[go: up one dir, main page]

CN107805436B - 酮基官能化聚合物粒子和聚合物珠粒的水性分散液 - Google Patents

酮基官能化聚合物粒子和聚合物珠粒的水性分散液 Download PDF

Info

Publication number
CN107805436B
CN107805436B CN201710690973.6A CN201710690973A CN107805436B CN 107805436 B CN107805436 B CN 107805436B CN 201710690973 A CN201710690973 A CN 201710690973A CN 107805436 B CN107805436 B CN 107805436B
Authority
CN
China
Prior art keywords
weight
polymer particles
range
composition
polymer beads
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710690973.6A
Other languages
English (en)
Other versions
CN107805436A (zh
Inventor
D·康纳
J·A·加拉赫尔
P·R·哈希
P·S·马宗达
E·努吉塞
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rohm and Haas Co
Original Assignee
Rohm and Haas Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rohm and Haas Co filed Critical Rohm and Haas Co
Publication of CN107805436A publication Critical patent/CN107805436A/zh
Application granted granted Critical
Publication of CN107805436B publication Critical patent/CN107805436B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
    • C08K5/24—Derivatives of hydrazine
    • C08K5/25—Carboxylic acid hydrazides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09D133/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/04—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C09D127/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/24—Homopolymers or copolymers of amides or imides
    • C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D177/00—Coating compositions based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Coating compositions based on derivatives of such polymers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

本发明涉及包含各自经酮基官能化的聚合物粒子和交联聚合物珠粒的水性分散液，和二胺或二酰肼交联剂的组合物。本发明的分散液适用于涂层应用。

Description

酮基官能化聚合物粒子和聚合物珠粒的水性分散液
本发明涉及各自经酮基官能化的聚合物粒子和交联聚合物珠粒的水性分散液。本发明的分散液适用于涂层应用。
具有低颜料容积浓度(PVC)的建筑涂层显示相比于高PVC涂层较好的耐久性和去污属性。低PVC涂层倾向于在半光泽至高光泽的光泽范围内，其中成膜聚合物驱动主要性能属性。高光泽涂料主要包含成膜聚合物和无机颜料。无机增量剂(如碳酸钙、粘土、二氧化硅等)用于降低调配物的成本和涂层的光泽，但最终以干燥涂层的性能为代价。增量剂增加的表面积导致增量剂与粘合剂之间相当大的相互作用，进而降低粘合剂可在干燥涂层中建立性能的效率。因此，发现在相对高性能的情况下实现低光泽的方式将是涂层配方领域中的进步。
发明内容
本发明通过提供包含以下的组合物而满足所属领域中的需要：
a)以下的水性分散液
1)具有75nm至350nm范围内的平均粒度的聚合物粒子，和
2)具有1μm至30μm范围内的平均粒度的交联聚合物珠粒；
其中聚合物粒子包含以聚合物粒子的重量计0.1至12重量％的含有酮基官能团的单体的结构单元；且交联聚合物珠粒包含以交联聚合物珠粒的重量计0.05至12重量％的含有酮基官能团的单体的结构单元；且
其中聚合物粒子与交联聚合物珠粒的重量与重量比在1:10至10:1范围内；和
b)以涂料组合物的重量计0.1至10重量％的二酰肼或多胺交联剂。
本发明组合物提供具有相比于未经类似官能化的双峰分散液出人意料地改进的耐擦洗性的涂层。
具体实施方式
本发明通过提供包含以下的组合物而满足所属领域中的需要：
a)以下的水性分散液
1)具有75nm至350nm范围内的平均粒度的聚合物粒子，和
2)具有1μm至30μm范围内的平均粒度的交联聚合物珠粒；
其中聚合物粒子包含以聚合物粒子的重量计0.1至12重量％的含有酮基官能团的单体的结构单元；且交联聚合物珠粒包含以交联聚合物珠粒的重量计0.05至12重量％的含有酮基官能团的单体的结构单元；且
其中聚合物粒子与交联聚合物珠粒的重量与重量比在1:10至10:1范围内；和
b)以涂料组合物的重量计0.1至10重量％的二酰肼或多胺交联剂。
聚合物粒子优选地为具有优选地在80nm至250nm范围内的平均粒度的丙烯酸或苯乙烯-丙烯酸聚合物粒子。如本文所用，聚合物粒子的平均粒度是指使用BrookhavenBI90粒子分析仪测量的粒度。
聚合物粒子优选地在环境温度下成膜；因此，聚合物粒子优选地具有小于25℃、更优选地小于15℃并且最优选地小于5℃的如通过福克斯方程式(Fox equation)计算的Tg。优选地，聚合物粒子包含甲基丙烯酸甲酯(Tg＝105℃)或苯乙烯(Tg＝100℃)的结构单元，和至少一种选自由以下组成的群组的单体：丙烯酸乙酯(Tg＝-22℃)、丙烯酸丁酯(Tg＝-54℃)、丙烯酸2-乙基己酯(Tg＝-85℃)和丙烯酸2-丙基庚酯(Tg＝-68℃)。
有利地使用常规单阶段或多阶段乳液聚合化学制备的聚合物粒子进一步包含以聚合物粒子的重量计0.1、更优选地0.5、并且最优选地1重量％至12、优选地10、并且更优选地8重量％的具有酮基官能团的单体，也就是说，含有酮或醛基的单体的结构单元。具有酮基官能团的优选单体是甲基丙烯酸乙酰乙酰氧基乙酯(AAEM，Tg＝3℃)，优选地，以聚合物粒子的重量计，其浓度在2至10重量百分比范围内；或二丙酮丙烯酰胺(DAAM，(Tg＝85℃))，优选地，以聚合物粒子的重量计，其浓度在1至5重量百分比范围内。另外，聚合物粒子优选地包含0.2、更优选地0.5、并且最优选地1重量％至优选地5、并且更优选3重量％的羧酸单体，如丙烯酸(Tg＝103℃)、甲基丙烯酸(Tg＝185℃)或衣康酸(Tg＝154℃)。
交联聚合物珠粒优选地具有2μm、并且更优选地5μm至优选地20μm、并且更优选地15μm范围内的平均粒度。如本文所用，聚合物珠粒的平均粒度是指如通过装备有2000uP模块的Malvern Mastersizer 2000分析仪所测量的尺寸。交联聚合物珠粒优选地包含以聚合物珠粒的重量计0.1、更优选地0.2、并且最优选地0.5至优选地10、更优选地8重量％的含有酮基官能团的单体的结构单元。
交联聚合物珠粒的水性分散液可通过多种方法，如美国专利公开案2013/0052454；US 4,403,003；US 7,768,602；和US 7,829,626中所公开的方法制备。在优选方法中，如羟乙基纤维素(HEC)、聚(乙烯醇)(PVOH)、聚(乙烯基吡咯烷酮)(PVP)或非离子表面活性剂的胶体稳定剂溶解于水中以形成水相；通过混合单体和交联剂，如二乙烯基苯或甲基丙烯酸烯丙酯且将引发剂溶解于单体混合物中而制备有机相。优选的引发剂为疏水性的，并且因此主要分成单体相；优选的引发剂的实例为过氧化苯甲酰、过氧化月桂酰和过辛酸叔丁酯。通过使用任何适合的方法，如机械搅拌使水相和有机相均质化而制备单体乳液。热引发方法为优选的。聚合可通过分批、半连续或连续法进行且聚合珠粒可通过单阶段或多阶段聚合方法制备。
如果聚合分多个阶段进行，那么优选的是一个阶段包含使交联单体和低Tg单体，如丙烯酸2-乙基己酯、丙烯酸乙酯、丙烯酸丁酯、或丙烯酸2-丙基庚酯共聚合，且另一阶段包含高Tg单体，如甲基丙烯酸甲酯或苯乙烯的聚合。含酮基的单体可发现于多阶段聚合的一个或多个阶段中。优选地，分两个阶段进行多阶段聚合反应。
聚合物粒子与交联聚合物珠粒的重量:重量比在1:10、优选地4:6至10:1、优选地8:2范围内。
组合物进一步包括以涂料组合物的重量计0.1、优选地0.2、并且更优选地0.5重量％至10、并且优选地5重量％的二酰肼或多胺交联剂。多胺交联剂的实例包括二胺，如3,3'-(乙烷-1,2-二基双(氧基))双(丙-1-胺)；4,9-二氧十二烷-1,12-二胺；4,9-二氧十二烷-1,12-二胺；4,7-二氧十二烷-1,10-二胺；和4,7,10--1,13-二胺。多胺的商业实例是聚醚胺，如JEFFAMINE D-230、JEFFAMINE D-400、JEFFAMINE D-2000、JEFFAMINE M-600、JEFFAMINE M-1000、JEFFAMINE ED-600、JEFFAMINE ED-900、T-403以及JEFFAMINE T-3000聚醚胺。
二酰肼交联剂的实例包括己二酸二酰肼(ADH)、碳二酰肼(carbodihydrazide；CDH)、癸二酸二酰肼(SDH)、缬氨酸二酰肼(VDH)、间苯二甲酸二酰肼(ISODH)以及二十烷二酰肼ICODH)。优选地，交联剂为二酰肼，更优选地ADH。
本发明组合物优选地包含基本上不存在的具有1.0至1.9范围内的折射率的无机增量剂，其倾向于对所得涂层的耐擦洗性和抗污性具有不良影响。如本文所用，“基本上不存在”是指小于10、优选小于5、更优选小于1并且最优选地0PVC的任何具有指定范围内的折射率的增量剂。组合物中基本上不存在的增量剂的实例包括二氧化硅、硅酸盐和铝硅酸盐，如滑石、粘土、云母和绢云母；CaCO3；霞石正长岩；长石；硅灰石；高岭石；磷酸二钙；和硅藻土。
本发明组合物有利地包含多种其他添加剂，如流变改性剂、消泡剂、中和剂、表面活性剂、分散剂、有机颜料(如不透明聚合物)和高折射率无机颜料(Rf>2)，如TiO2。已出人意料地发现由本发明组合物制备的涂层展现相比于来自未类似地经酮基官能化的聚合珠粒和粘合剂的含水分散体的涂层优良的耐擦洗性。
实例
中间实例1-合成DAAM官能化微球体珠粒
单体乳液的水相是通过将CELLOSIZETM羟乙基纤维素QP-3L(HEC，3.8g，陶氏化学公司(The Dow Chemical Company)或其附属公司的商标)溶解于去离子水(332.3g)中制备。一旦HEC完全溶解，将Polystep A-16-22阴离子表面活性剂(1.2g)和二丙酮丙烯酰胺(DAAM，1.5g)添加至溶液。用于单体乳液的有机相是通过混合甲基丙烯酸烯丙酯(ALMA，6.1g)与丙烯酸2-乙基己酯(2-EHA，145.1g)，接着溶解LuperoxLP过氧化月桂酰(0.87g)而制备。
水相和有机相在2L烧瓶中组合且使用Pro#250型转子-定子均质机均质化。乳液在1的功率设定下精制30s。精制的乳液转移至装备有半月形搅拌桨叶的1L反应器中。搅拌设定为130rpm且持续反应的剩余时间用N2喷洒反应器的内含物。
将乳液逐渐加热至且维持于75℃直至观测到自我维持的放热。峰值放热观测为约83℃，且放热的时长持续25至35min。一旦反应放热消退，将反应器冷却至80℃且再保持混合10min。
DAAM(0.3g)和甲基丙烯酸甲酯(MMA，36.3g)的溶液接着经45min添加至反应器，此后将反应温度维持于80℃下15min。将内含物冷却至65℃，此时将硫酸亚铁(5mL于水中的0.15％溶液)添加至反应器。残余单体用叔丁基过氧化氢(t-BHP，0.1g的70％溶液，用5mL水稀释)追加且经30min分开馈入异抗坏血酸(IAA，0.15g，用5mL水稀释)，其后将反应器冷却至室温。所得乳液过滤通过100孔筛。固体含量为35.7％。
比较中间实例1-合成未经DAAM官能化的微球珠粒
基本上如关于中间实例1所描述地制备比较中间实例1，除了对于ME1，不使用DAAM且使用额外1.5g 2-EHA；且对于ME2，不使用DAAM且使用额外0.3g MMA。
中间实例2-合成DAAM官能化粘合剂
通过混合去离子水(764.6g)与Rhodafac RS-610/A25表面活性剂(18.8g)制备单体乳液。单体以如下顺序混合为乳液：DAAM(36.6g)、丙烯酸丁酯(BA，356.7g)、二苯甲酮(28.0g)、丙烯酸乙基己酯(EHA，503.2g)、MMA(880.7g)和甲基丙烯酸(MAA，46.6g)。
向装备有桨式搅拌器、温度计、N2入口和回流冷凝器的5L四颈圆底烧瓶中添加去离子水(1029.0g)和Rhodafac RS-610/A25表面活性剂(98.2g)、碳酸钠(7.56g溶解于47g水中)，接着水冲洗(28g)。在N2下将烧瓶的内含物加热至85℃且起始搅拌。
将一部分第一单体乳液(ME1，117.2g)添加至反应器，接着添加过硫酸铵水溶液(5.67g溶解于25g去离子水中)。在放热起始之后，持续ME1馈入的其余时间将反应器温度维持于85℃。当反应器温度达到85℃时，经79min将ME1馈入至烧瓶。在ME1馈入起始之后40min将脲基甲基丙烯酸酯(46.6g)添加至ME1。一旦ME1馈入完成，将水冲洗(20mL)添加至反应器且反应维持于85℃下5min。
将七水合硫酸亚铁的促进溶液(6.32g 0.15％水溶液)添加至反应器，接着添加VERSENETMEDTA螯合剂(1.0g 1％水溶液，陶氏化学公司或其附属公司的商标)。
残余单体使用t-BHP(1.9g的70％水溶液)和去离子水(21.0mL)以及IAA(0.9g30.0mL水)追加，其经30min分开馈入至反应器。
将反应器冷却至室温，在此期间将氢氧化铵水溶液(15.2g的28％水溶液)添加至反应器。接着将己二酸二酰肼(18.8g)于水(32g)中的浆液添加至反应器。一旦反应器温度冷却至低于30℃，将KATHONTMLX 1.4Biocide 1.4(14.4g于15mL水中，陶氏化学公司或其附属公司的商标)添加至反应器。一旦反应器冷却至室温，将所得分散液过滤通过325孔筛。固体含量为47％。
比较中间实例2-合成未经DAAM官能化的粘合剂
比较中间实例2基本上如关于制备中间实例2所描述地制备，除了DAAM(36.6g)经额外量的MMA(36.6g)替换。
涂料制备
在0.25升塑料容器中，在顶部搅拌1min的情况下将粘合剂、TAMOLTM731A分散剂(0.7g)、TRITONTMCF-10表面活性剂(0.2g)和BYK-022消泡剂(0.3g)混合在一起。将TiO2浆液Ti Pure R-746(24g)和聚合物珠粒缓慢添加至以上溶液。调节搅拌速度以确保足够混合。继续混合5min。随后，将Texanol聚结剂(0.7g)和丙二醇(0.6g)缓慢添加至混合物且再继续混合2至3min。增加搅拌速度且缓慢添加ACRYSOLTMRM-2020流变改性剂(2g)。随后，在高速搅拌下添加ACRYSOL RM-8W流变改性剂(1.4g)和其余的下泄水(参见表1)以调节粘度。再继续混合5至10min。最终混合物为含有涂料的着色微球。(TAMOL、TRITON和ACRYSOL全部为陶氏化学公司或其附属公司的商标)。
表1说明涂料调配物中的珠粒和粘合剂量。C1、C2和C3是指比较涂料调配物1、2和3，且Ex 1是指实例1。DAAM珠粒是指涂料中的DAAM官能化微球珠粒(来自中间实例1)的量；非DAAM珠粒是指涂料中未经DAAM官能化的微球珠粒(来自比较中间实例1)的量；DAAM粘合剂是指涂料中的DAAM官能化粘合剂(来自中间实例2)的量；且非DAAM官能化粘合剂是指未经DAAM官能化的粘合剂(来自比较中间实例2)的量。所有量以克为单位。
表1-涂料调配物中的珠粒和粘合剂量
涂料实例 DAAM珠粒 非DAAM珠粒 DAAM粘合剂 非DAAM粘合剂
C1 0 26.5 0 38.5
C2 0 26.5 37.1 0
C3 25.7 0 0 38.5
Ex 1 25.7 0 37.1 0
耐擦洗性测试方法：
涂料使用7mil涂抹棒一式两份地在黑色莱内塔乙烯基图表(Black Leneta Vinylchart)上方取样且在77℉(25℃)、50％相对湿度下干燥7天。在干燥之后，每一图表纵向地切成两半以产生四个用于每一涂层的测试条。通过彻底混合莱内塔标准化研磨型擦洗介质(Leneta Standardized Abrasive Type Scrub Medium)SC-2(636g)、水(318g)和Airex901W消泡剂(1.5g)制备擦洗介质。在装备有Masterflex L/S管式泵、具有0.5"×10mil黄铜垫片的金属盘和尼龙鬃刷的机器上进行擦洗测试。将每一条在垫片上方置于金属盘上，涂布侧朝上且用夹钳固定。擦洗介质(10g)分配于所述涂层上且测试在计数器设定于0的情况下开始。在每400循环(在失效之前)之后，分配额外量的擦洗介质(10g)，随后继续测试。耐擦洗性报导为在跨越垫片的0.5"宽度的一条连续线中完全去除所述涂层所需的循环数目。用于涂层的擦洗循环的平均值是基于每个涂层八次测量报导且结果说明于表2中。
表2-涂层的平均擦洗值
涂料实例 擦洗(平均)
C1 357
C2 444
C3 253
Ex 1 734
结果显示使用各自经DAAM官能化的粘合剂和珠粒形成的涂层的明显优良的耐擦洗性。

Claims (7)

1.一种涂料组合物，其包含：
a)以下的水性分散液
1)具有75nm至350nm范围内的平均粒度的聚合物粒子，和
2)具有1μm至30μm范围内的平均粒度的交联聚合物珠粒；
其中所述聚合物粒子包含以所述聚合物粒子的重量计0.1至12重量％的含有酮基官能团的单体的结构单元；且所述交联聚合物珠粒包含以所述交联聚合物珠粒的重量计0.05至12重量％的含有酮基官能团的单体的结构单元；且
其中聚合物粒子与交联聚合物珠粒的重量与重量比在1:10至10:1范围内；和
b)以所述涂料组合物的重量计0.1至10重量％的二酰肼或多胺交联剂。
2.根据权利要求1所述的组合物，其中所述聚合物粒子包含以所述聚合物粒子的重量计0.5至10重量％的含有酮基官能团的单体的结构单元；且所述交联聚合物珠粒包含以所述交联聚合物珠粒的重量计0.2至10重量％的含有酮基官能团的单体的结构单元；其中所述聚合物粒子具有80nm至250nm范围内的平均粒度；且所述交联聚合物珠粒具有5μm至20μm范围内的平均粒度。
3.根据权利要求2所述的组合物，其中聚合物粒子与交联聚合物珠粒的重量与重量比在4:6至8:2范围内，其中所述交联聚合物珠粒具有5μm至15μm范围内的平均粒度。
4.根据权利要求1到3中任一项所述的组合物，其中所述含有酮基官能团的单体为浓度在以所述聚合物粒子的重量计的1至5重量％范围内的二丙酮丙烯酰胺，或浓度在以所述聚合物粒子的重量计的2至10重量％范围内的甲基丙烯酸乙酰乙酰氧基乙酯；且所述交联剂为二酰肼交联剂。
5.根据权利要求1至3中任一项所述的组合物，其中所述组合物进一步包含小于10PVC的具有1.0至1.9范围内的折射率的无机增量剂，其中所述二酰肼交联剂为己二酸二酰肼。
6.根据权利要求5所述的组合物，其中所述组合物包含小于5PVC的具有1.0至1.9范围内的折射率的无机增量剂。
7.根据权利要求1至3中任一项所述的组合物，其中所述组合物包含小于1PVC的具有1.0至1.9范围内的折射率的无机增量剂；其中所述组合物进一步包括至少一种选自由以下组成的群组的材料：流变改性剂、消泡剂、中和剂、表面活性剂、分散剂、不透明聚合物和TiO2。
CN201710690973.6A 2016-09-09 2017-08-14 酮基官能化聚合物粒子和聚合物珠粒的水性分散液 Active CN107805436B (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201662385497P 2016-09-09 2016-09-09
US62/385497 2016-09-09

Publications (2)

Publication Number Publication Date
CN107805436A CN107805436A (zh) 2018-03-16
CN107805436B true CN107805436B (zh) 2021-05-07

Family

ID=59901355

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710690973.6A Active CN107805436B (zh) 2016-09-09 2017-08-14 酮基官能化聚合物粒子和聚合物珠粒的水性分散液

Country Status (7)

Country Link
US (1) US10508213B2 (zh)
EP (1) EP3293231B1 (zh)
KR (1) KR102429132B1 (zh)
CN (1) CN107805436B (zh)
AU (1) AU2017219037B2 (zh)
BR (1) BR102017018070A2 (zh)
CA (1) CA2977114A1 (zh)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10858531B2 (en) * 2018-04-18 2020-12-08 Dow Global Technologies Llc Aqueous dispersion of keto- and phosphorus acid monomer-functionalized polymer particles
WO2021136705A1 (en) * 2019-12-31 2021-07-08 Basf Se A water-borne polymer composition, a method for making such and its application as removable pressure sensitive adhesive
KR20250080366A (ko) 2023-11-28 2025-06-05 주식회사 아이델 굴절율을 조절할 수 있는 폴리머 비드 제조용 조성물 및 이를 이용한 폴리머 비드의 제조방법

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030224184A1 (en) * 2002-05-07 2003-12-04 Hermes Ann Robertson Method of producing wear resistant traffic markings
US20070218291A1 (en) * 2006-03-15 2007-09-20 Shang-Jaw Chiou Aqueous compositions comprising polymeric duller particle
CN101250242A (zh) * 2008-03-08 2008-08-27 西北师范大学 两亲聚合物树脂及其制备和在生产智能呼吸涂料中的应用
US20130071453A1 (en) * 2007-12-17 2013-03-21 Milan F. Sojka Compositions Comprising Solid Particles Entrapped In Collapsed Polymeric Microspheres, And Methods Of Making The Same
CN105801898A (zh) * 2016-03-14 2016-07-27 华南理工大学 一种交联聚脲中空微球及其制备方法与应用

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0038127B1 (en) 1980-04-14 1984-10-17 Imperial Chemical Industries Plc Multi-layer coating process involving use of aqueous basecoat composition containing crosslinked polymer microparticles and having a pseudoplastic or thixotropic character
US7768602B2 (en) 2007-10-16 2010-08-03 Rohm And Haas Company Light diffusing article with GRIN lenses
BR112014000661A2 (pt) * 2011-07-26 2017-06-13 Rohm & Haas processo, e, formulação de revestimento
CN102952462B (zh) 2011-08-25 2016-06-29 罗门哈斯公司 底涂层/透明涂层涂料
CN104277649B (zh) * 2013-07-08 2019-09-27 罗门哈斯公司 双峰吸附胶乳
US10759959B2 (en) * 2016-05-18 2020-09-01 Ppg Industries Ohio, Inc. Waterborne compositions and compact processes of forming multi-component composite coating compositions on substrates

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030224184A1 (en) * 2002-05-07 2003-12-04 Hermes Ann Robertson Method of producing wear resistant traffic markings
US20070218291A1 (en) * 2006-03-15 2007-09-20 Shang-Jaw Chiou Aqueous compositions comprising polymeric duller particle
US20130071453A1 (en) * 2007-12-17 2013-03-21 Milan F. Sojka Compositions Comprising Solid Particles Entrapped In Collapsed Polymeric Microspheres, And Methods Of Making The Same
CN101250242A (zh) * 2008-03-08 2008-08-27 西北师范大学 两亲聚合物树脂及其制备和在生产智能呼吸涂料中的应用
CN105801898A (zh) * 2016-03-14 2016-07-27 华南理工大学 一种交联聚脲中空微球及其制备方法与应用

Also Published As

Publication number Publication date
KR20180028914A (ko) 2018-03-19
EP3293231B1 (en) 2020-11-04
US20180072913A1 (en) 2018-03-15
KR102429132B1 (ko) 2022-08-03
AU2017219037A1 (en) 2018-03-29
CN107805436A (zh) 2018-03-16
EP3293231A1 (en) 2018-03-14
BR102017018070A2 (pt) 2018-05-02
US10508213B2 (en) 2019-12-17
AU2017219037B2 (en) 2021-09-30
CA2977114A1 (en) 2018-03-09

Similar Documents

Publication Publication Date Title
CN101205267B (zh) 含磷的有机聚合物以及包括该有机聚合物的组合物和方法
AU2018202805B2 (en) Ureido-functionalized aqueous polymeric dispersion
EP2928934B1 (en) Stable aqueous dispersion of particle polymers containing structural units of 2-(methacryloyloxy)ethyl phosphonic acid and composites thereof
CN107805436B (zh) 酮基官能化聚合物粒子和聚合物珠粒的水性分散液
CN114174445B (zh) 聚丙烯酸和聚乙酸乙烯酯胶乳的共混物
AU2017232029B2 (en) Aqueous dispersion of adsorbing polymer particles and crosslinkable polymer particles
CN108219075A (zh) 具有橡实形态的氟烷基化聚合物粒子的水性分散液

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant