CN110520453A - 用碱可溶胀聚合物颗粒制备涂料调配物 - Google Patents
用碱可溶胀聚合物颗粒制备涂料调配物 Download PDFInfo
- Publication number
- CN110520453A CN110520453A CN201880025854.1A CN201880025854A CN110520453A CN 110520453 A CN110520453 A CN 110520453A CN 201880025854 A CN201880025854 A CN 201880025854A CN 110520453 A CN110520453 A CN 110520453A
- Authority
- CN
- China
- Prior art keywords
- weight
- alkali
- polymers capable
- swelling
- coating composition
- 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.)
- Granted
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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
-
- 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
- C08F212/00—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 an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- 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
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/02—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of acids, salts or anhydrides
-
- 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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, 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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
- C08L25/08—Copolymers of styrene
- C08L25/14—Copolymers of styrene with unsaturated esters
-
- 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
-
- 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
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- 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
- C09D7/66—Additives characterised by particle size
- C09D7/68—Particle size between 100-1000 nm
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2203—Oxides; Hydroxides of metals of lithium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/50—Aqueous dispersion, e.g. containing polymers with a glass transition temperature (Tg) above 20°C
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/52—Aqueous emulsion or latex, e.g. containing polymers of a glass transition temperature (Tg) below 20°C
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Nanotechnology (AREA)
- Paints Or Removers (AREA)
- Graft Or Block Polymers (AREA)
- Medicinal Preparation (AREA)
- Cosmetics (AREA)
Abstract
本发明涉及一种用于制备具有开放时间添加剂的涂料组合物的方法,所述方法包括以下步骤:a)使碱可溶胀聚合物颗粒的含水分散体与流变改性剂和粘合剂接触以形成具有小于50g/L的VOC的涂料组合物;以及b)在与所述流变改性剂和所述粘合剂接触后或接触时,用非挥发性碱中和所述碱可溶胀颗粒,以形成溶胀的多级聚合物颗粒;其中所述碱可溶胀聚合物颗粒包括具有不高于25℃的Tg的壳和酸官能化的核;并且其中核‑壳比在1:3.2到1:10的范围内。根据本发明的所述方法得到的所述组合物可用于增加特别是低VOC涂料应用的开放时间。在另一方面,本发明涉及制备具有开放时间添加剂的涂料组合物,所述制备包括以下步骤:a)使所述开放时间添加剂与流变改性剂和粘合剂接触以形成具有小于50g/L的VOC的涂料组合物,然后b)中和所述开放时间添加剂以形成溶胀的多级聚合物颗粒,其中具有所述开放时间添加剂的所述涂料组合物与不具有所述开放时间添加剂的所述涂料组合物相比显示出小于50%的粘度增加。
Description
背景技术
本发明涉及一种用于用碱可溶胀聚合物颗粒的含水分散体制备涂料调配物的方法。碱可溶胀聚合物颗粒的分散体可用作涂料调配物中的开放时间添加剂。
政府法规和市场运作不断趋向用于涂料调配物的零挥发性有机化合物(VOC)。因此,不含挥发性溶剂和聚结剂的水性调配物已在行业内变得越来越受欢迎。尽管如此,油漆特性已由于这种巨大的改变而损害;尤其为开放时间,所述开放时间为在其期间新施用的漆膜可二次加工而不留刷痕的时间段。在溶剂型系统中,开放时间为约30到45分钟;在典型的水性调配物中,开放时间为大约3到5分钟。因此,本领域中需要寻找一种用于水性调配物的添加剂,所述添加剂使开放时间延长超过目前可用的添加剂而不降低最终涂料的其它特性,如膜粘合和粘聚强度、硬度、耐粘连性、早期耐起泡性、耐擦洗性、耐污染性以及耐损性。
发明内容
本发明通过提供一种用于制备具有开放时间添加剂的涂料组合物的方法解决了本领域的需求,所述方法包括以下步骤:a)使碱可溶胀聚合物颗粒的含水分散体与流变改性剂和粘合剂接触以形成具有小于50g/L的VOC的涂料组合物;以及b)在与所述流变改性剂和所述粘合剂接触后或接触时,用非挥发性碱中和所述碱可溶胀颗粒,以形成溶胀的多级聚合物颗粒;其中所述碱可溶胀聚合物颗粒包括具有不高于25℃的Tg的壳和酸官能化的核;并且其中核-壳比在1:3.2到1:10的范围内。
在另一方面,本发明提供了一种用于制备具有开放时间添加剂的涂料组合物的方法,所述方法包括以下步骤:使作为碱可溶胀聚合物颗粒的含水分散体的开放时间添加剂与流变改性剂和粘合剂接触以形成具有小于50g/L的VOC的涂料组合物;其中在与所述流变改性剂和所述粘合剂接触后或接触时,用碱中和所述碱可溶胀颗粒,以形成溶胀的多级聚合物颗粒;其中所述碱可溶胀聚合物颗粒包括具有不高于25℃的Tg的壳和酸官能化的核;并且其中核-壳比在1:3.2到1:6的范围内,并且其中具有所述开放时间添加剂的所述涂料组合物与不具有所述开放时间添加剂的所述涂料组合物相比显示出小于50%的粘度增加。
与不含有所述溶胀的多级聚合物颗粒的可比调配物相比,根据本发明的方法得到的所述涂料组合物具有明显更长的开放时间。
具体实施方式
在第一方面,本发明是一种用于制备具有开放时间添加剂的涂料组合物的方法,所述方法包括以下步骤:a)使碱可溶胀聚合物颗粒的含水分散体与流变改性剂和粘合剂接触以形成具有小于50g/L的VOC的涂料组合物;以及b)在与所述流变改性剂和所述粘合剂接触后或接触时,用非挥发性碱中和所述碱可溶胀颗粒,以形成溶胀的多级聚合物颗粒;其中所述碱可溶胀聚合物颗粒包括具有不高于25℃的Tg的壳和酸官能化的核;并且其中核-壳比在1:3.2到1:10的范围内。
碱可溶胀聚合物颗粒的特征在于酸官能化的第一阶段部分(核),优选地羧酸官能化核,和第二阶段部分(壳),通过福克斯(Fox)方程式计算所述第二阶段部分的Tg不高于25℃。本文中使用的词语“核”和“壳”是为了方便描述聚合过程的第一和最后阶段(或者如果聚合物颗粒在两个阶段中产生,则为第一和第二阶段)。因此,最终的碱可溶胀聚合物颗粒可以但不必需具有核-壳形态。碱可溶胀聚合物颗粒可通过许多技术(包含本领域熟知的技术)中的任一种来制备。(参见US 4,468,498;US 5,326,843;和US 9,340,685)。例如,核可以通过单阶段或多阶段方法来产生,任选地在如正十二烷基硫醇或巯基乙醇的链转移剂的存在下生产。核也可以由种子方法来制备。然后核用于在一个或多个附加阶段中制备碱可溶胀聚合物颗粒。优选地,核-壳比在1:3.2到1:6的范围内。
优选地,核包括按核的重量计30重量%、更优选地35重量%并且最优选地38重量%到优选地50重量%、更优选地到45重量%并且最优选地到42重量%的羧酸单体的结构单元。如本文所使用的,术语“结构单元”是指在聚合之后引述单体的剩余部分。例如,甲基丙烯酸的结构单元如以下所说明:
酸官能化核还优选地包括50重量%、更优选地55重量%并且最优选地58重量%到优选地70重量%、更优选地到65重量%并且最优选地到62重量%的非离子烯键式不饱和单体的结构单元。
羧酸官能化单体的实例包含甲基丙烯酸、丙烯酸以及衣康酸,其中优选丙烯酸和甲基丙烯酸。非离子烯键式不饱和单体的实例包含一种或多种C1-C10丙烯酸烷酯和甲基丙烯酸酯,如甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸丁酯和丙烯酸2-乙基己酯;以及苯乙烯。甲基丙烯酸甲酯和甲基丙烯酸丁酯是优选的非离子烯键式不饱和单体。
核还可包括多烯键式不饱和单体的结构单元,如乙二醇二(甲基)丙烯酸酯、烯丙基(甲基)丙烯酸酯、1,3-丁二醇二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、三羟甲基丙烷三甲基丙烯酸酯,或二乙烯基苯。如果存在,多烯键式不饱和单体的结构单元按核的重量计优选地在0.1重量%、更优选地0.3重量%到10重量%、更优选地到3重量%的范围内。
在与碱接触之前,如通过BI-90 Plus Brookhaven颗粒分析仪所测量的,核的平均直径优选地在100nm、更优选地120nm、最优选地150nm到优选地500nm、更优选地到400nm、更优选地到350nm并且最优选地到250nm的范围内。
壳的Tg更优选地不大于20℃并且最优选地不大于15℃。优选地,壳包括一种或多种Tg>50℃的单体(即一种或多种高Tg单体)的结构单元,如甲基丙烯酸甲酯(Tg=105℃)或苯乙烯(Tg=100℃)或其组合,以及至少一种Tg低于10℃的单体(即一种或多种一种低Tg单体)的结构单元,如丙烯酸乙酯(Tg=-23℃)、丙烯酸丁酯(Tg=-53℃),或丙烯酸2-乙基己酯(Tg=-52℃)或其组合。壳优选地进一步包括酸单体、优选地羧酸单体、优选地甲基丙烯酸(Tg=228℃)或丙烯酸(Tg=101℃)的结构单元。(所述Tg是指由聚合物特性(Polymer Properties)2015报告的对应均聚物的Tg)。
优选地,壳中高Tg单体的结构单元(优选地甲基丙烯酸甲酯或苯乙烯、更优选地甲基丙烯酸甲酯)的浓度按壳的重量计在40重量%、更优选地42重量%并且最优选地44重量%到优选地60重量%、更优选地到55重量%、更优选地到50重量%并且最优选地到48重量%的范围内。
优选地,壳中低Tg单体的结构单元的浓度按壳的重量计在38重量%、更优选地45重量%、更优选地48重量%并且最优选地50重量%到优选地59重量%、更优选地到57重量%并且最优选地到54重量%的范围内。低Tg单体优选地为丙烯酸丁酯。
优选地,壳中羧酸单体的结构单元的浓度按壳的重量计在0.2重量%、更优选地0.5重量%到优选地5重量%、更优选地到3重量%并且最优选地到2重量%的范围内。
优选地,如通过BI-90 Plus Brookhaven颗粒分析仪所测量的,碱可溶胀聚合物颗粒的平均直径在150nm、更优选地200nm到900nm、更优选地到750nm、更优选地到550nm、更优选地到400nm、并且最优选地到300nm的范围内。
优选地,在与粘合剂和流变改性剂接触之前,碱可溶胀聚合物颗粒的浓度按水和碱可溶胀聚合物颗粒的重量计在10重量%、更优选地20重量%并且最优选地30重量%到60重量%、更优选地到50重量%的范围内。
一旦碱可溶胀聚合物颗粒与粘合剂和流变改性剂接触,优选地与包括粘合剂和流变改性剂的涂料组合物接触,就可以中和碱可溶胀聚合物颗粒以形成中和的多级聚合物颗粒,而无需进一步添加非挥发性碱(因为所述组合物含有足够量的碱来中和并且溶胀聚合物颗粒的核);然而,通常优选地将非挥发性碱后添加到涂料组合物中以确保pH在调配物的期望范围内。
如本文所用,非挥发性碱是指沸点高于150℃的碱。如本文所用,“中和”意指使核的pH升高到比用于制备酸官能化的核的酸单体的pKa高至少1.5个单位的pH。例如,如果使用甲基丙烯酸(pKa=4.65)制备酸官能化的核,则涂料组合物的pH为或被调整到至少6.15、优选地至少6.5、更优选地至少7并且最优选地至少8。优选地,相对于碱可溶胀聚合物颗粒的酸含量,添加的非挥发性碱的量或涂料调配物中已有的非挥发性碱的量为至少50%的化学计量、更优选地至少化学计量并且最优选地大于化学计量。
非挥发性碱增加了核的pH,从而将其中和并且使其溶胀。用于本发明该方面的合适的非挥发性碱的实例包含2-氨基-2-甲基-1-丙醇(可作为AMP 95中和剂商购)、正-丁基二乙醇胺(可作为Vantex T中和剂商购)、LiOH、NaOH或KOH。当需要低VOC调配物时,碱金属氢氧化物LiOH、NaOH或KOH是特别优选的。优选地,使碱与碱可溶胀聚合物颗粒在15℃、更优选地20℃到50℃、更优选地到40℃、并且最优选地到30℃范围内的温度下进行接触。
如本文所用,术语粘合剂是指当暴露于碱时表现出粒度的增加小于10nm的聚合物颗粒的含水分散体。如通过Brookhaven BI-90 Plus粒度分析仪所测定的,这些聚合物颗粒(粘结剂固体)的平均直径优选地在70nm、更优选地100nm到600nm、更优选地到500nm的范围内。粘合剂固体包括按粘结剂固体的重量计小于5重量%、优选地小于4重量%并且最优选地小于3重量%的酸单体的结构单元。
粘合剂有利地通过一种或多种烯键式不饱和单体的水乳液聚合来制备,所述一种或多种烯键式不饱和单体的实例包含苯乙烯、乙酸乙烯酯、丙烯酰胺、甲基丙烯酰胺、丙烯腈和甲基丙烯酸或丙烯酸的C1-C10烷基酯,所述C1-C10烷基酯包含甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-丙基庚酯和丙烯酸2-乙基己酯。
如本文所用,术语流变改性剂是指水溶性或水分散性缔合流变改性剂,如疏水改性环氧乙烷氨基甲酸酯聚合物(HEUR)、疏水改性碱可溶胀乳液(HASE)和苯乙烯-马来酸酐三元共聚物(SMAT)以及非缔合流变改性剂,如碱可溶胀乳液(ASE)和羟乙基纤维素(HEC)增稠剂。
涂料调配物中与粘合剂(粘结剂固体)相关联的聚合物颗粒的浓度按涂料组合物中固体的重量计优选地在3重量%、更优选地5重量%、并且最优选地10重量%到优选地50重量%、更优选地到40重量%、并且最优选地到30重量%的范围内。流变改性剂的浓度按涂料组合物中固体的重量计在0.5重量%到5重量%的范围内。
涂料组合物中中和的多级聚合物颗粒的浓度按涂料组合物的重量计优选地在0.1重量%、优选地0.2重量%并且更优选地0.5重量%到10重量%、优选地到5重量%、更优选地到4重量%并且最优选地到3重量%的范围内。尽管中和核将倾向于增加涂料组合物的粘度(参见US 4,468,498),但是使用本发明的方法中和后的粘度与中和前的涂料组合物的粘度相比变化小于50%、优选地小于40%并且最优选地小于30%。优选地,中和后粘度的增加小于30Ku、更优选地小于20Ku并且最优选地小于15KU。
如果确实发生增稠情况,则会相对较快地发生。优选地,在完成碱添加小于1小时内涂料组合物的最终粘度达到至少90%、更优选地至少95%并且最优选地至少99%。
因此,在第二方面,本发明提供了一种用于制备具有开放时间添加剂的涂料组合物的方法,所述方法包括以下步骤:a)使作为碱可溶胀聚合物颗粒的含水分散体的开放时间添加剂与流变改性剂和粘合剂接触以形成具有小于50g/L的VOC的涂料组合物;其中在与流变改性剂和粘合剂接触后或接触时,用碱中和碱可溶胀颗粒,以形成溶胀的多级聚合物颗粒;其中所述碱可溶胀聚合物颗粒包括具有不高于25℃的Tg的壳和酸官能化的核;其中核-壳比在1:3.2到1:6的范围内,并且其中具有开放时间添加剂的涂料组合物与不具有开放时间添加剂的涂料组合物相比显示出小于50%的粘度增加。在本发明的该方面,也可以使用挥发性碱,如氨、三甲胺、三乙胺或甲基异丙基胺;然而,在需要低VOC调配物的情况下,非挥发性碱,尤其是碱金属氢氧化物是优选的。
本发明的碱可溶胀聚合物颗粒的分散体虽然适用作涂料组合物的开放时间添加剂,但不适用作增稠剂;有意地将碱可溶胀聚合物颗粒的浓度维持在不会引起组合物明显增稠的水平下。
可以以任何顺序来组合碱可溶胀聚合物颗粒的含水分散体、粘合剂和流变改性剂。优选地,使碱可溶胀聚合物颗粒与粘合剂和流变改性剂的含水分散体接触,然后添加碱。通过本发明的方法制备的组合物可以进一步有利地包含以下组分中的任一种或全部:分散剂、颜料、消泡剂、表面活性剂、溶剂、增量剂、聚结剂、杀生物剂、不透明聚合物和着色剂。所述组合物是挥发性有机物含量(VOC)小于50g/L的低VOC组合物。
实例
中间实例—制备核-壳比为1:5的碱可溶胀聚合物
A.制备第1阶段(核)
如下制备第一阶段(核,60MMA/40MAA):5L四颈圆底烧瓶(釜)配备有浆式搅拌器、温度计、N2入口和回流冷凝器。将去离子水(1760g)添加到釜中并且在N2下加热到86℃。通过将去离子水(720g)、十二烷基苯磺酸钠(SDS,5.2g,23%活性)、甲基丙烯酸甲酯(780.0g)和甲基丙烯酸(10.0g)混合来制备单体乳液(ME1)。取出一部分ME1(164.0g)并且放在一边的一个单独的容器中。向剩余的ME1中添加SDS(50.0g,23%活性)和甲基丙烯酸(510.0g)。当釜温达到86℃时,将去离子水(160.0g)和SDS(5.0g,23%活性)的混合物添加到釜中,然后添加最初取出的ME1并且放在一边。接着将过硫酸钠(5.5g)于去离子水(40.0g)中的混合物添加到釜中。釜的温度降至约76℃,接着使其在15分钟的保持期内升高到85℃。接着将剩余的ME1在85℃下经2小时进料到釜中。在完成ME1进料之后,将分散体保持在85℃下持续15分钟,之后将分散体冷却到25℃并且过滤以去除任何凝结物。过滤后的分散体具有2.9的pH、31.7%的固含量和152nm的平均粒度。
B.具有1:5核-壳比率和于核中的40%甲基丙烯酸的碱可溶胀聚合物颗粒的分散体的制备
向配备有浆式搅拌器、温度计、N2入口和回流冷凝器的5L四颈圆底烧瓶(釜)中添加DI水(500g)并且在N2下加热到86℃。通过将DI水193g、SDS(14.3g,23%活性)、丙烯酸丁酯(655.2g)、甲基丙烯酸甲酯(585.9g)和甲基丙烯酸(18.9g)混合来制备单体乳液(ME2)。当釜温达到86℃时,将部分A(795.0g)的分散体添加到釜中并且将温度调节到60℃。接着将0.1%硫酸铁(II)于水(20g)中的溶液与和DI水(45g)混合的异抗坏血酸(0.6g)溶液一起添加到釜中。将过硫酸钠(3.8g)于DI水(90g)和亚硫酸氢钠(2.5g)于DI水(90g)中的共进料溶液以0.7克/分钟的速率添加到釜中。在开始添加共进料溶液三分钟后,以2克/分钟的速率添加ME2。在开始添加ME2十分钟后,进料速率增加到4g/m。再过十分钟后,ME2进料速率增加到8克/分钟。再过十分钟后,ME进料速率增加到16克/分钟。在整个ME2的添加过程中,釜的温度保持在59-61℃。在完成ME2的添加之后,共进料再过量进料二十分钟。在完成共进料添加后,将釜的内容物冷却到室温并且过滤以去除任何凝结物。过滤后的分散体具有2.1的pH、47.5%的固含量和275nm的平均粒度,如通过BI-90 Plus Brookhaven颗粒分析仪测量的。
比较中间实例—制备核-壳比为1:10的碱可溶胀聚合物
基本上如在中间实例中所描述的来制备碱可溶胀聚合物,不同之处在于核-壳的重量与重量之比为1:10。
通过将碱可溶胀颗粒(ASP)的分散体添加到表1所描述的调配物中来制备油漆调配物。
表1—具有开放时间添加剂的油漆调配物
材料名称 | 磅 | 加仑 |
RHOPLEX<sup>TM</sup> HG-706粘结剂 | 525.7 | 59.37 |
BYK-024消泡剂 | 1.0 | 0.1 |
丙二醇 | 4.3 | 0.5 |
TRITON<sup>TM</sup> X-100表面活性剂 | 4.4 | 0.5 |
水 | 16.7 | 2.0 |
KATHON<sup>TM</sup> LX 1.5%杀生物剂 | 1.5 | 0.2 |
TAMOL<sup>TM</sup> 2002分散剂 | 2.0 | 0.2 |
氨(28%) | 1.0 | 0.1 |
Ti-纯R-746TiO<sub>2</sub> | 285.0 | 14.7 |
水 | 20.0 | 2.4 |
TEXANOL聚结剂 | 7.9 | 1.0 |
ACRYSOL<sup>TM</sup> RM-2020E流变改性剂 | 20.0 | 2.3 |
ACRYSOL<sup>TM</sup> RM-725流变改性剂 | 3.0 | 0.4 |
BYK-024消泡剂 | 2.0 | 0.2 |
ASP(25%固体) | 95.5 | 11.4 |
水 | 38.7 | 4.63 |
总计 | 1030 | 100 |
RHOPLEX、TRITON、KATHON、TAMOL和ACRYSOL都是陶氏化学公司(The Dow ChemicalCompany)或其附属公司的商标。
通过添加足够量的每种碱以达到pH>7用以下三种不同的碱来调整三种独立的涂料调配物的pH:NH4、2-氨基-2-甲基-1-丙醇和NaOH。
开放时间是根据ASTM-D7488测量的。测试在恒定温度/湿度室(72℉,50%RH)中执行。使用刮涂棒以5密耳间隙将油漆沉积在黑色乙烯基擦洗卡片上。通过使用两个木制施加器在湿油漆中制作平行标记,立即对膜进行评分。接着使用涂有底漆的1"尼龙刷以定时间隔刷洗膜的区段。使膜干燥过夜。由至少三名读者构成的小组以视觉方式检查了小组,并将没有显示刻痕标记迹象的最后一个十字刷区部记录为开放时间。根据同样的油漆调配物制备但不具有开放时间添加剂的涂料的开放时间为6分钟以及使用核-壳比为1:10的碱可溶胀聚合物颗粒制备的涂料的开放时间为10分钟,与此相比,核-壳比为1:5并且用NH4OH、NaOH和2-氨基-2-甲基-1-丙醇中和的碱可溶胀聚合物样品的每种涂料的实测开放时间为12分钟。还观察到调配物显示出仅30%的粘度增加,这表明在所使用的浓度下碱可溶胀聚合物颗粒作为增稠剂无效。
Claims (9)
1.一种用于制备具有开放时间添加剂的涂料组合物的方法,所述方法包括以下步骤:a)使碱可溶胀聚合物颗粒的含水分散体与流变改性剂和粘合剂接触以形成具有小于50g/L的VOC的涂料组合物;以及b)在与所述流变改性剂和所述粘合剂接触后或接触时,用非挥发性碱中和所述碱可溶胀颗粒,以形成溶胀的多级聚合物颗粒;其中所述碱可溶胀聚合物颗粒包括具有不高于25℃的Tg的壳和酸官能化的核;并且其中核-壳比在1:3.2到1:10的范围内。
2.根据权利要求1所述的方法,其中所述碱可溶胀聚合物颗粒的含水分散体的固体含量按所述碱可溶胀聚合物颗粒的含水分散体的重量计在10重量%到60重量%的范围内。
3.根据权利要求2所述的方法,其中所述碱可溶胀聚合物颗粒的所述酸官能化的核包括按所述核的重量计30重量%到50重量%的羧酸单体的结构单元,和50重量%到70重量%的非离子烯键式不饱和单体的结构单元;并且其中所述碱可溶胀聚合物颗粒的所述壳具有不高于20℃的Tg并且包括Tg高于50℃的单体的结构单元、Tg低于10℃的单体的结构单元和酸单体的结构单元。
4.根据权利要求3所述的方法,其中所述碱可溶胀聚合物颗粒的所述酸官能化的核包括按所述核的重量计35重量%到45重量%的甲基丙烯酸或丙烯酸的结构单元;以及55重量%到65重量%的非离子烯键式不饱和单体的结构单元,其中所述非离子烯键式不饱和单体是甲基丙烯酸甲酯或甲基丙烯酸丁酯;其中所述壳包括40重量%到60重量%的苯乙烯或甲基丙烯酸甲酯的结构单元、38重量%至59重量%的丙烯酸丁酯的结构单元以及0.2重量%到5重量%的甲基丙烯酸或丙烯酸的结构单元;并且其中所述碱可溶胀聚合物颗粒的平均直径在150nm到900nm的范围内。
5.根据权利要求3或4所述的方法,其中在所述碱可溶胀颗粒与具有所述流变改性剂和所述粘合剂的所述碱可溶胀聚合物颗粒接触之后,在范围为15℃到50℃的温度下将作为LiOH、NaOH或KOH的所述碱添加到所述组合物中;并且其中所述碱可溶胀聚合物颗粒的平均直径在150nm到300nm的范围内。
6.根据权利要求3或4所述的方法,其中在所述碱可溶胀颗粒与具有所述流变改性剂和所述粘合剂的所述碱可溶胀聚合物颗粒接触之前,在范围为15℃到50℃的温度下将作为LiOH、NaOH或KOH的所述碱添加到所述组合物中;并且其中所述碱可溶胀聚合物颗粒的平均直径在150nm到300nm的范围内。
7.根据权利要求5或6所述的方法,其中中和的多级聚合物颗粒的浓度按所述涂料组合物的重量计在0.1重量%到5重量%的范围内;与所述粘结剂相关联的所述聚合物颗粒的浓度按所述涂料组合物的重量计在3重量%到50重量%的范围内;并且所述流变改性剂的浓度按所述涂料组合物的重量计在0.5重量%到5重量%的范围内。
8.根据权利要求7所述的方法,其中所述组合物进一步包含选自由以下组成的组的至少一种组分:分散剂、颜料、消泡剂、表面活性剂、溶剂、增量剂、聚结剂、杀生物剂、不透明聚合物和着色剂。
9.一种用于制备具有开放时间添加剂的涂料组合物的方法,所述方法包括以下步骤:a)使作为碱可溶胀聚合物颗粒的含水分散体的开放时间添加剂与流变改性剂和粘合剂接触以形成具有小于50g/L的VOC的涂料组合物;其中在与所述流变改性剂和所述粘合剂接触后或接触时,用碱中和所述碱可溶胀颗粒,以形成溶胀的多级聚合物颗粒;其中所述碱可溶胀聚合物颗粒包括具有不高于25℃的Tg的壳和酸官能化的核;并且其中核-壳比在1:3.2到1:6的范围内,并且其中具有所述开放时间添加剂的所述涂料组合物与不具有所述开放时间添加剂的所述涂料组合物相比显示出小于50%的粘度增加。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201762501159P | 2017-05-04 | 2017-05-04 | |
US62/501159 | 2017-05-04 | ||
PCT/US2018/030582 WO2018204450A1 (en) | 2017-05-04 | 2018-05-02 | Preparation of a coatings formulation with alkali swellable polymer particles |
Publications (2)
Publication Number | Publication Date |
---|---|
CN110520453A true CN110520453A (zh) | 2019-11-29 |
CN110520453B CN110520453B (zh) | 2022-10-28 |
Family
ID=62218328
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201880025854.1A Active CN110520453B (zh) | 2017-05-04 | 2018-05-02 | 用碱可溶胀聚合物颗粒制备涂料调配物 |
Country Status (8)
Country | Link |
---|---|
US (2) | US20180320007A1 (zh) |
EP (1) | EP3619247B1 (zh) |
CN (1) | CN110520453B (zh) |
AU (1) | AU2018261356B2 (zh) |
BR (1) | BR112019021844A2 (zh) |
CA (1) | CA3062163A1 (zh) |
MX (1) | MX2019012900A (zh) |
WO (1) | WO2018204450A1 (zh) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
MX2019011163A (es) * | 2017-03-27 | 2019-10-17 | Dow Global Technologies Llc | Preparacion de una formulacion de recubrimientos con particulas de polimero hinchables alcalinas. |
AU2019204492B2 (en) | 2018-07-19 | 2023-04-20 | Rohm And Haas Company | Aqueous dispersion of multistage polymer particles |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4468498A (en) * | 1980-06-12 | 1984-08-28 | Rohm And Haas Company | Sequential heteropolymer dispersion and a particulate materal obtainable therefrom, useful in coating compositions as a thickening and/or opacifying agent |
US4916171A (en) * | 1984-07-25 | 1990-04-10 | Rohm And Haas Company | Polymers comprising alkali-insoluble core/alkali-soluble shell and copositions thereof |
CN1077717A (zh) * | 1992-04-10 | 1993-10-27 | 罗姆和哈斯公司 | 乳液胶囊的合成 |
CN1182763A (zh) * | 1996-11-15 | 1998-05-27 | 罗姆和哈斯公司 | 低光泽涂层组合物 |
US20070100035A1 (en) * | 2003-11-25 | 2007-05-03 | Rosekelly George S | Paint with color change additive and method of application and painted substrate |
WO2008028062A2 (en) * | 2006-08-31 | 2008-03-06 | Benjamin Moore & Co. | Latex for low voc paint having improved block resistance, open time and water-softening resistance |
CN102993617A (zh) * | 2011-09-08 | 2013-03-27 | 罗门哈斯公司 | 可溶性壳聚合物组合物及其制备方法 |
CN105440835A (zh) * | 2015-12-09 | 2016-03-30 | 三棵树涂料股份有限公司 | 一种高抗划伤高性能水性木器哑光白面漆 |
CN106574136A (zh) * | 2014-07-07 | 2017-04-19 | 本杰明·摩尔公司 | 顺序聚合的杂化胶乳 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4427836A (en) | 1980-06-12 | 1984-01-24 | Rohm And Haas Company | Sequential heteropolymer dispersion and a particulate material obtainable therefrom, useful in coating compositions as a thickening and/or opacifying agent |
DE3902103A1 (de) * | 1989-01-25 | 1990-08-02 | Roehm Gmbh | Bindemittel fuer waessrige glanzfarben |
US5266646A (en) * | 1989-05-15 | 1993-11-30 | Rohm And Haas Company | Multi-stage polymer particles having a hydrophobically-modified, ionically-soluble stage |
US5326843A (en) | 1993-10-04 | 1994-07-05 | Rohm And Haas Company | Method for making an alkali-soluble emulsion copolymer |
US5494971A (en) | 1994-08-12 | 1996-02-27 | Rohm And Haas Company | Encapsulated hydrophilic polymers and their preparation |
CN104513533B (zh) | 2013-09-30 | 2018-11-06 | 罗门哈斯公司 | Hase流变改性剂vae乳液共聚物组合物 |
MX2019011163A (es) * | 2017-03-27 | 2019-10-17 | Dow Global Technologies Llc | Preparacion de una formulacion de recubrimientos con particulas de polimero hinchables alcalinas. |
-
2018
- 2018-05-02 MX MX2019012900A patent/MX2019012900A/es unknown
- 2018-05-02 CA CA3062163A patent/CA3062163A1/en active Pending
- 2018-05-02 AU AU2018261356A patent/AU2018261356B2/en active Active
- 2018-05-02 CN CN201880025854.1A patent/CN110520453B/zh active Active
- 2018-05-02 WO PCT/US2018/030582 patent/WO2018204450A1/en unknown
- 2018-05-02 BR BR112019021844-0A patent/BR112019021844A2/pt active Search and Examination
- 2018-05-02 US US15/968,939 patent/US20180320007A1/en not_active Abandoned
- 2018-05-02 EP EP18726287.8A patent/EP3619247B1/en active Active
- 2018-05-02 US US16/607,257 patent/US11155722B2/en active Active
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4468498A (en) * | 1980-06-12 | 1984-08-28 | Rohm And Haas Company | Sequential heteropolymer dispersion and a particulate materal obtainable therefrom, useful in coating compositions as a thickening and/or opacifying agent |
US4916171A (en) * | 1984-07-25 | 1990-04-10 | Rohm And Haas Company | Polymers comprising alkali-insoluble core/alkali-soluble shell and copositions thereof |
CN1077717A (zh) * | 1992-04-10 | 1993-10-27 | 罗姆和哈斯公司 | 乳液胶囊的合成 |
US5527613A (en) * | 1992-04-10 | 1996-06-18 | Rohm And Haas Company | Synthesis of latex capsules |
CN1182763A (zh) * | 1996-11-15 | 1998-05-27 | 罗姆和哈斯公司 | 低光泽涂层组合物 |
US20070100035A1 (en) * | 2003-11-25 | 2007-05-03 | Rosekelly George S | Paint with color change additive and method of application and painted substrate |
WO2008028062A2 (en) * | 2006-08-31 | 2008-03-06 | Benjamin Moore & Co. | Latex for low voc paint having improved block resistance, open time and water-softening resistance |
CN102993617A (zh) * | 2011-09-08 | 2013-03-27 | 罗门哈斯公司 | 可溶性壳聚合物组合物及其制备方法 |
CN106574136A (zh) * | 2014-07-07 | 2017-04-19 | 本杰明·摩尔公司 | 顺序聚合的杂化胶乳 |
CN105440835A (zh) * | 2015-12-09 | 2016-03-30 | 三棵树涂料股份有限公司 | 一种高抗划伤高性能水性木器哑光白面漆 |
Also Published As
Publication number | Publication date |
---|---|
WO2018204450A1 (en) | 2018-11-08 |
MX2019012900A (es) | 2019-12-16 |
BR112019021844A2 (pt) | 2020-05-26 |
US20200299527A1 (en) | 2020-09-24 |
EP3619247A1 (en) | 2020-03-11 |
AU2018261356A1 (en) | 2019-12-05 |
US20180320007A1 (en) | 2018-11-08 |
US11155722B2 (en) | 2021-10-26 |
CN110520453B (zh) | 2022-10-28 |
AU2018261356B2 (en) | 2023-05-11 |
CA3062163A1 (en) | 2018-11-08 |
EP3619247B1 (en) | 2023-10-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN103517928B (zh) | 水性多段聚合物分散体、其制备方法及其作为用于涂覆基材的粘合剂的用途 | |
CN101263205B (zh) | 提高含水涂料组合物耐染剂渗透的方法 | |
JP5294863B2 (ja) | 水性塗料用樹脂組成物及び水性塗料組成物 | |
US20170275407A1 (en) | Finely divided aqueous emulsion polymers and use thereof for hydrophobic coatings | |
CA1067236A (en) | Aqueous acrylic-carboxylated polyether compositions | |
CN105367717A (zh) | 包含乳胶和heur增稠剂的组合物 | |
CN107641409A (zh) | 用于制备被磷类酸和光引发剂基团官能化的胶乳的方法 | |
JPS61250066A (ja) | ラテツクス ペイント | |
CN109153876A (zh) | 水性聚合物分散体和包含其的水性涂料组合物 | |
CN110431161A (zh) | 具有开放时间添加剂的涂料配制物 | |
CA1295891C (en) | Method of painting | |
CN110520453A (zh) | 用碱可溶胀聚合物颗粒制备涂料调配物 | |
CN110461913A (zh) | 用碱可溶胀聚合物颗粒制备涂料配制物 | |
AU2017432752B2 (en) | Aqueous polymer composition | |
CN105623417A (zh) | 水性低温固化含氟密封件涂层 | |
CN108219075B (zh) | 具有橡实形态的氟烷基化聚合物粒子的水性分散液 | |
EP4028474A1 (en) | Aqueous dispersion of polymeric particles | |
JPS6131124B2 (zh) | ||
CN106905467A (zh) | 一种自干型环氧基水溶性丙烯酸树脂的制备方法 | |
CN108779318A (zh) | 制备水性粘合剂组合物的方法和由该水性粘合剂组合物制成的保护性涂层 | |
CN115215958A (zh) | 一种水性自交联丙烯酸二级分散体及其制备方法与应用 | |
CN105061693B (zh) | 丙烯酸复合环氧树脂及包含该树脂的环境友好型丙烯酸复合环氧一度漆及其制备方法 | |
CN108350287A (zh) | 具有改进的对于沾污物和脏污物的抵抗性的涂料 | |
CN104449020B (zh) | 用于涂料组合物的反应性多官能添加剂 | |
CN106752232B (zh) | 一种多功能复合防污剂 |
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 |