CN1394149A - 甲醛含量降低的低粘度蜜胺-甲醛树脂微胶囊分散体 - Google Patents
甲醛含量降低的低粘度蜜胺-甲醛树脂微胶囊分散体 Download PDFInfo
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- CN1394149A CN1394149A CN01803573A CN01803573A CN1394149A CN 1394149 A CN1394149 A CN 1394149A CN 01803573 A CN01803573 A CN 01803573A CN 01803573 A CN01803573 A CN 01803573A CN 1394149 A CN1394149 A CN 1394149A
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- melamine
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- 229920000877 Melamine resin Polymers 0.000 title claims abstract description 62
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 32
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- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-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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- JHXVRRJXCDAINK-UHFFFAOYSA-N NC(=O)N.N#CC#N Chemical compound NC(=O)N.N#CC#N JHXVRRJXCDAINK-UHFFFAOYSA-N 0.000 description 1
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- 229930040373 Paraformaldehyde Natural products 0.000 description 1
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- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
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- TZMFJUDUGYTVRY-UHFFFAOYSA-N ethyl methyl diketone Natural products CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
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- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08G12/30—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with substituted triazines
- C08G12/32—Melamines
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/20—After-treatment of capsule walls, e.g. hardening
- B01J13/206—Hardening; drying
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
- B41M5/165—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components characterised by the use of microcapsules; Special solvents for incorporating the ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
- C08G12/06—Amines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/40—Chemically modified polycondensates
- C08G12/42—Chemically modified polycondensates by etherifying
- C08G12/424—Chemically modified polycondensates by etherifying of polycondensates based on heterocyclic compounds
- C08G12/425—Chemically modified polycondensates by etherifying of polycondensates based on heterocyclic compounds based on triazines
- C08G12/427—Melamine
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08L61/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
- C08L61/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
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- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
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Abstract
本发明公开了一种制备微胶囊分散体的方法,该方法通过使蜜胺∶甲醛∶甲醇摩尔比为1∶3.0∶2.0-1∶6.0∶4.0的部分甲基化蜜胺-甲醛树脂在水中缩合而进行,其中通过在20-50℃的温度下预成型微胶囊,然后在>50-100℃下固化该预成型微胶囊的胶囊壁来使形成胶囊芯的基本水不溶性物质在3-6.5的pH下在2-丙烯酰胺基-2-甲基丙烷磺酸的均聚物或共聚物的碱金属盐存在下分散。该方法的特征在于在固化过程中添加5-100wt%的蜜胺,基于蜜胺-甲醛树脂。该微胶囊分散体的甲醛含量降低且粘度低。
Description
本发明涉及一种通过在水中缩合部分甲基化蜜胺-甲醛树脂来制备微胶囊分散体的方法,其中形成胶囊芯的基本水不溶性物质在阴离子保护胶体存在下以分散体存在。本发明进一步涉及通过该方法获得的微胶囊分散体和它们用于制备印刷油墨和纸张涂布组合物的用途。
直径在大约0.1到100μm范围内的微分散颗粒在各种领域中具有广泛的应用。它们例如用作抛光和/或清洁组合物中的固体珠粒、印刷油墨中的隔离剂、医学显微镜观察的刻度指示剂等。除了固体珠粒以外,其芯材料可以包括基本不溶于水或不溶于水的液体、固体或气体物质的微胶囊是已知的。胶囊壁常用材料的实例是蜜胺-甲醛聚合物,聚氨酯,明胶,聚酰胺,或聚脲。广泛的用途是制备无碳复印纸的充油微胶囊。
对于该应用,充油微胶囊引入到纸涂布组合物中,用该组合物涂布纸基材。目前常用的高涂布速度需要纸涂布组合物具有低粘度,这进而要求微胶囊分散体具有低粘度。然而,分散体的胶囊浓度应该尽可能高,以便避免不必要的湿操作。此外,为了获得良好的颜色浓度值,寻求非常窄的胶囊尺寸分布。
由于它们的制备方法的原因,包含氨基树脂,如蜜胺-甲醛树脂的微胶囊分散体含有或多或少的游离甲醛。由于生态学和职业卫生的原因,目的是保持甲醛含量尽可能低,而不会不利地影响微胶囊分散体的其它性能。这里应该在分散体本身的甲醛含量和用分散体涂布的材料的甲醛含量之间进行区分。含水胶囊分散体中的游离甲醛浓度低未必意味着涂层材料中的甲醛含量例如根据DIN EN645和DIN EN1541用冷水提取法来测定会出现低甲醛水平。
为了减少甲醛含量,通常将甲醛清除剂加到以蜜胺-甲醛树脂为基础的微胶囊分散体中。氨、脲、亚乙基脲和蜜胺对于减少胶囊分散体中的残余甲醛含量不同程度有效,属于最常使用的甲醛清除剂之列。
EP-A-0 383 358和DE-A-38 14 250公开了包括微胶囊的光敏材料,其壁由蜜胺-甲醛树脂形成。为了除去过量的甲醛,脲在固化阶段添加。
在EP-A-319 337和US-A-4,918,317中所述的工艺中,脲在固化结束时添加。
EP-A-0 415 273描述了蜜胺-甲醛缩合物的单和多分散固体珠粒的制备方法和用途。在该专利中,建议使用氨、脲或亚乙基脲来结合在缩合过程中释放的甲醛。
从EP-A-0 218 887和EP-A-0 026 914中已经得知以其均匀的胶囊尺寸和不渗透性著称的蜜胺-甲醛树脂微胶囊。然而,这些胶囊分散体还含有残留的游离甲醛,其存在从进一步加工的角度来说是不希望的。EP-A-0 026914因此推荐在固化后使用亚乙基脲和/或蜜胺作为甲醛清除剂来结合甲醛。
DE 198 35 114公开了以蜜胺-甲醛树脂为基础的微胶囊分散体,所述树脂被部分醚化并且包含水溶性伯、仲或叔胺或氨。在固化之前,添加作为甲醛清除剂的脲。
DE 198 33 347描述了通过缩合蜜胺-甲醛树脂和/或它们的甲基醚来制备微胶囊的方法,其中脲或其氨基通过亚乙基或亚丙基桥基连接的脲在固化之前作为甲醛清除剂添加。虽然所得分散体甲醛含量低,但在固化前添加的脲对微胶囊的稳定性和微胶囊分散体的粘度具有不利影响。
确实,上述甲醛清除剂添加到成品微胶囊分散体或在微胶囊分散体的制备过程中添加一般降低了分散体的甲醛含量。然而,用包括微胶囊分散体的涂料组合物涂布的纸的甲醛含量(可由冷水提取法测定)不能减少至一定的限度之下,即使添加大量的甲醛清除剂。
本发明的目的是提供一种制备微胶囊的甲醛降低的分散体的方法,其中用分散体涂布的纸的甲醛含量(可由冷水提取法测定)是非常低的。进一步的目的是提供低粘度微胶囊分散体,尤其具有高固体含量的低粘度微胶囊分散体。
我们已经发现,这些目的可通过本发明用于制备微胶囊分散体的方法来实现,该方法通过使蜜胺∶甲醛∶甲醇摩尔比为1∶3.0∶2.0-1∶6.0∶4.0的部分甲基化蜜胺-甲醛树脂在水中缩合而进行,其中通过在20-50℃的温度下预成型微胶囊,然后在>50-100℃下固化胶囊壁来使形成胶囊芯的基本水不溶性物质在3-6.5的pH下在作为保护胶体的2-丙烯酰胺基-2-甲基丙烷磺酸的均聚物或共聚物的碱金属盐存在下以分散体存在,该方法包括在固化过程中添加5-100wt%的蜜胺,基于蜜胺-甲醛树脂。
假设在通过添加甲醛清除剂,如氨、胺等降低甲醛含量的已知方法中,缩合过程中释放的甲醛由甲醛和清除剂形成加合物来结合。然而,在纸基材的涂布或涂层纸的干燥过程中,该加合物在酸性基团,例如没有引入到胶囊壁中的过量保护胶体的磺酸基团作用下明显裂开,使得甲醛继续在涂层纸的冷水提取中可测到。在本发明方法的情况下,假如所形成的产物沉积在胶囊壁上,释放的甲醛、过量的保护胶体和添加的蜜胺不可逆地结合。因此,除了降低可通过冷水提取检测到的甲醛含量以外,该方法还获得了微胶囊分散体粘度的下降,因为过量的保护胶体(现在不再以溶解的形式存在于水相中,而是以化学结合的形式存在于胶囊壁上)对分散体的粘度没有贡献。因此,根据本发明制备的分散体还可以有利地喷雾干燥,因为微胶囊彼此之间基本没有“粘着性”。
本发明的方法一般通过将所要包封的芯材料、具有1∶3.0∶2.0-1∶6.0∶4.0,优选1∶3.5∶2.2-1∶4.5∶2.8,以及尤其大约1∶3.9∶2.4的规定蜜胺∶甲醛∶甲醇摩尔比的部分甲基化蜜胺-甲醛树脂、保护胶体和水合并成预混物,使用酸,优选甲酸调节预混物至3-6.5的pH,以及使预混物经历剪切条件以便分散芯材料来进行。微胶囊在20-50℃,优选大约35℃的温度下预成型;即,在芯材料的分散液滴周围,形成了基本非交联蜜胺-甲醛树脂的壁。随后升高温度,以便通过形成交联物来固化微胶囊的壁。已经发现胶囊壁的固化在50℃以上;然而优选65℃,尤其优选75℃作为固化温度范围的下限。因为分散体是水分散体,作为温度上限,固化应该在100℃以下,优选95℃以下,和尤其优选80℃以下的温度进行。固化在不同的速度下进行,取决于分散体的pH,尤其良好的分散体固化发生在3和5之间的相对低pH值下。然而,在50℃以上,可明显观测到固化,即使是在弱酸性到中性pH范围。
胶囊预成型和胶囊固化这两步的最佳温度可以作为各pH的函数容易地通过简单的系列试验来测定。
胶囊分散体可以以各种方式加热至固化温度。在一个优选实施方案中,热蒸汽注入到胶囊分散体中。蒸汽的温度例如是105-120℃和压力是1.5-3巴。应该记住,分散体的固体含量在一定程度上被缩合物降低。
在本发明的方法中,在已经达到固化温度之后,将蜜胺,即氰脲酸三酰胺在固化过程中分批或连续添加至微胶囊分散体中,优选连续添加。蜜胺的添加量是5-100wt%,优选7-40wt%,尤其12.5-35wt%,以蜜胺-甲醛树脂为基准。一种尤其优选的添加方式包括在已经达到固化温度之后,以基本恒定的质量流速将蜜胺悬浮液物料加至预成型的微胶囊的分散体中。优先选择质量流速,使得添加超过固化期的至少50%,尤其至少65%。固化期一般是0.5-10小时,通常是1-3小时。
蜜胺适合以含水悬浮液的形式添加,其pH优选用酸,例如甲酸调节至3.8-5.0,优选大约4.5,以及例如具有15-80wt%,优选25-70wt%的干物质含量。悬浮液中蜜胺颗粒的平均尺寸优选是1-50μm,尤其大约1-5μm。平均粒度可以适宜地使用Malvern筛分器测定。
另外已经发现,脲的使用还对甲醛含量(可由冷水提取法测定)的降低具有协同效应。本发明的方法因此可以有利地以这样一种方式进行:在固化过程中,重量比例如为20∶1-1∶20,优选5∶1-1∶1的蜜胺和脲的混合物适宜地以含有溶解形式的脲的含水蜜胺悬浮液的形式添加。
用于壁材料的起始物质是部分甲基化蜜胺-甲醛树脂,即蜜胺∶甲醛∶甲醇的摩尔比为1∶3.0∶2.0-1∶6.0∶4.0,优选1∶3.5∶2.2-1∶4.5∶2.8,尤其大约1∶3.9∶2.4的蜜胺-甲醛树脂的部分甲基醚。例如以与DE 198 35 114中的说明书类似的方式制备甲基醚,所用醇是甲醇和方法是在没有添加蜜胺衍生物的情况下操作。用于胶囊制备的蜜胺-甲醛树脂中的蜜胺∶甲醛∶甲醇的摩尔比对胶囊分散体的最终粘度具有重要影响。用所述摩尔比获得了微胶囊分散体中固体含量和粘度的最有利结合。
用于微胶囊的适合芯材料是液体、固体或气体物质,其基本不溶于水或不溶于水。实例包括以下:液体,如烷基萘,部分氢化三联苯,芳族烃类,如二甲苯、甲苯、十二烷基苯,脂族烃类,如溶剂油和矿物油,石蜡,氯化石蜡,各种化学组成的蜡,含氟烃类,天然油,如花生油、大豆油,以及粘合剂,芳香剂,香料油,单体,如丙烯酸酯或甲基丙烯酸酯、苯乙烯,活性物质,如植物保护产品,红磷,有机和无机颜料,例如氧化铁颜料;此外,染料和尤其成色剂和颜料在烃类如烷基萘、部分氢化三联苯、十二烷基苯和其它高沸点液体中的溶液或悬浮液。适合的成色剂描述在开头引用的文件中。
如在EP-A-0 026 914中所述,根据所要制备的胶囊的尺寸,芯材料以普通方式分散。小胶囊,尤其当目的尺寸小于50μm时,需要均化或分散机器,其可以带强制流动或不带强制流动装置使用。必要的是,在预成型阶段的开始使用均化或分散机器。在固化阶段过程中,分散体仅仅在低剪切条件下循环或混合以便确保均匀的混合。
所用的保护胶体是2-丙烯酰胺基-2-甲基丙烷磺酸的均聚物或共聚物的碱金属盐,优选钠盐。适合的共聚单体包括丙烯酸,甲基丙烯酸,(甲基)丙烯酸C1-3-烷基酯,羟基-C2-4-(甲基)丙烯酸酯和/或N-乙烯基吡咯烷酮。共聚物优选含有至少40wt%的2-丙烯酰胺基-2-甲基丙烷磺酸单元。适合的均聚物和共聚物描述在EP-A-0 562 344中。保护胶体优选具有100-170的Fikentscher K值或200-5000mPas的粘度(在23℃,用50rpm下的Brookfield RVT,3号心轴在20wt%水溶液中测得)。尤其优选的聚合物是K值为115-150的那些和粘度为400-4000mPas的那些。
蜜胺-甲醛树脂与保护胶体的重量比优选是3∶1-4.5∶1,尤其3.5∶1-4.0∶1。树脂与保护胶体的比率以及保护胶体的性质影响胶囊尺寸和胶囊尺寸分布。
根据本发明制备的微胶囊分散体具有理想的低粘度,使得其可制备拥有有利的进一步加工性能的甚至高固体含量的微胶囊分散体。所得微胶囊分散体一般具有15-60wt%,但优选至少45wt%,尤其至少48wt%,以及尤其优选50-53wt%的固体含量。微胶囊分散体的粘度(在23℃下用50rpm下的Brookfield RVT,3号心轴测量)一般低于100mPas,尤其低于90mPas。
为制备具有高固体含量的微胶囊分散体,适宜的工序是制备包括蜜胺-甲醛树脂、保护胶体和形成胶囊芯的材料的预混物,所述预混物具有至少50wt%,优选大约55wt%的固体含量,使微胶囊在20-50℃下预成型,以及通过喷射热蒸汽将分散体加热至固化温度以便固化,分散体的固体含量用蒸汽冷凝物降低至所需水平,例如大约50wt%。
使用本发明的方法,可获得具有有利的窄胶囊尺寸分布的微胶囊分散体,该分布例如以0.3-0.8,优选0.3-0.5的商(d90-d10)/d50(跨度)来表征。d10,d50和d90数值表示界限,对于该界限,10%,50%和90%的胶囊分别具有小于或等于该界限的直径。d10,d50和d90数值可以适当地使用Malvern筛分器测定。令人惊奇的是,与熟练工作人员所预料的相反,即使从具有高固体含量,例如高于50wt%的预混物起始,也获得了具有理想的窄尺寸分布的微胶囊分散体。微胶囊通常具有1-50μm,尤其3-8μm范围内的平均直径(d50)。
以下的实施例用来说明本发明的方法。除非另有规定,在实施例中所述的份和百分数按重量计。
实施例
所用测量方法
1、固体含量
在实施例中所述的固体含量通过干燥(4h,105℃)测定,主要由微胶囊和水溶性聚合物组成。胶囊直径是在显微镜下主观测定,使用Malvern筛分器客观测定。胶囊直径描述为d50数值(μm)。
2、粘度
胶囊分散体和水溶性保护胶体的20%浓度溶液的粘度使用具有3号心轴的Brookfield RVT在23℃和50rpm下测得。用0.5%水溶液测定Fikentscher K值(Cellulosechemie 13(1932)58 ff.)。
3、根据DIN EN645和DIN EN1541测量纸中甲醛浓度
用通过彻底均化8.75g的水,8.25g的微胶囊分散体,1.30g的作为隔离剂的磨细纤维素(ArbocelBSM 55)和1.30g的50wt%基于苯乙烯和丙烯酸丁酯的共聚物的标准工业粘结剂分散体(Acronal320D)所获得的着色增滑剂涂布(大约4.6g/m2)的纸根据DIN EN645撕碎,形成冷水提取物。滤液中的甲醛根据DIN 1541使用乙酰基丙酮以光度方式测定。
实施例实施例1
在装于带有直径为50mm的标准工业分散盘片的无级可调分散器上的2L圆柱形搅拌容器中连续加入400g的荧烷反应性染料混合物(由5份PergascriptI-2RN,20份PergascriptI-2GN,8份PergascriptI-G,67份PergascriptI-R组成,购自CIBA)在比率为80∶20的二异丙基萘和线性链烷烃(沸点220℃)的混合物中的5%溶液、69g的甲基化蜜胺-甲醛树脂(蜜胺∶甲醛∶甲醇摩尔比1∶3.9∶2.4)的70%溶液、64g的聚-2-丙烯酰胺基-2-甲基丙烷磺酸/钠盐的20%溶液(K值123;Brookfield粘度770mPas)、350g的自来水和15g的10%甲酸,该加料通过将搅拌速度调节至大约20m/s的圆周速度来加工成胶囊分散体。温度保持在大约35℃下。在60分钟的分散之后,分散体是无油的;自身形成了大约5μm的粒度。分散盘片的搅拌速度然后减至足以保持容器内容物均匀循环的水平。通过喷射热蒸汽来设定75℃的固化温度之后,开始供给pH4.5的蜜胺在甲酸中的27%悬浮液,并在1小时的过程中计量加入;总共计量加入67g的悬浮液。随后是120分钟的固化期。在分散体已经冷却至大约55℃之后,用二乙醇胺中和,以及使用氨调节至9.5的pH。
这样获得了固体含量50%和83mPas粘度的均匀胶囊分散体。冷水提取物中甲醛含量经分析为130ppm。胶囊尺寸分布具有0.43的跨度。实施例2
重复实施例1的工序,只是蜜胺悬浮液还含有9g的溶解脲。胶囊在90℃固化。
所得分散体的胶囊尺寸分布具有0.36的跨度。粘度是83mPas,以及固体含量是50%。冷水提取物中甲醛含量是80ppm。
实施例1和2的胶囊分散体的加工和复印性能满足现在的要求。对比实施例1
在装于带有直径为50mm的标准工业分散盘片的无级可调分散器上的2L圆柱形搅拌容器中添加286自来水,该初始加料与86g的粘度为275mPas(DIN 51562)和pH为8.5的蜜胺-甲醛树脂(蜜胺∶甲醛∶甲醇摩尔比1∶3.9∶2.4)的70%溶液混合。向该混合物添加80g的聚-2-丙烯酰胺基-2-甲基丙烷磺酸/钠盐的20%溶液(粘度770mPas;K值123),再混合各组分。随后,添加如实施例1的成色剂在比率为80∶20的二异丙基萘和线性链烷烃(沸点220℃)的混合物中的5%反应性染料溶液。混合物用15ml的10%甲酸酸化,再将搅拌速度设置至大约20m/s的圆周速度。将温度保持在大约35℃。在60分钟的分散之后,分散体是无油的;自身形成了大约5μm的粒度。分散盘片的搅拌速度然后减至足以保持容器内容物均匀循环的水平。分散体的温度随后在30分钟的过程中通过注入热蒸汽来升至75℃。随后是120分钟的固化期。在分散体已冷却至大约55℃之后,用二乙醇胺中和,并使用氨调节至9.5的pH。
该分散体的Brookfield粘度是大约120mPas,固体含量40%,和冷水提取物中甲醛含量大约360ppm。对比实施例2
在固化和用二乙醇胺代替氨中和之后,将10g脲加到根据对比实施例1制备的微胶囊分散体中。Brookfield粘度是大约120mPas和冷水提取物中甲醛是大约260ppm。对比实施例3
重复对比实施例2,但在分散阶段的开始添加脲。
在冷水提取物中甲醛含量是大约80ppm,而粘度是大约350mPas和微胶囊的强度和稳定性低。对比实施例4
重复对比实施例1,但在达到固化温度时将18.1g蜜胺一次添加到胶囊分散体中,所述蜜胺已经制备成27%淤浆和使用甲酸酸化为4.5的pH。分散体立即增稠。形成了絮凝物,并且分散体凝聚。剩余胶囊残余物的复印能力大大下降。对比实施例5
重复对比实施例1,但使用具有1∶5.3∶3.4的蜜胺∶甲醛∶甲醇摩尔比的部分甲基化蜜胺-甲醛树脂。在加热期间,注意到粘度显著增加。最终的Brookfield粘度是150mPas和冷水提取物中甲醛含量是260ppm。
从实施例可以明显看出,当使用氨或脲作为甲醛清除剂(参见对比实施例1和2),获得了中等良好粘度和在冷水提取物中高甲醛水平的分散体。脲在分散阶段的开始添加(对比实施例3)虽然降低了甲醛含量,但急剧升高了粘度。使用具有特殊摩尔比的蜜胺∶甲醛∶甲醇的部分甲基化蜜胺-甲醛树脂(在固化过程中加入了蜜胺在甲酸中的悬浮液)(实施例1)获得了高固体含量、低粘度和在冷水提取物中可接收的甲醛含量的分散体。当蜜胺和脲在甲酸中的混合物在固化过程中添加时(实施例2),同样的蜜胺-甲醛树脂获得了具有50%的固体含量、非常低粘度和在冷水提取物中甲醛含量低的分散体。
Claims (9)
1、一种制备微胶囊分散体的方法,该方法通过使蜜胺∶甲醛∶甲醇摩尔比为1∶3.0∶2.0-1∶6.0∶4.0的部分甲基化蜜胺-甲醛树脂在水中缩合而进行,其中通过在20-50℃的温度下预成型微胶囊,然后在>50-100℃下固化该预成型微胶囊的胶囊壁来使形成胶囊芯的基本水不溶性物质在3-6.5的pH下在作为保护胶体的2-丙烯酰胺基-2-甲基丙烷磺酸的均聚物或共聚物的碱金属盐存在下以分散体存在,该方法包括在固化过程中添加5-100wt%的蜜胺,基于蜜胺-甲醛树脂。
2、如权利要求1所要求的方法,其中在达到固化温度之后,用基本恒定的质量流速开始蜜胺悬浮液的加料。
3、如权利要求1或2所要求的方法,其中在固化过程中添加蜜胺/脲重量比为1∶20-20∶1的蜜胺和脲的混合物。
4、如前述权利要求中任一项所要求的方法,其中部分甲基化蜜胺-甲醛树脂与2-丙烯酰胺基-2-甲基丙烷磺酸的均聚物或共聚物的碱金属盐的重量比是3∶1-4.5∶1。
5、如前述权利要求中任一项所要求的方法,其中通过将蒸汽注入到微胶囊分散体中将微胶囊分散体加热至固化温度。
6、如前述权利要求中任一项所要求的方法,其中所得微胶囊分散体具有至少45wt%的固体含量。
7、一种可通过权利要求1-6中任一项所要求的方法获得的微胶囊分散体。
8、一种具有包含基本水不溶性物质的芯和包含缩合蜜胺-甲醛树脂的胶囊壁的微胶囊分散体,微胶囊直径的d50值在3-8μm的范围内,商(d90-d10)/d50在0.3-0.8的范围内,分散体的固体含量是至少45wt%,以及分散体在23℃和50rpm下的Brookfield粘度低于100mPas。
9、如权利要求7或8所要求的微胶囊分散体用于制备印刷油墨或纸涂布组合物的用途。
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DE10000621A DE10000621A1 (de) | 2000-01-10 | 2000-01-10 | Niedrigviskose, formaldehydreduzierte Dispersionen von Mikrokapseln aus Melamin-Formaldehyd-Harzen |
DE10000621.3 | 2000-01-10 |
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EP (1) | EP1246693B1 (zh) |
JP (1) | JP5044077B2 (zh) |
CN (1) | CN1247298C (zh) |
AT (1) | ATE263623T1 (zh) |
AU (1) | AU2001230173A1 (zh) |
BR (1) | BR0107475B1 (zh) |
DE (2) | DE10000621A1 (zh) |
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2001
- 2001-01-09 AT AT01902297T patent/ATE263623T1/de not_active IP Right Cessation
- 2001-01-09 AU AU2001230173A patent/AU2001230173A1/en not_active Abandoned
- 2001-01-09 JP JP2001551607A patent/JP5044077B2/ja not_active Expired - Lifetime
- 2001-01-09 US US10/169,092 patent/US6719931B2/en not_active Expired - Lifetime
- 2001-01-09 EP EP01902297A patent/EP1246693B1/de not_active Expired - Lifetime
- 2001-01-09 ES ES01902297T patent/ES2214392T3/es not_active Expired - Lifetime
- 2001-01-09 TR TR2004/00589T patent/TR200400589T4/xx unknown
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101205310B (zh) * | 2006-12-06 | 2012-09-19 | 巴斯福股份公司 | 三聚氰胺-甲醛树脂的甲醛降低的微胶囊分散体 |
CN101554573B (zh) * | 2009-04-22 | 2011-05-18 | 东南大学 | 聚脲-蜜胺树脂双层壁材十六烷微胶囊及其制备方法 |
CN101712862B (zh) * | 2009-11-27 | 2012-07-25 | 东南大学 | 用于降低大体积混凝土内部温升的导热流体及其制备方法 |
CN105200859A (zh) * | 2015-08-24 | 2015-12-30 | 广东冠豪高新技术股份有限公司 | 一种环保型无碳复写纸及其制备方法 |
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DE10000621A1 (de) | 2001-07-12 |
ATE263623T1 (de) | 2004-04-15 |
US20030004226A1 (en) | 2003-01-02 |
CN1247298C (zh) | 2006-03-29 |
JP5044077B2 (ja) | 2012-10-10 |
US6719931B2 (en) | 2004-04-13 |
EP1246693B1 (de) | 2004-04-07 |
TR200400589T4 (tr) | 2004-06-21 |
BR0107475A (pt) | 2002-10-08 |
EP1246693A1 (de) | 2002-10-09 |
WO2001051197A1 (de) | 2001-07-19 |
DE50101906D1 (de) | 2004-05-13 |
ES2214392T3 (es) | 2004-09-16 |
JP2003519724A (ja) | 2003-06-24 |
BR0107475B1 (pt) | 2011-07-12 |
AU2001230173A1 (en) | 2001-07-24 |
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