマーと有機溶剤の混合物、アルキ
ルベンゼンスルホン酸ナトリウム3ｇ、蒸留水370ｇを仕
込み攪拌することで分散させた後、過硫酸アンモニウム
3%の水溶液を30ｇ加え、70℃で3時間反応させ、フッ素
原子を含有する(共)重合体の水分散物B−1〜４を得た。 Synthesis Example 2 (Synthesis of B1 to B4) In a 1000 ml flask equipped with a stirrer, a heating device, a dropping funnel, a thermometer, a reflux cooling device, and a nitrogen inlet tube, Table 2 was prepared.
After mixing and stirring and dispersing a mixture of a monomer and an organic solvent having the composition described in (3), sodium alkylbenzene sulfonate (3 g) and distilled water (370 g), ammonium persulfate
30 g of a 3% aqueous solution was added and reacted at 70 ° C. for 3 hours to obtain aqueous dispersions B-1 to B-4 of a (co) polymer containing a fluorine atom.
【００４４】[0044]
【表２】 [Table 2]
【００４５】任意成分である架橋剤（C成分）を表３に
示す。Table 3 shows the optional crosslinking agent (component C).
【００４６】[0046]
【表３】 [Table 3]
【００４７】実施例１〜７および比較例１〜５ 合成例１で得られた水分散体Ａ１〜Ａ４と表２に示した
Ｂ１〜Ｂ４、表３に示したＣ１、Ｃ２を用いて、これら
を表４に示す成分濃度になるように混合及び／又は希釈
して、実施例１〜７の水性組成物と比較例１〜５の水性
組成物を調製した。 Examples 1 to 7 and Comparative Examples 1 to 5 The aqueous dispersions A1 to A4 obtained in Synthesis Example 1, B1 to B4 shown in Table 2, and C1 and C2 shown in Table 3 were used. Was mixed and / or diluted so as to have the component concentrations shown in Table 4, to prepare the aqueous compositions of Examples 1 to 7 and the aqueous compositions of Comparative Examples 1 to 5.
【００４８】[0048]
【表４】 [Table 4]
【００４９】得られた各水性組成物をガラス板の表面に
１００ｇ／ｍ２塗布した。塗布した基材は、約１２０℃
で１０分間かけ、造膜させた後、下記の項目について試
験を実施した。また水洗テストは、室温(２３℃)の蒸留
水に１０分間浸析し、室温にて乾燥した後、同様の項目
について試験を実施した。Each of the obtained aqueous compositions was applied to the surface of a glass plate at 100 g / m 2. The applied substrate is about 120 ° C
After 10 minutes for forming a film, the following items were tested. Further, in the water washing test, after immersion in distilled water at room temperature (23 ° C.) for 10 minutes and drying at room temperature, the same items were tested.
【００５０】 表面固有抵抗値 ２０℃、６５％ＲＨの環境に試料を２４時間放置し、ウ
ルトラハイレジスタンスメーターＲ８３４０（アドバン
テスト社製）、を用いて表面固有抵抗値を測定した。Surface Specific Resistance The sample was left in an environment of 20 ° C. and 65% RH for 24 hours, and the surface specific resistance was measured using an ultra high resistance meter R8340 (manufactured by Advantest).
【００５１】接触角 ＪＩＳ−６７６８濡れ試験法に準じて、接触角を測定し
た。実施例１〜７および比較例１〜５の試験結果を表５
に示す。Contact Angle The contact angle was measured according to JIS-6768 wetting test method. Table 5 shows the test results of Examples 1 to 7 and Comparative Examples 1 to 5.
Shown in
【００５２】[0052]
【表５】 [Table 5]
【００５３】実施例１〜７は良好な表面抵抗値及び撥水
性を示しており、さらに、耐温水性試験(水洗テスト)で
も表面固有抵抗値および撥水性とも低下が無い。これに
対して、Ａ成分のみを造膜させた比較例１や、Ｂ成分の
みを造膜させた比較例２，３やＡ成分の重量比が小さい
比較例４では撥水性は良好であるが、表面固有抵抗値が
高い。またフッ素原子含有量が２５％未満である比較例
５では、表面固有抵抗値は良好であるが、撥水性が悪
い。Examples 1 to 7 show good surface resistance and water repellency, and there is no decrease in the surface specific resistance and water repellency in the warm water resistance test (washing test). On the other hand, Comparative Example 1 in which only the component A was formed, Comparative Examples 2 and 3 in which only the component B was formed, and Comparative Example 4 in which the weight ratio of the component A was small had good water repellency. High surface resistivity. In Comparative Example 5 in which the fluorine atom content was less than 25%, the surface resistivity was good, but the water repellency was poor.
【００５４】[0054]
【発明の効果】以上のように、本発明の水性組成物によ
れば、特定のカチオン変性共重合体と特定のフッ素原子
含有重合体とを組み合わせることにより、硬化させた帯
電防止膜が、帯電防止性に優れるだけでなく、耐温水
性、撥水性にも優れる。As described above, according to the aqueous composition of the present invention, by combining a specific cation-modified copolymer and a specific fluorine atom-containing polymer, the cured antistatic film can be charged. It is not only excellent in prevention, but also excellent in warm water resistance and water repellency.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０９Ｋ 3/18 １０２ Ｃ０９Ｋ 3/18 １０２ //(Ｃ０８Ｆ 210/02 (Ｃ０８Ｆ 210/02 220:00 220:00 220:60） 220:60） ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C09K 3/18 102 C09K 3/18 102 // (C08F 210/02 (C08F 210/02 220: 00 220: 00 220: 60) 220: 60)
Claims (3)
成物であって、Ａ成分とＢ成分の合計量に対するＡ成分
の重量比が０．０５〜０．５０である水性組成物。 Ａ：式（１）で表されるエチレン構造単位７０〜９９モ
ル％と、 一般式（２）で表されるアクリレート構造単位０〜１５
モル％と、 一般式（３）で表されるアクリルアミド構造単位１〜３
０モル％とを含有し、重量平均分子量が１,０００〜８
０,０００であるカチオン変性共重合体。 【化１】 （式中、Ｒ１は水素原子又は炭素数１〜４のアルキル基
を示し、Ｒ２は炭素数２〜８のアルキレン基を示し、Ｒ
３、Ｒ４、Ｒ５はそれぞれ独立に炭素数１〜１２のアル
キル基、炭素数７〜１２のアリールアルキル基又は炭素
数６〜１２の脂環アルキル基を示し、Ｘはハロゲン原
子、ＣＨ３ＯＳＯ３、Ｃ２Ｈ５ＯＳＯ３又はＲ６ＳＯ３
を示し、ここで、Ｒ６は炭素数１〜１２のアルキル基、
炭素数７〜１２のアリールアルキル基又は炭素数６〜１
２の脂環アルキル基を示す。） Ｂ：フッ素原子を重量分率で２５％以上含む重合体又は
共重合体。An aqueous composition containing the following components A and B, wherein the weight ratio of the component A to the total amount of the components A and B is 0.05 to 0.50. . A: 70 to 99 mol% of an ethylene structural unit represented by the formula (1) and an acrylate structural unit 0 to 15 represented by the general formula (2)
Mol%, and acrylamide structural units 1 to 3 represented by the general formula (3)
0 mol%, and the weight average molecular weight is 1,000 to 8
A cation-modified copolymer having a molecular weight of 10,000. Embedded image (Wherein, R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R2 represents an alkylene group having 2 to 8 carbon atoms,
3, R4 and R5 each independently represent an alkyl group having 1 to 12 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms or an alicyclic alkyl group having 6 to 12 carbon atoms, and X is a halogen atom, CH3OSO3, C2H5OSO3 or R6SO3
Wherein R6 is an alkyl group having 1 to 12 carbon atoms,
An arylalkyl group having 7 to 12 carbon atoms or 6 to 1 carbon atoms
2 represents an alicyclic alkyl group. B) Polymer or copolymer containing 25% or more by weight of fluorine atoms.
Ｂ成分を５〜４０重量％含有してなる請求項１記載の水
性組成物。2. The aqueous composition according to claim 1, comprising 2 to 40% by weight of the component A and 5 to 40% by weight of the component B.
を含有し、Ａ成分とＢ成分の合計量に対するＡ成分の重
量比が０．０５〜０．５０である帯電防止膜。3. An antistatic film containing the components A and B according to claim 1 or 2, wherein the weight ratio of the component A to the total amount of the components A and B is 0.05 to 0.50. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000154520A JP2001329124A (en) | 2000-05-25 | 2000-05-25 | Water-based composition and antistatic film using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000154520A JP2001329124A (en) | 2000-05-25 | 2000-05-25 | Water-based composition and antistatic film using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001329124A true JP2001329124A (en) | 2001-11-27 |
Family
ID=18659601
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000154520A Pending JP2001329124A (en) | 2000-05-25 | 2000-05-25 | Water-based composition and antistatic film using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001329124A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006510748A (en) * | 2002-08-09 | 2006-03-30 | アクゾ ノーベル コーティングス インターナショナル ビー ヴィ | Acid-capped quaternized polymers and compositions comprising such polymers |
| KR101243050B1 (en) | 2010-12-07 | 2013-03-13 | 도레이첨단소재 주식회사 | Composition for Anti-Static Coating, Anti-Static Polyester Film Using the Same and Manufacturing Method thereof |
| JP2019081884A (en) * | 2017-10-31 | 2019-05-30 | 株式会社イーテック | Composition |
-
2000
- 2000-05-25 JP JP2000154520A patent/JP2001329124A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006510748A (en) * | 2002-08-09 | 2006-03-30 | アクゾ ノーベル コーティングス インターナショナル ビー ヴィ | Acid-capped quaternized polymers and compositions comprising such polymers |
| JP4695390B2 (en) * | 2002-08-09 | 2011-06-08 | アクゾ ノーベル コーティングス インターナショナル ビー ヴィ | Acid-capped quaternized polymers and compositions comprising such polymers |
| KR101243050B1 (en) | 2010-12-07 | 2013-03-13 | 도레이첨단소재 주식회사 | Composition for Anti-Static Coating, Anti-Static Polyester Film Using the Same and Manufacturing Method thereof |
| JP2019081884A (en) * | 2017-10-31 | 2019-05-30 | 株式会社イーテック | Composition |
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