CN1145084A - 水稀释性气干涂漆粘合剂的制备方法及其用途 - Google Patents
水稀释性气干涂漆粘合剂的制备方法及其用途 Download PDFInfo
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Abstract
本发明涉及制备基于丙烯酸和乙烯基改性的醇酸树脂乳液的水稀释性气干涂漆粘合剂的方法。后者含有通过特定的(甲基)丙烯酸酯单体引入的聚氧化烯基团，并且即使不使用“助溶剂”，也特别适合用作高光泽涂漆的粘合剂。
Description
本发明涉及基于丙烯酸改性和乙烯基改性的醇酸树脂乳液的水稀释性气干涂漆粘合剂的制备方法及其在氧化干燥涂漆配方中的用途。
在EP0267562A2中，将除C-C双键外不含其它反应基团的(甲基)丙烯酸和/或乙烯基单体在特定乳化剂树脂的含水溶液存在下进行聚合，所述乳化剂树脂可以是醇酸树脂、氨基甲酸乙酯-醇酸树脂或环氧树脂酯。
类似组成的改性醇酸树脂公开于EP0295402A2中，为制备此树脂，除了常规原料外，还使用了特定的脂肪酸共聚物。
对于按照EP0267562A2和EP0295403A2制得的产品，就加工性能和薄膜性能来说，可在很大程度上满足水稀释性气干涂漆粘合剂的涂漆技术要求，但是为了配制光泽面漆，还必须使用有机溶剂如乙二醇醚(尽管所用的比例很小)。
目前已发现按照EP0295403A2制备的醇酸树脂乳液，如果再含有通过特定(甲基)丙烯酸酯单体方式引入的聚氧化烯基团，则即使不用“助溶剂”，也特别适合用作高光泽面漆的粘合剂。
因此，本发明涉及基于丙烯酸改性和乙烯基改性的醇酸树脂乳液的水稀释性气干涂漆粘合剂的制备方法，其特征在于A)将含有：
a1)25至50％(重量)的不饱和脂肪酸，
a2)10至25％(重量)的甲基丙烯酸，
a3)1至15％(重量)的含聚氧化烯基团的(甲基)丙烯酸
酯单体，和
a4)25至50％(重量)的除C-C双键外不含其它官能基团的其它
(甲基)丙烯酸酯和/或乙烯基单体的单体混合物在游离基引发剂的存在下聚合至转化至少95％(重量)，及B)在进一步的反应步骤中，将
b1)33至44％(重量)的共聚物(A)，
b2)20至42％(重量)的不饱和脂肪酸，
b3)10至25％(重量)的具有2至6个羟基的多元醇，
b4)10至20％(重量)的芳族和/或脂族二羧酸，
b5)0至15％(重量)的环和/或多环羧酸反应形成改性醇酸树脂(B)，组分a1)至a4)及组分b1)至b5)的百分数之和在每一情况下都必须分别为100，条件是在阶段(B)将组分b2)至b5)预酯化至达到透明熔体和酸值3至30mg KOH/g为止，所述醇酸树脂(B)含有30至70％(重量)，优选40至60％(重量)(按固含量计)的不饱和脂肪酸，其极限粘度为8至15ml/g(氯仿，20℃)和酸值为25至70mg KOH/g，并且共聚物(A)的至少80％的甲基丙烯酸单元衍生自相应的羧基，如此制得的改性醇酸树脂(B)不用有机溶剂就能在水中乳化。
本发明还涉及按照本发明方法制备的涂漆粘合剂在水稀释性涂漆配方中的用途，所述涂漆在温度高达100℃下氧化干燥，并且甚至不加入有机溶剂，也能得到光泽极好的涂膜。
为了制备共聚物(A)，按照独立权利要求中所述的比例使用单体。
使用的不饱和脂肪酸(组分a1)是具有碘值大于135(优选160至200)和具有一个双键突出孤立位的脂肪酸。合适的例子是亚麻子油脂肪酸和红花脂肪酸，若需要如与高达25％(重量)的脱水蓖麻油脂肪酸或通过异构化制备的比较的共轭二烯(conjuene)脂肪酸的共混物。
对于含有聚氧化烯基团的(甲基)丙烯酸酯单体(组分a3)，可以使用含至少三个氧化烯基团并符合如下结构通式的(甲基)丙烯酸酯化合物：
这些化合物的典型例子是(甲基)丙烯酸与乙二醇低聚体和/或丙二醇低聚体的酯，其中乙二醇和丙二醇单元可以无规或嵌段方式排列。
其它除C-C双键外不含其它官能基团的(甲基)丙烯酸酯单体和/或乙烯基单体(组分a4)优选为那些形成可溶于汽油中的均聚物的(甲基)丙烯酸化合物和芳族乙烯基化合物。
这些化合物合适的是(甲基)丙烯酸与正丁醇、异丁醇、叔丁醇或2-乙基己醇的酯和乙烯基甲苯。此外，也可以使用比例高达30％(重量)的形成不溶于汽油的聚合物的单体，如甲基丙烯酸甲酯或苯乙烯。
共聚按已知方式在合适的引发剂如过苯甲酸叔丁酯或过氧化二苯甲酰存在下进行。
在进一步的反应步骤中，将b1)33至44％(重量)的共聚物(A)，b2)20至42％(重量)的不饱和脂肪酸，b3)10至25％(重量)的具有2至6个羟基的多元醇，b4)10至20％(重量)的芳族和/或脂族二羧酸，b5)0至15％(重量)的环和/或多环羧酸反应得到水稀释性醇酸树脂(B)，其中在最终产品中对于衍生自组分b1)和b2)的不饱和脂肪酸的总比例应为30至70％(重量)，优选40至60％(重量)，组分b1)至b5)的百分数之和同样必须为100。
对于不饱和脂肪酸(组分b2)，在此阶段可以使用具有碘值大于120的植物和动物脂肪酸，一些双键优选应处于共轭位置。大豆脂肪酸、亚麻子油脂肪酸、红花油脂肪酸、妥尔油脂肪酸和蓖麻脂肪酸是合适的。
对于用于制备醇酸树脂的多元醇(组分b3)和二羧酸(组分b4)，特别合适的产品是进入尽可能对水解稳定的酯键的那些产品，作为多醇的例子是三羟甲基丙烷、季戊四醇和山(梨)糖醇，作为二羧酸的例子是间苯二甲酸和对苯二甲酸。
为了调整薄膜的硬度，任选地使用作为组分b5)的环或多环单羧酸如苯甲酸或树脂酸。
将组分b2)至b5)预酯化至达到透明熔体和酸值3至30mg KOH/g为止。加入共聚物(A)之后，将该酯化反应进行至极限粘度达到8至15ml/g(氯仿，20℃)和酸值达到25至70mg KOH/g，选取的最终酸值应使其相当于至少80％，实际上高达约90％的衍生自甲基丙烯酸的羧基基团浓度。由于这些酸基在聚合物链中具有一个叔位并因此是位阻的，所以可以假定它们进行酯化反应实质上比其它羧基慢并在反应结束后构成游离酸基的主要部分。
按照本发明制备的醇酸树脂在减压下无残余惰性有机溶剂。制备含水乳液不用“助溶剂”，除了优选的氨外，有机胺和碱金属氢氧化物适合用于中和酸基。
用于制备水稀释性气干涂漆的颜料、填料和助剂如催干剂、防结皮剂、防沉降剂和消泡剂是本领域熟练技术人员已知的或可从相关文献中查到。
通过将乳液与颜料和添加剂混合，并且将混合物在研磨设备上进行分散来制备涂漆。
除了刷涂外，该涂漆还可以通过喷涂、滴涂或流涂施用。若合适，干燥可在高达约100℃下进行。
下列实施例用于说明本发明而不限制本发明的范围。除非另有说明，所用份数和百分数都以重量为单位。给出的极限粘度(IV)是在20℃下在氯仿中测定的并以ml/g表示。1.实施例1至4和比较例V1.1.制备共聚物(A1)至(A4)和(VA)
将脂肪酸和二甲苯在135至140℃下加热，在此温度下，在6至9小时内以均匀速率加入单体混合物和过氧化物混合物。加料结束后，保持反应温度直至测定残余物显示至少95％的聚合转化率为止。若反应进展太慢，则用过氧化物进行调节。这些起始产品的比例和共聚物的酸值(按固体计)概列于表1中。比较例(VA)与EP0267562A2和EP0295402A2中的共聚物C1相同。1.2.制备改性醇酸树脂(B1)至(B4)和(VB)
根据表2中的数据，将取自部分1的组分在230℃下预酯化至获得透明熔体和酸值3至30mg KOH/g为止。加入部分2之后，将反应混合物保持于200℃下直至达到所需的最终值为止。比较例(VB)与EP0295402A2中的醇酸树脂A1相当。1.3.乳化改性醇酸树脂(B1)至(B4)和(VB)
将100份醇酸树脂(按固体计)除去残留的有机溶剂(来自共聚物)之后，在70℃下用氨水溶液(150份水和约5份NH3/在水中浓度25％)乳化。如此生产出具有显著特性粘度、pH值为8.2至8.6及固含量为约40％(重量)的乳状至透明的乳液。
表1
| (A1) | (A2) | (A3) | (A4) | (VA) | |
| 亚麻子油脂肪酸 | 31 | 28 | 22 | 33 | 30 |
| 异构化亚油酸1) | 2 | 5 | |||
| 红花脂肪酸 | 5 | ||||
| 二甲苯 | 5 | 5 | 5 | ||
| 单体混合物： | |||||
| 甲基丙烯酸异丁酯 | 25 | 26 | 36 | 25 | 32 |
| 乙烯基甲苯 | 6 | 8 | 3 | 6 | |
| 甲基丙烯酸甲酯 | 1 | ||||
| 苯乙烯 | 3 | 2 | |||
| 甲基丙烯酸乙基三甘醇酯 | 7 | 2 | 12 | 1 | |
| PPM5S2) | 6 | ||||
| MPEG 3503) | 2 | ||||
| 甲基丙烯酸 | 21 | 24 | 13 | 20 | 21 |
| 过氧化物混合物： | |||||
| 亚麻子油脂肪酸 | 10 | 7 | 5 | 9 | 21 |
| 过苯甲酸叔丁酯 | 2 | 3 | 3 | 2 | 3 |
| 过氧化物调节： | |||||
| 过氧化二苯甲酰50％浓度 | 1 | 1 | 1 | 1 | 1 |
| 二甲苯 | 5 | 5 | 10 | 10 | 5 |
| 酸值[mg KOH/g] | 209 | 231 | 135 | 213 | 209 |
| (B1) | (B2) | (B3) | (B4) | (VB) | |
| 部分1 | |||||
| 红花脂肪酸 | 231 | 231 | |||
| 异构化亚油酸 | 127 | 162 | 130 | 153 | 127 |
| 大豆脂肪酸 | 238 | 152 | 60 | ||
| 三羟甲基丙烷 | 43 | 235 | |||
| 季戊四醇 | 133 | 108 | 108 | 133 | |
| 间苯二甲酸 | 116 | 103 | 100 | 176 | 116 |
| 苯甲酸 | 76 | ||||
| 部分2(固体) | |||||
| (A1) | 393 | ||||
| (A2) | 346 | ||||
| (A3) | 434 | ||||
| (A4) | 376 | ||||
| (VA) | 393 | ||||
| IV[ml/g] | 12.5 | 13.5 | 11.5 | 9.5 | 12.3 |
| 酸值[mg KOH/g] | 48 | 44 | 33 | 55 | 45 |
用醇酸树脂乳液按已知方式通过在搅拌球磨机(Dyno-Mill型)上研磨按照以下配方制备白色涂漆：
250 树脂乳液，浓度40％
1.5 氨水溶液，在水中浓度25％
100 TiO2，金红石型
1 混合干燥剂，水稀释性的
2 防结皮剂(肟)
1 消泡剂(无有机硅)
30 水
若合适，将该涂漆的pH值调至8.8-9.1并稀释至使用粘度后涂于金属板上，然后在室温下空气干燥24小时后，目测其光泽和色泽。
用按照本发明制备的醇酸树脂乳液配制的白色涂漆显示极好的光泽。对比白色涂漆则显示较差的光泽和截然不同的色泽。
Claims (3)
1.基于丙烯酸改性和乙烯基改性的醇酸树脂乳液的水稀释性气干涂料粘合剂的制备方法，其特征在于A)将含有：
a1)25至50％(重量)的不饱和脂肪酸，
a2)10至25％(重量)的甲基丙烯酸，
a3)1至15％(重量)的含聚氧化烯基团的(甲基)丙烯酸
酯单体，和
a4)25至50％(重量)的除C-C双键外不含其它官能基团的其它
(甲基)丙烯酸酯和/或乙烯基单体的单体混合物在游离基引发剂的存在下聚合至转化至少95％(重量)，及B)在进一步的反应步骤中，将
b1)33至44％(重量)的共聚物(A)，
b2)20至42％(重量)的不饱和脂肪酸，
b3)10至25％(重量)的具有2至6个羟基的多元醇，
b4)10至20％(重量)的芳族和/或脂族二羧酸，
b5)0至15％(重量)的环和/或多环羧酸反应形成改性醇酸树脂(B)，组分a1)至a4)及组分b1)至b5)的百分数之和在每一情况下都必须分别为100，条件是在阶段(B)将组分b2)至b5)预酯化至达到透明熔体和酸值3至30mg KOH/g为止，所述醇酸树脂(B)含有30至70％(重量)，优选40至60％(重量)(按固含量计)的不饱和脂肪酸，其极限粘度为8至15ml/g(氯仿，20℃)和酸值为25至70mg KOH/g，并且共聚物(A)的至少80％的甲基丙烯酸单元衍生自相应的羧基，如此制得的改性醇酸树脂(B)不用有机溶剂就能在水中乳化。
2.根据权利要求1的方法，其特征在于对于组分(a3)，可以使用含至少三个氧化烯基团并符合如下结构通式的(甲基)丙烯酸酯单体：
3.根据权利要求1和2制备的涂料粘合剂用于配制在温度高达100℃下氧化干燥的水稀释性涂料的用途。
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| Application Number | Priority Date | Filing Date | Title |
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| AT0071194A AT400719B (de) | 1994-04-07 | 1994-04-07 | Verfahren zur herstellung von wasserverdünnbaren lufttrocknenden lackbindemitteln und deren verwendung |
| ATA711/1994 | 1994-04-07 | ||
| ATA711/94 | 1994-04-07 |
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| US (1) | US5698625A (zh) |
| EP (1) | EP0758365B1 (zh) |
| JP (1) | JP3822235B2 (zh) |
| KR (1) | KR100354199B1 (zh) |
| CN (1) | CN1060791C (zh) |
| AT (2) | AT400719B (zh) |
| AU (1) | AU2208295A (zh) |
| BR (1) | BR9507292A (zh) |
| CA (1) | CA2186599C (zh) |
| CZ (1) | CZ287508B6 (zh) |
| DE (1) | DE59503078D1 (zh) |
| DK (1) | DK0758365T3 (zh) |
| ES (1) | ES2122578T3 (zh) |
| HU (1) | HU221739B1 (zh) |
| NO (1) | NO311091B1 (zh) |
| SI (1) | SI0758365T1 (zh) |
| WO (1) | WO1995027762A1 (zh) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1114632C (zh) * | 1997-08-12 | 2003-07-16 | 伊斯曼化学公司 | 丙烯酸改性水性磺化醇酸分散液 |
| CN100372882C (zh) * | 2005-12-07 | 2008-03-05 | 江苏三木集团有限公司 | 快干醇酸树脂及制备方法 |
| CN1957048B (zh) * | 2004-05-25 | 2010-10-13 | 阿克佐诺贝尔国际涂料股份有限公司 | 含有乙烯基改性的醇酸树脂的涂料组合物 |
| CN101652397B (zh) * | 2006-12-28 | 2013-04-03 | 树脂核动力工业有限公司 | 水性聚合物分散体 |
| CN103183997A (zh) * | 2011-12-27 | 2013-07-03 | 纳路控股股份有限公司 | 汽车用水溶性底涂层组合物及用其形成涂层的方法 |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6008291A (en) * | 1997-11-28 | 1999-12-28 | Vianova Resins Ag | Aqueous polyester dispersions of stabilized viscosity, their preparation and their use as binders for water-thinnable coatings |
| US20040152830A1 (en) * | 2002-12-23 | 2004-08-05 | Kyu-Jun Kim | Hydrolytically stable polymer dispersion |
| AT412647B (de) * | 2003-07-23 | 2005-05-25 | Surface Specialties Austria | Wasserverdünnbare alkydharze |
| EP1705197A1 (en) * | 2005-03-02 | 2006-09-27 | Cytec Surface Specialties Austria GmbH | Urethane modified water-reducible alkyd resins |
| EP2000491A1 (en) | 2007-06-04 | 2008-12-10 | Cytec Surface Specialties Austria GmbH | Polysiloxane and urethane modified water-reducible alkyd resins |
| EP2202281B1 (en) * | 2008-12-29 | 2011-10-19 | Rohm and Haas Company | High gloss extended alkyd emulsion paints |
| EP2410028A1 (en) | 2010-07-24 | 2012-01-25 | Cytec Austria GmbH | Urethane modified water-reducible alkyd resin compositions |
| EP2410000A1 (en) | 2010-07-24 | 2012-01-25 | Cytec Austria GmbH | Aqueous binder compositions |
| PL236351B1 (pl) | 2011-07-24 | 2021-01-11 | Allnex Austria Gmbh | Mieszaniny co najmniej jednej dyspersji żywicy akrylowej i ich zastosowanie |
| CZ2012147A3 (cs) * | 2012-03-01 | 2013-05-22 | SYNPO, akciová spolecnost | Zpusob prípravy alkydových pryskyric, urethanizovaných alkydu a urethanových oleju |
| EP2889318A1 (en) | 2013-12-31 | 2015-07-01 | ALLNEX AUSTRIA GmbH | Modified water-borne alkyd resin |
| EP3088432A1 (en) | 2015-04-27 | 2016-11-02 | ALLNEX AUSTRIA GmbH | Aqueous dispersions |
| CN105566578B (zh) * | 2016-02-04 | 2018-01-05 | 武汉双虎涂料有限公司 | 一种气干型丙烯酸‑醇酸杂化乳液及其制备方法 |
| EP3575333B1 (en) * | 2017-01-25 | 2023-09-06 | DIC Corporation | Active-energy-ray-curable aqueous resin composition and undercoat agent for inorganic-material thin film |
| WO2018200488A1 (en) * | 2017-04-26 | 2018-11-01 | Arkema Inc. | Thermal insulating coating with low thermal conductivity |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT387971B (de) * | 1986-11-14 | 1989-04-10 | Vianova Kunstharz Ag | Verfahren zur herstellung wasserverduennbarer lufttrocknender lackbindemittel und deren verwendung |
| AT388921B (de) * | 1987-06-17 | 1989-09-25 | Vianova Kunstharz Ag | Wasserverduennbare streichlacke auf der basis von wasserloeslichen alkydharzen |
| DE3728597A1 (de) * | 1987-08-27 | 1989-03-16 | Herberts Gmbh | Verwendung einer waessrigen emulsion oxidativ trocknender polyethylenmodifizierter alkydharze als unter druck stehende aerosolanstrichzusammensetzung |
| JP3003279B2 (ja) * | 1991-06-24 | 2000-01-24 | 大日本インキ化学工業株式会社 | 水性被覆組成物 |
| JPH05301933A (ja) * | 1992-04-27 | 1993-11-16 | Japan Synthetic Rubber Co Ltd | 共重合体ラテックス |
| US6594306B1 (en) * | 1999-09-03 | 2003-07-15 | Motorola, Inc. | Method and apparatus for a start-up procedure for digital and analog modems utilizing pulse code modulation for data transmission |
| US7267135B2 (en) * | 2001-11-16 | 2007-09-11 | The Coleman Company, Inc. | Tent corner construction |
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- 1995-04-06 DK DK95915056T patent/DK0758365T3/da not_active Application Discontinuation
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- 1995-04-06 DE DE59503078T patent/DE59503078D1/de not_active Expired - Lifetime
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- 1995-04-06 SI SI9530107T patent/SI0758365T1/xx unknown
- 1995-04-06 CZ CZ19962935A patent/CZ287508B6/cs not_active IP Right Cessation
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1114632C (zh) * | 1997-08-12 | 2003-07-16 | 伊斯曼化学公司 | 丙烯酸改性水性磺化醇酸分散液 |
| CN1957048B (zh) * | 2004-05-25 | 2010-10-13 | 阿克佐诺贝尔国际涂料股份有限公司 | 含有乙烯基改性的醇酸树脂的涂料组合物 |
| CN100372882C (zh) * | 2005-12-07 | 2008-03-05 | 江苏三木集团有限公司 | 快干醇酸树脂及制备方法 |
| CN101652397B (zh) * | 2006-12-28 | 2013-04-03 | 树脂核动力工业有限公司 | 水性聚合物分散体 |
| CN103183997A (zh) * | 2011-12-27 | 2013-07-03 | 纳路控股股份有限公司 | 汽车用水溶性底涂层组合物及用其形成涂层的方法 |
| CN103183997B (zh) * | 2011-12-27 | 2016-04-20 | 纳路控股股份有限公司 | 汽车用水溶性底涂层组合物及用其形成涂层的方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| HU221739B1 (hu) | 2002-12-28 |
| NO311091B1 (no) | 2001-10-08 |
| NO964057L (no) | 1996-09-26 |
| AT400719B (de) | 1996-03-25 |
| DK0758365T3 (da) | 1999-05-03 |
| CZ287508B6 (en) | 2000-12-13 |
| DE59503078D1 (de) | 1998-09-10 |
| HUT74969A (en) | 1997-03-28 |
| CN1060791C (zh) | 2001-01-17 |
| NO964057D0 (no) | 1996-09-26 |
| JPH09512566A (ja) | 1997-12-16 |
| KR970702337A (ko) | 1997-05-13 |
| EP0758365B1 (de) | 1998-08-05 |
| CA2186599A1 (en) | 1995-10-19 |
| ATE169327T1 (de) | 1998-08-15 |
| AU2208295A (en) | 1995-10-30 |
| EP0758365A1 (de) | 1997-02-19 |
| ES2122578T3 (es) | 1998-12-16 |
| CA2186599C (en) | 2006-05-23 |
| CZ293596A3 (en) | 1997-03-12 |
| HU9602737D0 (en) | 1996-11-28 |
| ATA71194A (de) | 1995-07-15 |
| KR100354199B1 (ko) | 2005-01-25 |
| WO1995027762A1 (de) | 1995-10-19 |
| JP3822235B2 (ja) | 2006-09-13 |
| US5698625A (en) | 1997-12-16 |
| BR9507292A (pt) | 1997-09-23 |
| MX9604325A (es) | 1997-12-31 |
| SI0758365T1 (en) | 1998-10-31 |
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