CN106459551B - 具有改进的耐变黄性的抗菌涂料组合物 - Google Patents
具有改进的耐变黄性的抗菌涂料组合物 Download PDFInfo
- Publication number
- CN106459551B CN106459551B CN201480080058.XA CN201480080058A CN106459551B CN 106459551 B CN106459551 B CN 106459551B CN 201480080058 A CN201480080058 A CN 201480080058A CN 106459551 B CN106459551 B CN 106459551B
- Authority
- CN
- China
- Prior art keywords
- coating composition
- polymer
- dry weight
- silver
- group
- 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.)
- Expired - Fee Related
Links
Classifications
-
- 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
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic 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
- C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
- C09D123/02—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D123/04—Homopolymers or copolymers of ethene
- C09D123/08—Copolymers of ethene
- C09D123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09D123/0853—Vinylacetate
-
- 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
- C09D133/08—Homopolymers or copolymers of acrylic 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
- 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
- C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- 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
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
-
- 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
- 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
- C08F220/38—Esters containing sulfur
- C08F220/382—Esters containing sulfur and containing oxygen, e.g. 2-sulfoethyl (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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
-
- 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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Plant Pathology (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明涉及一种抗菌涂料组合物,其包含:i)第一聚合物;ii)50ppm到2000ppm的银离子和银元素中的至少一种;以及iii)10%到60%的二氧化钛粒子。50%到100%的所述二氧化钛粒子由第二聚合物包封;并且所述第一和所述第二聚合物的总量是根据所述涂料组合物的总干重以干重计5%到80%。
Description
技术领域
本发明涉及一种具有改进的耐变黄性的抗菌涂料组合物。
背景技术
银离子或银元素用于涂料中时为涂料提供极佳的抗菌性能。涂料中的银含量越高,抗菌性能越好。然而,当银含量在涂料中的浓度高于100ppm时,涂料可能变黄。
因此,在涂料行业中需要银含量高于100ppm但仍具有较好耐变黄性能的抗菌涂料组合物。
发明内容
本发明提供一种抗菌涂料组合物,其包含:i)第一聚合物;根据所述涂料组合物的总干重以干重计,ii)50ppm到2000ppm的银离子和银元素中的至少一种;以及iii)10%到60%的二氧化钛粒子。50%到100%的二氧化钛粒子由第二聚合物包封。第一和第二聚合物的总量是根据涂料组合物的总干重以干重计5%到80%。
具体实施方式
本发明的涂料组合物包含:i)第一聚合物;以及根据所述涂料组合物的总干重以干重计,ii)50ppm到2000ppm、优选地100ppm到1000ppm、并且更优选地200ppm到700ppm的银;和iii)10%到60%、优选地15%到50%、并且更优选地20%到40%的二氧化钛粒子。50%到100%、优选地60%到100%、并且更优选地70%到100%的二氧化钛粒子由第二聚合物包封。
第一和第二聚合物的总量是根据涂料组合物的总干重以干重计5%到80%、优选地10%到70%、并且更优选地15%到60%。
第一和第二聚合物
本发明的第一和第二聚合物可以相同或不同。
第一和第二聚合物都包含至少一种聚合的烯系不饱和非离子性单体。如本文所用,术语“非离子性单体”是指在pH=1-14之间不带有离子电荷的单体。烯系不饱和非离子性单体的合适实例包括(甲基)丙烯酸的烷基酯,如丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯、丙烯酸癸酯、丙烯酸十二烷酯、甲基丙烯酸甲酯、甲基丙烯酸丁酯、甲基丙烯酸异癸酯、甲基丙烯酸十二烷酯、甲基丙烯酸羟乙酯、甲基丙烯酸羟丙酯和其任何组合;(甲基)丙烯腈;(甲基)丙烯酰胺;氨基官能单体和脲基官能单体,如甲基丙烯酸羟乙基亚乙基脲酯;带有乙酰乙酸酯官能团的单体,如甲基丙烯酸乙酰乙酰氧基乙酯(AAEM);带有含羰基基团的单体,如二丙酮丙烯酰胺(DAAM);具有苯环(如苯乙烯和被取代的苯乙烯)的烯系不饱和单体;丁二烯;α-烯烃,如乙烯、丙烯和1-癸烯;乙酸乙烯酯、丁酸乙烯酯、叔碳酸乙烯酯和其它乙烯酯;乙烯基单体,如氯乙烯和偏二氯乙烯;(甲基)丙烯酸缩水甘油酯;以及其任何组合。
优选地,烯系不饱和非离子性单体选自甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯、苯乙烯、乙酸乙烯酯、丁酸乙烯酯以及其任何组合。
第一和第二聚合物中的至少一种可以进一步包含根据所述聚合物的总干重以干重计少于10%、优选地少于5%、并且更优选地少于2.5%的稳定剂单体。稳定剂单体的合适实例包括苯乙烯磺酸钠(SSS)、乙烯基磺酸钠(SVS)、2-丙烯酰胺基-2-甲基丙烷磺酸(AMPS)、丙烯酰胺(AM)、丙烯酸(AA)、甲基丙烯酸(MAA)以及衣康酸(IA)。
银
在本发明中,银以银元素(即,Ag0)形式或以氧化态银离子(即,Ag1+)形式并入涂料组合物中,并且以银溶液形式提供。银溶液的合适实例包括含硝酸银、乙酸银、柠檬酸银、碘化银、乳酸银、苦味酸银、硫酸银的去离子(“DI”)水以及其任何组合。银溶液的优选实例是硝酸银和碘化银。除去离子水以外,还可使用其它液体介质,如水、水性缓冲溶液和有机溶液,如聚醚或醇。这些溶液中的银浓度可以在向抗菌涂料组合物中添加已知量的银(即,如在本发明中,根据涂料组合物的总干重以干重计,50ppm到2000ppm、优选地100ppm到1000ppm、并且更优选地200ppm到700ppm)所需的浓度到饱和银溶液的范围内变化。可商购的银溶液包括来自陶氏化学公司(The Dow Chemical Company)的SILVADURTM 900、SILVADUR 930、SILVADUR 961和SILVADUR ET以及来自巴斯夫公司(BASF Company)的IRGAGUARDTM B 5000、IRGAGUARD B5120、IRGAGUARD B 6000、IRGAGUARD D 1071和IRGAGUARD H 6000。
二氧化钛粒子
任何二氧化钛(TiO2)粒子都可以用于本发明的涂料组合物中。可商购的二氧化钛粒子包括来自杜邦公司(DuPont)的TI-PURETM R-706和TI-PURE R-902+、MillenniumInorganic Chemicals的TIONATM 595、来自亨斯迈公司的TIOXIDETM TR92、龙蟒集团(LOMONCorporation)的LOMONTM R-996和LOMON LR-997、来自河南佰利联化学股份有限公司(HenanBillions Chemical co.,Ltd.)的BILLIONTM BLR-688和BILLION BLR-699、来自山东东佳集团股份有限公司(Shandong Doguide Group Co.,Ltd.)的DOGUIDETM SR-237、来自宁波新福钛白粉有限公司(Ningbo Xinfu Titanium Dioxide Co.,Ltd.)的NTR-606、以及来自道恩集团(Dawn Group)的R-2195和R-2295。优选地,二氧化钛粒子选自可购自杜邦公司的TI-PURETM R-706和TI-PURE R-902+。
第二聚合物在二氧化钛粒子表面上的包封可以通过聚合方法来实现。聚合方法可以是所属领域中已知的任何方法,包括乳液聚合、微乳液聚合和机械分散技术。
抗菌涂料组合物
涂料组合物可以进一步包含其它颜料或增量剂。
如本文所用,术语“颜料”是指能够实质上有助于涂料的不透明度或隐藏能力的颗粒状无机材料。颜料的折射率通常等于或大于1.8,并且包括氧化锌、硫化锌、硫酸钡和碳酸钡。出于明晰的目的,本发明的二氧化钛粒子不包括在本发明的“颜料”中。
术语“增量剂”是指折射率小于或等于1.8并且大于1.3的颗粒状无机材料,并且包括碳酸钙、氧化铝(Al2O3)、粘土、硫酸钙、铝硅酸盐、硅酸盐、沸石、云母、硅藻土、实心或空心玻璃、以及瓷珠。涂料组合物可以任选地含有Tg大于60℃的实心或空心聚合粒子,此类聚合粒子在本文中出于颜料体积浓度(PVC)计算的目的而分类为增量剂。空心聚合粒子的细节描述于EP 22633、EP 915108、EP 959176、EP 404184、US5360827、WO 00/68304以及US20100063171中。实心聚合物粒子的粒子大小为1到50微米,并且优选地5到20微米。聚合粒子的合适实例是可商购自陶氏化学公司的ROPAQUETM Ultra E不透明聚合物。出于明晰的目的,本发明的聚合粒子与本发明的第一或第二聚合物不同。碳酸钙、粘土、云母和氧化铝(Al2O3)是优选的增量剂。
涂料组合物的PVC(颜料体积浓度)如下计算:
PVC(%)=[颜料的体积+增量剂的体积]/涂料的总干燥体积。
在一个优选实施例中,涂料组合物的PVC为10%到75%,并且优选地20%到70%。
涂料组合物的制备
涂料组合物的制备涉及以下方法:选择并且以恰当比例混合适当涂料成分以提供具有特定加工和处理特性的涂料以及具有所需特性的最终干燥涂料膜。
涂料组合物的涂覆
涂料组合物可以通过常规涂覆方法涂覆,如涂刷、辊涂和喷雾方法,如空气雾化喷雾、空气辅助喷雾、无空气喷雾、高体积低压喷雾和空气辅助无空气喷雾。
用于涂料涂覆的合适的衬底包括混凝土、水泥板、中等密度纤维板(MDF)和粒子板、石膏板、木材、石材、金属、塑料、墙纸以及纺织品等。优选地,所有衬底都由水基性或溶剂型底漆预涂布。
实例
I.原材料
II.测试程序
耐变黄性测定
用200um Bird涂膜器在涂布有底漆的水泥板上进行刮涂,并且接着使其在恒定温度房间(CTR)中干燥1天。将经过干燥的涂料膜放置在玻璃窗边进行日晒。在两周内通过BYK-Gardner色标卡球形分光光度计测量膜的B值。
III.实验实例
1.第二聚合物包封二氧化钛粒子分散液的制备
向配备有电磁搅拌器、N2入口、回流冷凝器、加热套以及热电偶的250ml烧瓶中装入20g SEM、4g DMAEMA、10g BA、16g MMA、1.1g n-DDM、0.5g AIBN以及100g正丙醇。用N2吹扫烧瓶,并且加热到60℃,此时关闭加热套并且使反应混合物在放热的情况下加热到80℃。开启加热套并且使反应混合物在80℃下保持3小时。接着使温度升高到93℃,并且添加含0.25g AIBN的2.0g正丙醇。使温度在93℃下保持1小时。接着使烧瓶冷却到室温。将产物倾入100ml己烷中,并且接着收集固体聚合物并且将其干燥。将干燥聚合物溶解于足够的水和NH3中以制得pH为5.0的21.3%溶液。
向钢研磨罐中装入31.7g所述溶液和95.2g水。在使用来自耐驰集团(NetzschGroup)的配备有圆盘刀片的50型实验室分散器以2000rpm研磨的同时,缓慢添加450g TI-PURE R-706TiO2。将混合物研磨20分钟,并且接着再添加11.3g水以制得76.5%TI-PURE R-706TiO2浆液。
向配备有浆式搅拌器、N2入口、冷凝器、加热套以及热电偶的1加仑四颈圆底烧瓶中装入1816g所述浆液以及13.81g DS-4(23%固体)于251.05g去离子水中的溶液。用N2吹扫烧瓶,并且加热到30℃。接着向反应器中添加50g 0.1%硫酸铁和4g 1%EDTA。两分钟后,将由溶解于110.53g去离子水中的2g t-BHP组成的1号共馈料和由溶解于96.25g去离子水中的8.28g IAA组成的2号共馈料馈入到反应器中。在添加共馈料溶液之后两分钟后,将先前通过混合56.52g去离子水、6.9g DS-4、119.3g BA、139.7g MMA和2.6g MAA来制备的第一单体乳液(ME1)馈入到反应器中。接着,将先前通过混合269.5g去离子水、20.71g DS-4、355.5g BA、416.3g MMA和7.8g MAA来制备的第二单体乳液(ME2)馈入到反应器中。再继续反应20分钟。接着使反应器内含物冷却到室温,随后在40分钟内馈入84g NaOH溶液(6%固体)。通过100目过滤器过滤少量凝胶。其余部分是本发明的第二聚合物包封二氧化钛粒子分散液。分散液包含33%二氧化钛、26%第二聚合物以及水。
2.抗菌涂料组合物的制备
根据表1使用以下程序来制备含有不同量的二氧化钛粒子(100%未被包封)的比较性涂料(比较实例)1、4、6和8。使用高速Cowles分散器混合研磨成分。使用常规实验室混合器来添加稀释成分。比较性涂料1、4、6和8的PVC分别是45%、26%、67%和45%。
根据表2使用与比较性涂料制备中所描述相同的程序来制备含有不同量的第二聚合物包封二氧化钛粒子的涂料2、3、5、7和9。根据涂料的总重量,涂料3包含11.1%未被包封的二氧化钛和25.9%第二聚合物包封二氧化钛。涂料2、3、5、7和9的PVC分别是45%、45%、26%、67%和45%。
比较性涂料8和涂料9使用亚硝酸银(1%),而其它涂料使用SILVERDUE ET作为银组分,并且银含量中的每一个都在表3中列出。
表1
表2
IV.结果和分析
表3
*表3中列出的银浓度是根据涂料组合物总干重的干重;
#比较性涂料8和涂料9使用亚硝酸银(1%),而其它涂料使用SILVERDUE ET作为银组分。
如表3中所示,与包含未被包封的TiO2的涂料组合物相比较,包含第二聚合物包封TiO2的含银涂料组合物具有改进的耐变黄性。对于细节,涂料2与比较性涂料(实例)1相比较,涂料5与比较实例4相比较,涂料7与比较实例6相比较,涂料9与比较实例8相比较,都展示减小的ΔB值,其指示由涂料组合物中的银造成的变黄问题通过包封TiO2而得到改进。如由涂料3的结果所指示,TiO2的70%(25.9/(11.1+25.9)=70%)包封足以实现改进的耐变黄性能。
Claims (13)
1.一种抗菌涂料组合物,其包含:
i)第一聚合物;以及
根据所述涂料组合物的总干重以干重计,
ii)50ppm到2000ppm的银离子和银元素中的至少一种;和
iii)10%到60%的二氧化钛粒子;
其中50%到100%的所述二氧化钛粒子由第二聚合物包封;并且所述第一聚合物和所述第二聚合物的总量是根据所述涂料组合物的总干重以干重计5%到80%;
其中所述第二聚合物包含烯系不饱和非离子单体和稳定剂单体,
其中所述烯系不饱和非离子单体选自甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯、苯乙烯、乙酸乙烯酯、丁酸乙烯酯以及其任何组合;
其中所述稳定剂单体选自苯乙烯磺酸钠、乙烯基磺酸钠、2-丙烯酰胺基-2-甲基丙烷磺酸、丙烯酰胺、丙烯酸、甲基丙烯酸、衣康酸及其组合。
2.根据权利要求1所述的涂料组合物,其中所述银离子选自硝酸银、碘化银以及其组合。
3.根据权利要求1所述的涂料组合物,其包含根据所述涂料组合物的总干重以干重计,200ppm到700ppm的银离子和银元素中的至少一种。
4.根据权利要求1所述的涂料组合物,其包含根据所述涂料组合物的总干重以干重计,20%到40%的二氧化钛粒子。
5.根据权利要求1所述的涂料组合物,其中70%到100%的所述二氧化钛粒子由所述第二聚合物包封。
6.根据权利要求1所述的涂料组合物,其中所述第一聚合物包含选自以下的烯系不饱和非离子性单体:甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯、苯乙烯、乙酸乙烯酯、丁酸乙烯酯以及其任何组合。
7.根据权利要求1所述的涂料组合物,其中所述第一聚合物和所述第二聚合物的总量是根据涂料组合物的总干重以干重计15%到60%。
8.根据权利要求1所述的涂料组合物,其中所述第一聚合物进一步包含稳定剂单体,所述稳定剂单体选自苯乙烯磺酸钠、乙烯基磺酸钠、2-丙烯酰胺基-2-甲基丙烷磺酸、丙烯酰胺、丙烯酸、甲基丙烯酸以及衣康酸。
9.根据权利要求1所述的涂料组合物,其中所述涂料组合物进一步包含选自以下的增量剂:碳酸钙、粘土、云母和氧化铝。
10.一种抗菌涂料组合物,其包含:
i)第一聚合物;以及
根据所述涂料组合物的总干重以干重计,
ii)200ppm到700ppm的银离子和银元素中的至少一种;和
iii)20%到40%的二氧化钛粒子;
其中70%到100%的所述二氧化钛粒子由第二聚合物包封;并且所述第一聚合物和所述第二聚合物的总量是根据所述涂料组合物的总干重以干重计15%到60%;
其中所述第二聚合物包含烯系不饱和非离子单体和稳定剂单体,
其中所述烯系不饱和非离子单体选自甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯、苯乙烯、乙酸乙烯酯、丁酸乙烯酯以及其任何组合;
其中所述稳定剂单体选自苯乙烯磺酸钠、乙烯基磺酸钠、2-丙烯酰胺基-2-甲基丙烷磺酸、丙烯酰胺、丙烯酸、甲基丙烯酸、衣康酸及其组合。
11.根据权利要求10所述的抗菌涂料组合物,其中所述第一聚合物包含选自以下的烯系不饱和非离子性单体:甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯、苯乙烯、乙酸乙烯酯、丁酸乙烯酯以及其任何组合;并且所述银离子选自硝酸银、碘化银以及其组合。
12.根据权利要求10所述的抗菌涂料组合物,其中所述烯系不饱和非离子性单体选自甲基丙烯酸甲酯、丙烯酸丁酯、苯乙烯、乙酸乙烯酯以及其任何组合;并且所述稳定剂单体是甲基丙烯酸。
13.根据权利要求10所述的抗菌涂料组合物,其中所述烯系不饱和非离子性单体是甲基丙烯酸甲酯和丙烯酸丁酯;并且所述稳定剂单体是甲基丙烯酸。
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/CN2014/081170 WO2016000131A1 (en) | 2014-06-30 | 2014-06-30 | Antimicrobial coating composition with improved yellowing resistance |
Publications (2)
Publication Number | Publication Date |
---|---|
CN106459551A CN106459551A (zh) | 2017-02-22 |
CN106459551B true CN106459551B (zh) | 2020-05-12 |
Family
ID=55018225
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201480080058.XA Expired - Fee Related CN106459551B (zh) | 2014-06-30 | 2014-06-30 | 具有改进的耐变黄性的抗菌涂料组合物 |
Country Status (8)
Country | Link |
---|---|
US (1) | US10550279B2 (zh) |
EP (1) | EP3161070A4 (zh) |
KR (1) | KR20170023105A (zh) |
CN (1) | CN106459551B (zh) |
AU (1) | AU2014399854B2 (zh) |
BR (1) | BR112016029633A2 (zh) |
CA (1) | CA2952667A1 (zh) |
WO (1) | WO2016000131A1 (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB202007701D0 (en) * | 2020-05-22 | 2020-07-08 | Univ Manchester | Antiviral polymers |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101891971A (zh) * | 2009-05-19 | 2010-11-24 | 罗门哈斯公司 | 不透明颜料颗粒 |
CN102206393A (zh) * | 2010-03-31 | 2011-10-05 | 罗门哈斯公司 | 抗菌聚合物乳液和涂料组合物 |
CN102942816A (zh) * | 2011-04-27 | 2013-02-27 | 贝洱工艺公司 | 通过sip形成氧化钛间隙 |
CN103062961A (zh) * | 2011-10-22 | 2013-04-24 | Tcl空调器(中山)有限公司 | 一种热泵热水器的钛金蒸发器及其制备方法 |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3890268A (en) * | 1973-09-07 | 1975-06-17 | Goodrich Co B F | Weather resistant polyvinyl chloride compounds and method of making same |
EP0040418B1 (en) | 1978-09-12 | 1985-07-03 | Fujisawa Pharmaceutical Co., Ltd. | Process for preparing an 1h-indazol-3-ylacetic acid derivative |
CA1180474A (en) | 1979-06-26 | 1985-01-02 | Alexander Kowalski | Sequential heteropolymer dispersion and a particulate material obtainable therefrom useful in coating compositions as a thickening and/or opacifying agent |
US5360827A (en) | 1992-03-31 | 1994-11-01 | Nippon Zeon Co., Ltd. | Process for preparation of latex of hollow polymer |
US6020435A (en) | 1997-11-05 | 2000-02-01 | Rohm And Haas Company | Process for preparing polymer core shell type emulsions and polymers formed therefrom |
EP0959176B1 (en) | 1998-05-18 | 2012-09-05 | Rohm And Haas Company | Hollow sphere organic pigment for paper or paper coatings |
FI991051A (fi) | 1999-05-07 | 2000-11-08 | Neste Chemicals Oy | Huokosia sisältävien polymeerihiukkasten valmistamismenetelmä |
US7579081B2 (en) | 2004-07-08 | 2009-08-25 | Rohm And Haas Company | Opacifying particles |
US7482054B2 (en) | 2004-08-09 | 2009-01-27 | Behr Process Corporation | Pigment spacing |
KR20070000639A (ko) * | 2005-06-28 | 2007-01-03 | 삼성전자주식회사 | 백라이트 어셈블리 및 이를 구비한 평판 표시 장치 |
DE102005033516A1 (de) | 2005-07-14 | 2007-01-18 | Basf Ag | Verfahren zur Herstellung von Emulsionspolymerisaten |
US7601212B2 (en) | 2005-08-29 | 2009-10-13 | E.I. Du Pont De Nemours And Company | Pigment particles coated with polysaccharides and having improved properties |
NZ571932A (en) | 2006-04-03 | 2010-10-29 | Univ Sydney | Polymer product and interfacial polymerisation process using chain transfer agent (CTA) |
GB0903016D0 (en) * | 2009-02-23 | 2009-04-08 | Univ Gent | Method for alleviating intestinal problems and novel bacterial strains therefor |
KR101350635B1 (ko) * | 2009-07-03 | 2014-01-10 | 엘지디스플레이 주식회사 | 듀얼 쉬프트 레지스터 |
CN103738035B (zh) * | 2013-10-21 | 2015-07-15 | 江阴华东装饰材料有限公司 | 防污抗菌高分子家具装饰膜及其制备方法 |
-
2014
- 2014-06-30 WO PCT/CN2014/081170 patent/WO2016000131A1/en active Application Filing
- 2014-06-30 AU AU2014399854A patent/AU2014399854B2/en not_active Ceased
- 2014-06-30 CA CA2952667A patent/CA2952667A1/en not_active Abandoned
- 2014-06-30 EP EP14896694.8A patent/EP3161070A4/en not_active Withdrawn
- 2014-06-30 BR BR112016029633A patent/BR112016029633A2/pt not_active Application Discontinuation
- 2014-06-30 KR KR1020177001673A patent/KR20170023105A/ko not_active Application Discontinuation
- 2014-06-30 CN CN201480080058.XA patent/CN106459551B/zh not_active Expired - Fee Related
- 2014-06-30 US US15/313,156 patent/US10550279B2/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101891971A (zh) * | 2009-05-19 | 2010-11-24 | 罗门哈斯公司 | 不透明颜料颗粒 |
CN102206393A (zh) * | 2010-03-31 | 2011-10-05 | 罗门哈斯公司 | 抗菌聚合物乳液和涂料组合物 |
CN102942816A (zh) * | 2011-04-27 | 2013-02-27 | 贝洱工艺公司 | 通过sip形成氧化钛间隙 |
CN103062961A (zh) * | 2011-10-22 | 2013-04-24 | Tcl空调器(中山)有限公司 | 一种热泵热水器的钛金蒸发器及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
KR20170023105A (ko) | 2017-03-02 |
US20170183530A1 (en) | 2017-06-29 |
AU2014399854A1 (en) | 2017-02-02 |
EP3161070A1 (en) | 2017-05-03 |
US10550279B2 (en) | 2020-02-04 |
AU2014399854B2 (en) | 2018-11-01 |
CN106459551A (zh) | 2017-02-22 |
CA2952667A1 (en) | 2016-01-07 |
BR112016029633A2 (pt) | 2017-08-22 |
WO2016000131A1 (en) | 2016-01-07 |
EP3161070A4 (en) | 2018-01-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5837961B2 (ja) | 多段エマルションポリマーおよび向上した顔料効率 | |
EP2371870B1 (en) | Multistage emulsion polymer and coatings formed therefrom | |
AU2003262113B2 (en) | Aqueous coating composition | |
CN109601001B (zh) | 二苯甲酮衍生物、水性共聚物分散液和水性涂料组合物 | |
EP2371913A1 (en) | Aqueous copolymer dispersion and coating composition | |
CA2977932A1 (en) | Latex functionalized with structural units of an amino acid | |
CN106459551B (zh) | 具有改进的耐变黄性的抗菌涂料组合物 | |
WO2013053101A1 (en) | Aqueous polymer dispersion | |
KR20180055842A (ko) | 폴리머 에멀젼 및 이를 포함하는 항균성 코팅 조성물 | |
AU2014218472A1 (en) | Polymer encapsulated titanium dioxide particles | |
EP3325564B1 (en) | An aqueous coating composition | |
CN107532033B (zh) | 具有有效不透明度的低光泽涂料组合物 | |
EP1614732A2 (en) | Acrylic based aqueous coating composition | |
CA2989142A1 (en) | Latex functionalized with structural units of an arginine functionalized monomer | |
KR20180041139A (ko) | 황변 저항이 개선된 항미생물 코팅 조성물 | |
KR20230093285A (ko) | 저광택 딥 베이스 코팅 조성물 | |
KR20150143528A (ko) | 설페이트법에 의한 이산화티탄의 캡슐화 입자 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | 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 | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200512 Termination date: 20210630 |