CN109971327B - 水性涂料与其形成方法 - Google Patents
水性涂料与其形成方法 Download PDFInfo
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- CN109971327B CN109971327B CN201811053327.XA CN201811053327A CN109971327B CN 109971327 B CN109971327 B CN 109971327B CN 201811053327 A CN201811053327 A CN 201811053327A CN 109971327 B CN109971327 B CN 109971327B
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- Prior art keywords
- surfactant
- resin
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- water
- siloxane compound
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000003973 paint Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000004094 surface-active agent Substances 0.000 claims abstract description 73
- -1 siloxane compound Chemical class 0.000 claims abstract description 51
- 229920005989 resin Polymers 0.000 claims abstract description 43
- 239000011347 resin Substances 0.000 claims abstract description 43
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 36
- 238000000576 coating method Methods 0.000 claims abstract description 31
- 239000011248 coating agent Substances 0.000 claims abstract description 29
- 239000004593 Epoxy Substances 0.000 claims abstract description 26
- 239000013067 intermediate product Substances 0.000 claims abstract description 22
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 13
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 10
- 229920001515 polyalkylene glycol Polymers 0.000 claims abstract description 10
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 150000001412 amines Chemical class 0.000 claims description 26
- 239000004971 Cross linker Substances 0.000 claims description 16
- 125000002947 alkylene group Chemical group 0.000 claims description 13
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- 239000000463 material Substances 0.000 claims description 6
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- 239000004925 Acrylic resin Substances 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims 8
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims 2
- 239000000047 product Substances 0.000 claims 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 28
- 238000006460 hydrolysis reaction Methods 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
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- 229920002803 thermoplastic polyurethane Polymers 0.000 description 11
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- 230000000694 effects Effects 0.000 description 7
- 230000007062 hydrolysis Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 229920005668 polycarbonate resin Polymers 0.000 description 5
- 239000004431 polycarbonate resin Substances 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 3
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 3
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- 150000001875 compounds Chemical class 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
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- 238000007142 ring opening reaction Methods 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
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- 125000006681 (C2-C10) alkylene group Chemical group 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
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- 229920001519 homopolymer Polymers 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
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- 238000002310 reflectometry Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C07F7/0872—Preparation and treatment thereof
- C07F7/0876—Reactions involving the formation of bonds to a Si atom of a Si-O-Si sequence other than a bond of the Si-O-Si linkage
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Abstract
一种水性涂料的形成方法，包括：取(a)水解后的硅氧烷化合物与(b2)环氧基交联剂反应后形成中间产物；使中间产物的环氧基开环，以形成界面活性剂，且该界面活性剂具有聚烷二醇的亲水链段、硅氧烷的疏水链段以及末端羟基；以及混合该界面活性剂与水性树脂，以形成水性涂料。
Description
技术领域
本发明涉及水性涂料技术领域，尤其涉及一种水性涂料与其形成方法。
背景技术
防雾剂应具有防雾效果好、持效期长、使用方便，且对人体无危害等特性。防雾剂除了将表面活性剂直接涂到对象表面上之外，更多的是涂覆高分子膜如丙烯酸酯类防雾涂料、有机聚硅氧烷防雾剂或聚氧乙烯多元醇类防雾剂等。对玻璃和镜面而言，硅树脂是经济有效的防雾涂料，其可作为汽车玻璃的防雾剂。但是硅树脂必须高温烧结，不适用于塑料材质的对象。高分子材料涂覆法为在对象表面涂覆高分子膜，此方法行之有年且被用户广泛接受，其防雾效果好、效力长、机械性能好、较为耐擦、耐磨、耐溶剂，其中最常用的是亲水性丙烯酸酯、甲基丙烯酸酯、其均聚物或其共聚物。丙烯酸酯防雾剂的防雾原理，是利用树脂涂层的吸水性吸收表面凝聚的水分，因此不会影响材料的透光率和反射性，起到防雾作用。高分子薄膜层在摩托车的头盔上具有极佳的防雾性，且特别适用于门窗、冷冻窗柜、浴室镜面、镜片、面罩、仪表板、车灯等。然而此类涂料属于溶剂型。
综上所述，目前亟需水性环保且长效型的防雾涂料。
发明内容
本发明一实施例提供的水性涂料，包括：水性树脂；以及界面活性剂，具有聚烷二醇的亲水链段、硅氧烷化合物的疏水链段以及末端的亲水基。
本发明一实施例提供的水性涂料的形成方法，包括：取(a)水解后的硅氧烷化合物与(b1)胺基交联剂反应，以形成界面活性剂，且界面活性剂具有聚烷二醇的亲水链段、硅氧烷的疏水链段以及末端胺基；以及混合该界面活性剂与水性树脂，以形成水性涂料。
本发明一实施例提供的水性涂料的形成方法，包括：取(a)水解后的硅氧烷化合物与(b2)环氧基交联剂反应后形成中间产物；使中间产物的环氧基开环，以形成界面活性剂，且界面活性剂具有聚烷二醇的亲水链段、硅氧烷的疏水链段以及末端羟基；以及混合界面活性剂与水性树脂，以形成水性涂料。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明白，以下结合具体实施例，并参照附图，对本发明作进一步的详细说明。
本发明一实施例提供的水性涂料，包括：水性树脂；以及界面活性剂，具有聚烷二醇的亲水链段、硅氧烷的疏水链段以及末端的亲水基。上述水性树脂与界面活性剂之间不会产生反应。在一些实施例中，水性树脂与界面活性剂的重量比介于100∶1至100∶25之间。若界面活性剂的比例过低，则水性树脂涂层无法产生明显抗雾效果。若界面活性剂的比例过高，则水性树脂涂层耐水性差而造成树脂因水气溶解流失。上述界面活性剂的重均分子量可介于6,000至10,000之间。若界面活性剂的重均分子量过低，则易因水气自涂层加速迁移释出。若界面活性剂的重均分子量过高，则水性树脂中的界面活性剂安定性差。在一实施例中，界面活性剂为由(a)水解后的硅氧烷化合物与(b1)胺基交联剂反应而成，且末端的亲水基为胺基。举例来说，硅氧烷化合物的结构为：
举例来说，(b1)胺基交联剂的结构为：
在一实施例中，界面活性剂为由(a)水解后的硅氧烷化合物与(b2)环氧基交联剂反应形成中间产物后，使中间产物的环氧基开环而成，且末端的亲水基为羟基。硅氧烷化合物的结构同前述，在此不重复。举例来说，(b2)环氧基交联剂的结构为：
在一些实施例中，水性树脂包括聚氨酯树脂、碳酸酯树脂、丙烯酸树脂或上述的组合。举例来说，水性树脂的重均分子量可介于10,000-100,000之间。若水性树脂的重均分子量过低，则水性树脂的耐水性不足。若水性树脂的重均分子量过高，则水性树脂黏度过高而不易使用。
在一实施例中，水性涂料的形成方法包括：取(a)水解后的硅氧烷化合物与(b1)胺基交联剂反应，以形成界面活性剂。上述硅氧烷化合物的水解反应如下。在下式中，R1、R2、R3、R4、m、n与p的定义如前述，在此不重复。值得注意的是，下述反应式仅用以说明可能的反应机制，并非唯一的反应。举例来说，部份硅氧烷化合物在水解后可能具有两个Si-OH基而非一个Si-OH基。此外，硅氧键水解断裂以形成Si-OH的位置，除了下式中的末端亦可能发生在其他位置。另一方面，除了碱水解以外，亦可采用酸水解。
取(a)水解后的硅氧烷化合物与(b1)胺基交联剂反应，以形成界面活性剂的反应如下。在下式中，R1、R2、R3、R4、R5、R6、R7、m、n、p、q的定义如前述，在此不重复。r为(b1)胺基交联剂的聚合程度，其可介于1至10之间。上述界面活性剂具有聚烷二醇的亲水链段、硅氧烷的疏水链段以及末端胺基。上述(a)水解后的硅氧烷化合物与(b1)胺基交联剂的重量比可介于100∶10至100∶200之间。接着混合界面活性剂与水性树脂，以形成水性涂料，水性树脂与界面活性剂的重量比可介于100∶1至100∶25之间。
在另一实施例中，水性涂料的形成方法，包括取(a)水解后的硅氧烷化合物与(b2)环氧基交联剂反应后形成中间产物如下式。在下式中，R1、R2、R3、R4、R8、R9、m、n与p的定义如前述，在此不重复。r为(b2)环氧基交联剂的聚合程度，其可介于1至10之间。
接着使中间产物的环氧基开环，以形成界面活性剂。界面活性剂具有聚烷二醇的亲水链段、硅氧烷的疏水链段以及末端羟基。在下式中，使环氧基开环的反应采用酸催化，且酸可为盐酸、草酸或醋酸。但在其他实施例中，可采用碱催化使环氧基开环，且碱可为常见碱如氢氧化钠。上述(a)水解后的硅氧烷化合物与(b2)环氧基交联剂的重量比可介于100∶10至100∶200之间。接着混合界面活性剂与水性树脂，以形成水性涂料，水性树脂与界面活性剂的重量比可介于100∶1至100∶25之间。
上述水性涂料在涂布至基材(如镜片)上后烘干，可形成防雾涂层以保护基材。值得注意的是，上述界面活性剂与水性树脂之间具有氢键作用力，因为氢键作用力的存在，界面活性剂较不易流失，而且，由于氢键作用力为可逆平衡反应，当涂层表面因磨耗影响抗雾性时，界面活性剂可迁移至涂层表面，使表面恢复抗雾性。经实验证实，上述防雾涂层具有耐水洗、耐擦拭磨耗、耐高温水蒸气与长效性等特性。
为了让本发明的上述和其他目的、特征、和优点能更明显易懂，下文特举数实施例，作详细说明如下：
实施例
实施例1-1
取硅氧烷化合物(Dow Corning super-wetting agent)与10wt％NaOH溶液混合静置数天，进行水解反应。水解反应后过滤取滤液以得水解后的硅氧烷化合物。将上述滤液、异丙醇与水搅拌均匀以得混合物。将胺基交联剂N-(2-胺基乙基)-3-胺基丙基三乙氧基硅烷(简称AEAPTES，Aldrich)缓慢添加至上述混合物中，再持续于室温下搅拌5小时，使胺基交联剂与水解后的硅氧烷化合物反应形成界面活性剂。上述水解后的硅氧烷化合物、异丙醇、水与胺基交联剂的用量，以及界面活性剂的溶液外观如表1所示。
实施例1-2
与实施例1-1类似，差别在于水解后的硅氧烷化合物、异丙醇、水与胺基交联剂的用量。实施例1-2的水解后的硅氧烷化合物、异丙醇、水与胺基交联剂的用量，以及界面活性剂的溶液外观如表1所示。
实施例1-3
与实施例1-1类似，差别在于水解后的硅氧烷化合物、异丙醇、水与胺基交联剂的用量。实施例1-3的水解后的硅氧烷化合物、异丙醇、水与胺基交联剂的用量，以及界面活性剂的溶液外观如表1所示。
实施例1-1至1-3的硅氧烷化合物的水解反应如下，其中p为1-10。
实施例1-1至1-3中，水解反应后的硅氧烷化合物与胺基交联剂的反应如下：
值得注意的是，上述反应式仅用以说明可能的反应机制，并非唯一的反应。举例来说，部份硅氧烷化合物在水解后可能具有两个Si-OH基而非一个Si-OH基。此外，上式中的r为胺基交联剂的聚合程度，其可介于1至5之间。
表1(单位均为克)
实施例2-1
将实施例1-2中界面活性剂的溶液缓慢添加至水性聚氨酯树脂(AnFong UN-3000Series)中，以形成水性涂料。上述界面活性剂与水性聚氨酯树脂的用量如表2所示。
实施例2-2
与实施例2-1类似，差别在于界面活性剂的用量。实施例2-2的界面活性剂与水性聚氨酯树脂的用量如表2所示。
实施例2-3
与实施例2-1类似，差别在于界面活性剂的用量。实施例2-3的界面活性剂与水性聚氨酯树脂的用量如表2所示。
表2(单位均为克)
| 实施例 | 2-1 | 2-2 | 2-3 |
| 水性聚氨酯树脂 | 100 | 100 | 100 |
| 界面活性剂 | 4 | 8 | 16 |
取实施例2-1至2-3的水性涂料涂布至透明聚碳酸酯树脂试片上后，于120℃下烘干水性涂料以形成涂层。将上述样品泡水96小时后，确认样品上的涂层是否脱落(浸水测试)。
将50℃的水置入容器中，并将样品(涂层朝下)覆盖容器口，以测试样品表面起雾的时间。起雾时间需大于或等于30秒才算通过蒸气测试(ASTM F659)，即具有防雾效果。
实施例2-1至2-3的样品经上述浸水测试与蒸气测后的结果如表3所示：
表3
| 水性涂料 | 2-1 | 2-2 | 2-3 |
| 蒸气测试 | 通过 | 通过 | 通过 |
| 浸水测试 | 通过 | 通过 | 通过 |
实施例3-1
取硅氧烷化合物(Dow Corning super-wetting agent)与10wt％NaOH溶液混合静置数天，进行水解反应。水解反应后过滤取滤液以得水解后的硅氧烷化合物。将上述滤液、异丙醇与水搅拌均匀以得混合物。将环氧基交联剂(Aldrich，GLYMO)缓慢添加至上述混合物中，再持续于室温下搅拌8小时，使环氧基交联剂与水解后的硅氧烷化合物反应形成中间产物。接着将1NHCl加入中间产物，使中间产物的环氧基开环形成羟基，即得界面活性剂。上述水解后的硅氧烷化合物、异丙醇、水、环氧基交联剂与HCl的用量，以及界面活性剂的溶液外观如表4所示。
实施例3-2
与实施例3-1类似，差别在于水解后的硅氧烷化合物与环氧基交联剂的用量。实施例3-2的水解后的硅氧烷化合物、异丙醇、水、环氧基交联剂与HCl的用量，以及界面活性剂的外观如表4所示。在实施例3-2中，NaOH水解前的硅氧烷化合物其重均分子量为600-1000，水解后的硅氧烷化合物其重均分子量为1000-1200、中间产物其重均分子量为6000-10000、且界面活性剂其重均分子量为6000-10000。上述重均分子量的量测方法为胶体渗透层析(GPC)。此外，中间产物具有环氧基的IR特征峰910cm-1。界面活性剂具有IR特征峰840cm-1，且环氧基的IR特征峰910cm-1减弱，证明中间产物的环氧基已开环形成界面活性剂。
实施例3-3
与实施例3-1类似，差别在于水解后的硅氧烷化合物与环氧基交联剂的用量。实施例3-3的水解后的硅氧烷化合物、异丙醇、水、环氧基交联剂与HCl的用量，以及界面活性剂的溶液外观如表4所示。
实施例3-1至3-3的硅氧烷化合物的水解反应如下，其中p为1-10。
实施例3-1至3-3中，水解反应后的硅氧烷化合物与环氧基交联剂反应形成中间产物的反应如下：
实施例3-1至3-3中，中间产物经由酸催化使环氧基进行开环反应，以形成界面活性剂的反应如下：
值得注意的是，上述反应式仅用以说明可能的反应机制，并非唯一的反应。举例来说，部份硅氧烷化合物在水解后可能具有两个Si-OH基而非一个Si-OH基。此外，上式中的r为环氧基交联剂的聚合程度，其可介于1至5之间。
表4(单位均为克)
实施例4-1
将实施例3-2中界面活性剂的溶液缓慢添加至第一水性聚氨酯树脂(AnFongUN-3000Series)与第二水性聚氨酯树脂(AnFongCUD-4835)的混合物中，以形成水性涂料。上述界面活性剂、第一水性聚氨酯树脂与第二水性聚氨酯树脂的用量如表5所示。
实施例4-2
与实施例4-1类似，差别在于界面活性剂的用量。实施例4-2的界面活性剂、第一水性聚氨酯树脂与第二水性聚氨酯树脂的用量如表5所示。上述水性涂料的室温下黏度约为80cps，于常温下放置一个月后的室温下黏度为约100cps。由上述可知，界面活性剂仅与水性树脂混合而未产生反应。
实施例4-3
与实施例4-1类似，差别在于界面活性剂与水性聚氨酯树脂的用量。实施例4-3的界面活性剂、第一水性聚氨酯树脂与第二水性聚氨酯树脂的用量如表5所示。
表5(单位均为克)
| 实施例 | 4-1 | 4-2 | 4-3 |
| 第一水性聚氨脂树脂 | 50 | 50 | 50 |
| 第二水性聚氨脂树脂 | 50 | 50 | 50 |
| 界面活性剂 | 4 | 8 | 16 |
取实施例4-1至4-3的水性涂料涂布至透明聚碳酸酯树脂试片上后，于120℃下烘干水性涂料以形成涂层。将上述样品进行前述的浸水测试、蒸气测试与擦拭测试后的结果如表6所示。
擦拭测试的条件如下：将80℃热水置于烧杯中，并将样品(涂层朝下)覆盖烧杯。取下样品以干布擦拭涂层一次后再置回烧杯上。每10秒重复上述动作一次，直到防雾效果失效。烧杯置于保温装置或加热装置上，以确保烧杯中的水维持80℃。上述擦拭次数需大于或等于10次才算通过擦拭测试。
表6
| 水性涂料 | 4-1 | 4-2 | 4-3 |
| 蒸气测试 | 通过 | 通过 | 通过 |
| 浸水测试 | 通过 | 通过 | 通过 |
| 擦拭测试 | 通过 | 通过 | 通过 |
比较例1
取实施例3-2的中间产物(未与酸进行开环反应)缓慢添加至第一水性聚氨酯树脂(AnFongUN-3000Series)与第二水性聚氨酯树脂(AnFongCUD-4835)的混合物中，以形成水性涂料。上述中间产物的用量等于实施例4-2的界面活性剂的用量，而第一水性聚氨酯树脂与第二水性聚氨酯的用量与实施例4-2相同。上述水性涂料的室温下黏度约为80cps，于常温下放置一个月后的室温下黏度为约1000cps。由此可知，若中间产物不先进行开环反应即与水性树脂混合，则水性树脂将与中间产物的环氧基反应而大幅增加水性涂料的黏度。
另一方面，取比较例1的水性涂料涂布至透明聚碳酸酯树脂试片上后，于120℃下烘干水性涂料以形成涂层。将上述样品进行前述的擦拭测试，仅3-5次即丧失防雾性(未通过测试)。
比较例2
取市售的溶剂型涂料(FSI公司/VPP)涂布至透明聚碳酸酯树脂试片上后，于120℃下烘干溶剂型涂料以形成涂层。将上述样品进行前述的擦拭测试，仅5次即丧失防雾性(未通过测试)。
比较例3
取市售的溶剂型涂料(NSC公司/AF332)涂布至透明聚碳酸酯树脂试片上后，于120℃下烘干溶剂型涂料以形成涂层。将上述样品进行前述的擦拭测试，仅5次即丧失防雾性(未通过测试)。将上述样品进行前述的蒸气测试，其防雾效果不佳(未通过蒸气测试)。
以上所述仅为本发明的具体实施例而已，并不用于限制本发明，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (13)
1.一种水性涂料，包括：
一水性树脂；以及
一界面活性剂，具有聚烷二醇的亲水链段、硅氧烷的疏水链段以及末端的亲水基，
其中该界面活性剂为由(a)水解后的硅氧烷化合物与(b1)胺基交联剂反应而成，且末端的亲水基为胺基；或由(a)水解后的硅氧烷化合物与(b2)环氧基交联剂反应形成中间产物后，使中间产物的环氧基开环而成，且末端的亲水基为羟基，
其中硅氧烷化合物的结构为：
每一R1各自为C1-6的烷基，
R2为C2-10的烷撑基，
R3为C2-4的烷撑基，
R4为H或C1-4的烷基，
m＝0-10，
n＝1-10，以及
p＝2-50；
其中(b1)胺基交联剂的结构为：
每一R5各自为C1-6的烷基，
R6为C1-10的烷撑基，
R7为C2-4的烷撑基，以及
q＝0或1，
其中(b2)环氧基交联剂的结构为：
每一R8各自为C1-6的烷基，以及
R9为C1-10的烷撑基。
2.根据权利要求1所述的水性涂料，其中该水性树脂与该界面活性剂的重量比介于100:1至100:25之间。
3.根据权利要求1所述的水性涂料，其中(a)水解后的硅氧烷化合物与(b1)胺基交联剂的重量比介于100:10至100:200之间。
4.根据权利要求1所述的水性涂料，其中(a)水解后的硅氧烷化合物与(b2)环氧基交联剂的重量比介于100:10至100:200之间。
5.根据权利要求1所述的水性涂料，其中该水性树脂为聚氨酯树脂、碳酸酯树脂、丙烯酸树脂或上述的组合。
6.一种水性涂料的形成方法，包括：
取(a)水解后的硅氧烷化合物与(b1)胺基交联剂反应，以形成一界面活性剂，且该界面活性剂具有聚烷二醇的亲水链段、硅氧烷的疏水链段以及末端胺基；以及
混合该界面活性剂与一水性树脂，以形成一水性涂料，
其中硅氧烷化合物的结构为：
每一R1各自为C1-6的烷基，
R2为C2-10的烷撑基，
R3为C2-4的烷撑基，
R4为H或C1-4的烷基，
m＝0-10，
n＝1-10，以及
p＝2-50；
其中(b1)胺基交联剂的结构为：
每一R5各自为C1-6的烷基，
R6为C1-10的烷撑基，
R7为C2-4的烷撑基，以及
q＝0或1。
7.根据权利要求6所述的水性涂料的形成方法，其中该水性树脂与该界面活性剂的重量比介于100:1至100:25之间。
8.根据权利要求6所述的水性涂料的形成方法，其中(a)水解后的硅氧烷化合物与(b1)胺基交联剂的重量比介于100:10至100:200之间。
9.根据权利要求6所述的水性涂料的形成方法，其中该水性树脂为聚氨酯树脂、碳酸酯树脂、丙烯酸树脂或上述的组合。
10.一种水性涂料的形成方法，包括：
取(a)水解后的硅氧烷化合物与(b2)环氧基交联剂反应后形成一中间产物；
使中间产物的环氧基开环，以形成一界面活性剂，且该界面活性剂具有聚烷二醇的亲水链段、硅氧烷的疏水链段以及末端羟基；以及
混合该界面活性剂与一水性树脂，以形成一水性涂料，
其中硅氧烷化合物的结构为：
每一R1各自为C1-6的烷基，
R2为C2-10的烷撑基，
R3为C2-4的烷撑基，
R4为H或C1-4的烷基，
m＝0-10，
n＝1-10，以及
p＝2-50；
其中(b2)环氧基交联剂的结构为：
每一R8各自为C1-6的烷基，以及
R9为C1-10的烷撑基。
11.根据权利要求10所述的水性涂料的形成方法，其中该水性树脂与该界面活性剂的重量比介于100:1至100:25之间。
12.根据权利要求10所述的水性涂料的形成方法，其中(a)水解后的硅氧烷化合物与(b2)环氧基交联剂的重量比介于100:10至100:200之间。
13.根据权利要求10所述的水性涂料的形成方法，其中该水性树脂为聚氨酯树脂、碳酸酯树脂、丙烯酸树脂或上述的组合。
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