CN108727933B - 一种水性隔热涂料及其组合物 - Google Patents
一种水性隔热涂料及其组合物 Download PDFInfo
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- CN108727933B CN108727933B CN201810601414.8A CN201810601414A CN108727933B CN 108727933 B CN108727933 B CN 108727933B CN 201810601414 A CN201810601414 A CN 201810601414A CN 108727933 B CN108727933 B CN 108727933B
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Abstract
一种水性隔热涂料,在其成分中使用均匀分散于树脂中且以溶胶‑凝胶法制得的二氧化硅分散液为隔热剂,其不但细度很高,且具有大的比表面积,介于30.1‑100m2/g;涂布到建物表面,可形成既结构紧密、表面光滑且表面反射率又高达85%以上的涂层,除了有效阻隔红外线,还具有优异的热遮蔽效果、抗污性及耐久性。
Description
技术领域
本发明涉及一种水性隔热涂料,特别是一种成分中使用以溶胶-凝胶法制得的二氧化硅分散液作为隔热剂的水性隔热涂料。
背景技术
隔热涂料主要应用于作为建材表面的涂层。为了避免太阳热能进入室内,隔热涂料必须具备较高的太阳光反射率(Total Solar Reflectance;TSR),避免吸收光线。当太阳光照射到隔热涂料时,隔热涂料必须具备较低的热传导能力,避免隔热涂料吸收光线,并且转换成热能造成室温上升。
现有技术中常见的具备高太阳光反射率的隔热材料,包括:中空陶瓷隔热材料和含球状金属氧化物颗粒的隔热涂料。但是,所述中空陶瓷隔热材料因为中空结构而含有空气层,有易劣化及材料表面蓄热的缺点。
相对地,所述隔热涂料的球状金属氧化物颗粒,例如,呈高圆球度的球状二氧化硅颗粒,是使用火焰熔融法制得呈高的圆球度(达0.7以上)但比表面积在30m2/g以下的球状颗粒,因为比表面积过小,导致所述隔热涂料的红外线阻隔效果较差。除此之外,所述球状金属氧化物颗粒的粒径介于0.05-20μm,是决定所述隔热涂料是否具备优异隔热效果的关键因素,当球状金属氧化物颗粒的粒径过大,将造成建材的隔热涂层表面呈现粗糙表面,从而造成太阳光反射率(TSR)下降,隔热效果较差。
发明内容
为解决上述隔热涂料的问题,本发明的一个主要目的在于公开一种水性隔热涂料,其基于涂料组合物总重量,包含以下成分,且以下各成分的总和为100wt%:
a)水性亚克力树脂50-75wt%;
b)隔热剂1-10wt%,其为使用溶胶-凝胶法制得的二氧化硅,比表面积介于30.1-100m2/g;
c)无机粉体11-35wt%,其选自二氧化钛(TiO2)、氢氧化铝(Al(OH)3)、氢氧化镁(Mg(OH)2)、碳酸钙(CaCO3)、磷酸钙、硫酸钙、氧化铝(Al2O3)、氧化锆、氧化锌、滑石粉、高岭土或膨胀珍珠岩;及
d)助剂3-5wt%,其选自成膜助剂、分散剂、消泡剂、流平剂、抗菌剂、抗冻剂或光稳定剂。
本发明的另一个主要目的在于公开一种水性隔热涂料,在涂料组合物的成分中,使用以溶胶-凝胶法制得且比表面积较大的二氧化硅分散液作为隔热剂,
作为优选实施例,所述隔热剂为阴离子型二氧化硅粒子,悬浮于钠离子或铵离子溶液中,pH值控制在9~10。
作为优选实施例,所述无机粉体的粒径介于0.08μm-3μm。
作为优选实施例,所述无机粉体的粒径介于0.1μm-0.3μm。
作为优选实施例,所述成膜助剂及所述抗冻剂的用量,各介于0.5%-5%;所述分散剂、所述消泡剂、所述流平剂、所述抗菌剂及所述光稳定剂的用量,各介于0.01%-1%。
作为优选实施例,所述成膜助剂使用醇醚类溶剂、醇酯类溶剂、乙二醇单丁醚/二丙二醇丁醚混合物溶剂或增塑剂中的至少一种。
作为优选实施例,所述分散剂使用聚丙烯酸共聚物钾盐、改性聚羧酸钾盐、硬脂酸单甘油酯、三硬脂酸甘油酯、油酸酰胺或聚合物型阴离子分散剂中的至少一种。
作为优选实施例,所述消泡剂使用聚硅氧烷-聚醚共聚物、正辛醇、磷酸三丁酯、磷酸三苯酯、乳化甲基硅油、乳化苯甲基硅油、非硅酮含疏水粒子矿物油混合物或改性聚硅氧烷中的至少一种。
作为优选实施例,所述流平剂使用丙烯酸共聚物或非反应型聚醚改性聚硅氧烷的中至少一种;
作为优选实施例,所述抗菌剂使用亚硝酸盐或氟化钠中的至少一种;所述抗冻剂使用甲醇、乙醇或乙二醇中的至少一种;所述光稳定剂使用二苯甲酮类或苯并三唑类有机物中的至少一种。
本发明的水性隔热涂料,当作为建材表面的隔热涂层使用时,有益效果包括:不但结构紧密且具备较高的太阳光反射率(TSR),可以有效阻隔红外线,并且具有优异的热遮蔽效果、抗污性及耐久性。
附图说明
图1为比较例1添加7wt%二氧化硅粉末的隔热涂料,经过搅拌1小时后的扫描电子显微镜(SEM)图。
图2为图1的隔热涂料再经过研磨1小时后的SEM图。
图3为图1的隔热涂料再经过研磨2小时后的SEM图。
图4为实施例1添加7wt%二氧化硅分散液的隔热涂料,经过搅拌1小时后的SEM图。
图5为实施例2添加3.5wt%二氧化硅分散液的隔热涂料,经过搅拌1小时后的SEM图。
图6为实施例4添加3.5wt%二氧化硅分散液的隔热涂料,经过研磨1小时后的SEM图。
图7为比较例5添加7wt%的40μm中空玻璃珠的隔热涂料,经过搅拌1小时后的SEM图。
图8为图7的隔热涂料再经过研磨1小时后的SEM图。
具体实施方式
本发明教导一种水性隔热涂料组合物,其基于涂料组合物总重量,包含以下成分,且以下各成分的总和为100wt%:
a)水性亚克力树脂50-75wt%;
b)隔热剂 1-10wt%;
c)无机粉体 11-35wt%;
d)助剂 3-5wt%。
本发明的水性隔热涂料组合物的关键性技术,是使用具备高的比表面积的二氧化硅分散液作为隔热剂,有别于现有技术中的隔热涂料在于强调其成分中所含的球状金属氧化物颗粒的圆球度需要达到0.7以上的高圆球度。
本发明的水性隔热涂料组合物,其成分中的隔热剂,是一种使用溶胶-凝胶法制得的二氧化硅分散液,而且二氧化硅分散液的比表面积介于30.1-100m2/g,有别于以火焰熔融法制得且比表面积在30m2/g以下的二氧化硅粉体。
在调制水性隔热涂料的过程中,所述二氧化硅分散液以溶胶-凝胶法制得,具有良好分散性,仅需搅拌,即可将二氧化硅分散液均匀分散于树脂中,不会因粒子聚集而形成粗粒,既减少调配制程的步骤,也降低分散不均匀造成的影响。
此外,所述二氧化硅分散液的比表面积介于30.1-100m2/g,符合隔热涂料中的隔热颗粒比表面积越大,则颗粒越细,在隔热涂料中的分散度就越高,形成涂层后的表面平整性及光滑程度越高的条件。
因此,本发明的水性隔热涂料,经涂布到建材表面时,可以达到涂料涂层表面光滑,且表面太阳光反射率高达85%以上的效果。尤其是,与高材质强度的中空陶瓷隔热材料相比,本发明的水性隔热涂料不会因热胀冷缩而破裂,且使用寿命长。
所述二氧化硅分散液是以盐的特性制造,将盐酸加于硅酸钠溶液,经游离出来单分子硅酸,形成硅酸溶胶。将电解质加于此溶胶中,pH值控制在9-10,则凝结变成以水为分散媒的二氧化硅分散液(或称凝胶),其组成为xSiO2·yH2O化合物悬浮于含钠离子或铵离子的水溶液中,pH值控制在9-10,且每克二氧化硅分散液具有的表面积介于30.1-100m2/g。
所述二氧化硅分散液具有优异的流动性及稳定性,适合与水性树脂、无机粉体及助剂共同调制成本发明的水性隔热涂料组合物。
所述无机粉体选自二氧化钛(TiO2)、氢氧化铝(Al(OH)3)、氢氧化镁(Mg(OH)2)、碳酸钙(CaCO3)、磷酸钙、硫酸钙、氧化铝(Al2O3)、氧化锆、氧化锌、滑石粉、高岭土、膨胀珍珠岩及其他色料等。所述无机粉体的粒径介于0.08-3.0μm,优选为介于0.1-0.3μm,因为粒径过大无法以搅拌完成分散,反之,粒径过小则摇变性过高,会造成搅拌不均。
本发明的水性隔热涂料,在调制过程中需加入各种助剂,以维持涂料成品具有良好的涂布性及适用性。所述助剂包括成膜助剂、分散剂、消泡剂、流平剂、抗菌剂、抗冻剂、光稳定剂等,基于涂料组合物总重量,使用量占3-5wt%。
成膜助剂的使用目的,在于协助涂料具备成膜性,避免涂料干燥时龟裂、破损等。所述成膜助剂的使用量,介于0.5-5.0wt%。当使用量小于0.5wt%时,无法避免涂料干燥时龟裂或破损,而大于5.0wt%时,则造成涂料的干燥性不佳。所述成膜助剂选自醇醚类溶剂、醇酯类溶剂或乙二醇单丁醚/二丙二醇丁醚混合溶剂等高沸点溶剂或增塑剂中的至少一种。
分散剂的使用目的,在于让无机粉体及隔热剂均匀分散在树脂中,避免颗粒因聚集而形成细度不足的粗粒,从而造成涂层表面粗糙、表面反射率下降及隔热效果变差。所述分散剂的使用量,介于0.01-1.0wt%。当使用量小于0.01wt%时,将造成无机粉体及隔热剂无法均匀分散,而大于1wt%时,同样会造成因搅拌时气泡过多而分散不均匀。所述分散剂选自聚丙烯酸共聚物钾盐、改性聚羧酸钾盐、硬脂酸单甘油酯、三硬脂酸甘油酯、油酸酰胺或聚合物型阴离子分散剂中的至少一种。
消泡剂的使用目的,在于协助涂料在调制过程中将气泡消散,避免影响涂料的涂布质量。所述消泡剂的使用量,介于0.01-1.0wt%。当使用量小于0.01wt%时,涂料的消泡效果不佳,而大于1.0wt%时,将造成涂料的表面张力发生变化,反而形成涂布时的缺陷。所述消泡剂选自聚硅氧烷-聚醚共聚物、正辛醇、磷酸三丁酯、磷酸三苯酯、乳化甲基硅油、乳化苯甲基硅油、非硅酮含疏水粒子矿物油混合物或改性聚硅氧烷中的至少一种。
流平剂的使用目的,在于协助去除涂料的各种涂布缺陷,增加涂料的适用性,可适用于采用如滚涂、刷涂或喷涂等不同涂布方式。所述流平剂的使用量,介于0.01-1.0wt%。当使用量小于0.01wt%时,涂料的流平效果不佳,而大于1wt%时,将造成涂料的表面张力发生变化,反而形成涂布时的缺陷。所述流平剂选自丙烯酸共聚物或非反应型聚醚改性聚硅氧烷中的至少一种。
抗冻剂的使用目的,在于使涂料增加低温的适用性,避免涂料在低温时因为结块或冰冻而无法使用。所述抗冻剂选自甲醇、乙醇或乙二醇中的至少一种,使用量介于0.5-5.0wt%。
抗菌剂的使用目的,在于避免涂料在存放或涂布过程中发霉而造成功能性降低。所述抗菌剂选自亚硝酸盐或氟化钠中的至少一种,使用量介于0.01-1.0wt%。
光稳定剂的使用目的,在于使涂料达到光稳定作用,避免涂料发生光氧化反应、减缓涂料的紫外光遮蔽能力衰退以及减缓涂料的黄变程度。所述光稳定剂选自二苯甲酮类或苯并三唑类有机物中的至少一种,使用量介于0.01-1.0wt%。
以下举实施例及比较例制得的水性隔热涂料,按照下列测试方法评估水性隔热涂料的效果。
1、全波长反射率%测试
将隔热涂料涂布于基材上,使用紫外光/可见光分光光谱仪(Perkin ElnerLambda 750)搭配60nm积分球(integrating sphere)进行300-2500nm波长的反射率量测,再依日光透反射公式计算全波长反射率%。
2、细度(μm)测试:
使用刮板细度计(grindometer)刨刮基材上的涂层,用肉眼观察刮板细度计上的细度沟槽,读取细度沟槽显著出现颗粒的相应刻度即为细度(单位μm)。
3、遮盖力(hiding power)测试:
根据美国ASTM D2805规范,使用遮盖力测试仪将涂料涂于所设的两块玻璃板间,前后滑动顶部玻璃板,读出一条明显分界线交替出现和消失分界线出现点在标尺上之读数。
4、百格试验测试:
将涂料涂于钢板上,待完全干燥后,以百格刀于涂层上划出百格,再以胶带贴合已划出百格之涂层处用力拉动,让胶带完全脱离涂层,目视钢板上涂层脱落程度。
5、表面温度(℃)测试:
将涂料涂于钢板上,待完全干燥后,以飞利浦250W CR 7 120V红外线灯照射两小时,再以红外线测温枪,量测涂层照光面的温度,评估隔热效果。
6、热传系数(W/(m·℃))测试:
将涂料制成薄膜,再以热传导系数分析仪以固定功率的热源下,量测涂料将热源传导出去的能力。
7、遮热涂料的热传导率(又称U值,W/(m2·K))测试:
按照JIS(日本工业标准)A5759规范,计算涂层的涂膜外侧表面温度与内侧表面的温差到达1℃时,每小时在1平方公尺(m2)面积下流出的热量。
8、QUV 1000hrsΔb*测试:
将涂料涂于钢板上,待完全干燥后,置入紫外光耐候试验仪(ATLAS UV TEST),以UVB 313nm波长,50-60℃,4小时照射-4小时蒸湿的循环条件,测试1000小时后,再以分光仪(X-rite color Eye 7000a)量测b值变化,确认黄变程度。
9、耐水性(72小时)测试:
将涂料涂于钢板上,待完全干燥后,置入水中72小时,观察涂膜外观变化。
10、耐碱性(饱和石灰水72小时)测试:
将涂料涂于钢板上,待完全干燥后,置入饱和石灰水72小时,观察涂膜外观变化。
11、耐刷洗性测试(450克负重,0.5%肥皂水2000次)测试:
将涂料涂于钢板上,待完全干燥后,以450克负重,0.5%中性肥皂水,以刷洗测试机刷洗2000次后,观察涂膜外观变化。
实施例1
按表1的组成,取水性亚克力树脂60克(固体组分50%),在搅拌过程中,依序加入0.4克分散剂、0.65克消泡剂后,再加入19克粒径0.3μm的二氧化钛粉体、5.1克粒径0.3μm的碳酸钙粉体及4.07克其它无机粉体,搅拌均匀后,再加入7克以溶胶-凝胶法制得的二氧化硅分散液为隔热剂,搅拌均匀后静置消泡后,再导入3.78克其它助剂(包括1.5克成膜助剂、0.65克流平剂、0.08克抗菌剂、1.07克抗冻剂及0.48克光稳定剂),搅拌均匀后,完成涂料的调配。
将涂料以250μm涂布棒涂布于150μm PET膜及钢板,置于室温下干燥24小时,进行各项物性评估。
所制得的隔热涂料,经过搅拌1小时后的SEM图,如图4所示。
实施例2
同实施例1,但涂料的碳酸钙粉体的用量从5.1克改为8.6克以及二氧化硅分散液的用量从7克改为3.5克。进行涂料的各项物性评估。
所制得的隔热涂料,经过搅拌1小时后的SEM图,如图5所示。
实施例3
同实施例1,但涂料的碳酸钙粉体的用量从5.1克改为11.1克以及二氧化硅分散液的用量从7克改为1克。进行涂料的各项物性评估。
实施例4
同实施例2,但涂料的二氧化硅分散液再经过砂磨机研磨细化。进行涂料的各项物性评估。
所制得的隔热涂料,经过研磨1小时后的SEM图,如图6所示。
实施例5
同实施例2,但涂料的二氧化钛粉体的粒径从0.3μm改为0.1μm、碳酸钙粉体的粒径从0.3μm改为2.7μm。进行涂料的各项物性评估。
比较例1
同实施例1,但涂料使用以火焰熔融法制得且经过砂磨机研磨细化的20-25μm二氧化硅粉体取代实施例1以溶胶-凝胶法制得的15-20μm二氧化硅分散液。进行涂料的各项物性评估。
所制得的隔热涂料,经过搅拌1小时后的SEM图,如图1所示;之后,再经过研磨1小时及2小时后的SEM图,如图2及图3所示。
比较例2
同比较例1,但涂料使用的二氧化硅粉体,不经过砂磨机研磨细化,且细度超过100μm。进行涂料的各项物性评估。
比较例3
同实施例4,但涂料的碳酸钙粉体的粒径从0.3μm改为2.7μm、且使用以火焰熔融法制得且经过砂磨机研磨细化的20-25μm二氧化硅粉体取代实施例4以溶胶-凝胶法制得的15-20μm二氧化硅分散液。进行涂料的各项物性评估。
比较例4
同实施例1,但涂料不添加碳酸钙粉体,且涂料的二氧化硅分散液的用量从7克改为12.1克。进行涂料的各项物性评估。
比较例5
同实施例1,但涂料使用3M中空玻璃珠K37(40μm)取代实施例1以溶胶-凝胶法制得的二氧化硅分散液。进行涂料的各项物性评估。
所制得的隔热涂料,经过搅拌1小时后的SEM图,如图7所示;之后,再经过研磨1小时后的SEM图,如图8所示。
表1:成分组成(单位:克)及其物性
注:1、SiO2分散液以溶胶-凝胶法制得;
2、SiO2粉体以火焰熔融法制得。
3、水性隔热涂料的物性,符号“○”表示优良;
符号“Δ”表示尚可;
符号“X”表示不佳。
结果
1、实施例1至3的隔热涂料,使用1-7克以溶胶-凝胶法制得的二氧化硅分散液为隔热剂,其全波长反射率达88%以上、光照表面温度皆在61-63℃,显示具有良好的隔热效果。
2、实施例2、4及5的隔热涂料,皆使用3.5克以溶胶-凝胶法制得的二氧化硅分散液为隔热剂,即使实施例5是使用2.7μm粒径碳酸钙粉体,在调制过程中,不管是否需进一步经砂磨机研磨细化,二氧化硅的细度皆介于15-20μm,而且其全波长反射率达88%以上、光照表面温度皆在61-63℃。此说明:本发明的隔热涂料在调配过程中,仅需搅拌,就可将纳米二氧化硅粒子均匀分散于树脂中,既减少调配制程的步骤,也降低分散不均匀造成的影响。
3、比较例1及2的差别,在于隔热涂料使用火焰熔融法制得的二氧化硅粉体为隔热剂时,在调配隔热涂料的过程中,比较例1的二氧化硅粉体需使用砂磨机研磨细化分散。否则,如比较例2的二氧化硅粉体颗粒无法均匀分散于树脂中,造成粉体聚集而形成粗粒,以致细度高达100μm以上,涂料涂层表面粗糙,而表面反射率下降至80%,光照表面温度高达67-70℃,隔热效果变差。
此外,比较例3使用以火焰熔融法制得的二氧化硅粉体且将其用量降至3.5%,光照表面温度也增加至67-70℃,此说明:隔热涂料使用以火焰熔融法制得的二氧化硅粉体为隔热粒子,其用量需达到一定程度,才具有良好的隔热效果。
4、比较例4的隔热涂料,不添加碳酸钙粉体,但使用用量高达12.1克的以溶胶-凝胶法制得的二氧化硅分散液为隔热剂,隔热涂料的光照表面温度反而增加至64-67℃,与比较例2不使用二氧化硅分散液的隔热涂料的隔热效果相当。此说明:
1)隔热涂料中的二氧化硅分散液如果用量过多,易在涂料内部凝聚,结果造成隔热粒子分散不均匀以及涂料的隔热效果变差;及
2)本发明的二氧化硅分散液的用量,基于隔热涂料总重量,介于1-10wt%之间时,在调配隔热涂料的过程中,仅需搅拌,即可将纳米二氧化硅粒子均匀分散于树脂中,且隔热涂料具有良好的隔热效果。
5、比较例5的隔热涂料,使用7wt%粒径达40μm的中空玻璃珠为隔热剂,在调配的搅拌过程中,以目视就见到玻璃珠在树脂中分散不均匀,经砂磨机研磨分散后,虽目视不再看到明显颗粒,但隔热涂料的表面反射率下降至70%、光照表面温度高达67-70℃,观察图8的SEM图得确认中空玻璃珠已碎裂,造成表面反射率及隔热效果变差。此说明,市售隔热涂料使用中空玻璃珠为隔热剂,作为建材表面的涂层,因为中空玻璃珠的强度不足,在外在环境下易发生劣化,且需要定期再重新涂布。
Claims (12)
1.一种水性隔热涂料组合物,其基于涂料组合物总重量,包含以下成分,且以下各成分的总和为100wt%:
a)水性亚克力树脂50-75wt%;
b)隔热剂1-7wt%,其为使用溶胶-凝胶法制得的阴离子型二氧化硅粒子,悬浮于钠离子或铵离子溶液中,表面积介于30.1-100m2/g,且隔热剂的pH值控制在9~10;
c)无机粉体11-35wt%,其选自二氧化钛(TiO2)、氢氧化铝(Al(OH)3)、氢氧化镁(Mg(OH)2)、碳酸钙(CaCO3)、磷酸钙、硫酸钙、氧化铝(Al2O3)、氧化锆、氧化锌、滑石粉、高岭土或膨胀珍珠岩;及
d)助剂3-5wt%,其选自成膜助剂、分散剂、消泡剂、流平剂、抗菌剂、抗冻剂或光稳定剂。
2.根据权利要求1所述的水性隔热涂料组合物,其特征在于,所述无机粉体的粒径介于0.08μm-3μm。
3.根据权利要求1所述的水性隔热涂料组合物,其特征在于,所述无机粉体的粒径介于0.1μm-0.3μm。
4.根据权利要求1所述的水性隔热涂料组合物,其特征在于,所述成膜助剂及所述抗冻剂的用量,各介于0.5%-5%;所述分散剂、所述消泡剂、所述流平剂、所述抗菌剂及所述光稳定剂的用量,各介于0.01%-1%。
5.根据权利要求4所述的水性隔热涂料组合物,其特征在于,所述成膜助剂使用醇醚类溶剂、醇酯类溶剂或增塑剂中的至少一种。
6.根据权利要求4所述的水性隔热涂料组合物,其特征在于,所述成膜助剂使用乙二醇单丁醚/二丙二醇丁醚混合物溶剂。
7.根据权利要求4所述的水性隔热涂料组合物,其特征在于,所述分散剂使用聚丙烯酸共聚物钾盐、改性聚羧酸钾盐、硬脂酸单甘油酯、三硬脂酸甘油酯或油酸酰胺中的至少一种。
8.根据权利要求4所述的水性隔热涂料组合物,其特征在于,所述分散剂使用聚合物型阴离子分散剂。
9.根据权利要求4所述的水性隔热涂料组合物,其特征在于,所述消泡剂使用聚硅氧烷-聚醚共聚物、正辛醇、磷酸三丁酯、磷酸三苯酯、乳化甲基硅油、乳化苯甲基硅油或非硅酮含疏水粒子矿物油混合物中的至少一种。
10.根据权利要求4所述的水性隔热涂料组合物,其特征在于,所述消泡剂使用改性聚硅氧烷。
11.根据权利要求4所述的水性隔热涂料组合物,其特征在于,所述流平剂使用丙烯酸共聚物或非反应型聚醚改性聚硅氧烷中的至少一种;
所述抗菌剂使用亚硝酸盐或氟化钠中的至少一种;
所述抗冻剂使用甲醇、乙醇或乙二醇中的至少一种;以及
所述光稳定剂使用二苯甲酮类或苯并三唑类有机物中的至少一种。
12.一种水性隔热涂料,以权利要求1所述的水性隔热涂料组合物制成。
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