CN102300945A - 混合式涂料及相关的施加方法 - Google Patents
混合式涂料及相关的施加方法 Download PDFInfo
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- IFHVCUGTUBHOML-UHFFFAOYSA-N trimethyl (3-methyloxiran-2-yl) silicate Chemical compound CC1C(O1)O[Si](OC)(OC)OC IFHVCUGTUBHOML-UHFFFAOYSA-N 0.000 claims description 5
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- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 claims description 2
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 claims description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 2
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- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
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- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 2
- 229920006397 acrylic thermoplastic Polymers 0.000 claims 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims 1
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- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/14—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
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Abstract
包括有机硅烷组分、金属醇盐组分和表面活性剂组分的混合物的混合式涂料。
Description
技术领域
本专利申请涉及混合式耐磨涂料(hybrid abrasion resistantcoatings)、用于制造混合式耐磨涂料的方法以及用于处理和弥补遭受磨损的表面的相关方法。
背景技术
磨损对机械构件和暴露表面的影响普遍存在于各种应用中。对于透明构件和需要透明性的表面而言,磨损的影响尤其普遍。例如,飞行器的窗户在飞行中和在地面上都容易遭受磨损。
因而,科学家和工程师继续寻找抵抗磨损影响的涂料,从而通过延长在连续的更换/修复操作之间的时间间隔,减少与维护相关的时间和花费。此外,科学家和工程师继续寻找可用来修复刮擦的和磨损的基底(substrate)的涂料,从而通过促进基底的修复——否则其将需要更换,来减少维护费用。环境友好的涂料将是特别吸引人的。
发明内容
一方面,公开的混合式涂料可包括有机硅烷组分、金属醇盐组分和表面活性剂组分的混合物。更具体的方面,混合物可基本上不含大于大约11μm的微粒。
另一方面,公开的混合式涂料可包括(3-环氧丙氧丙基)三甲氧基硅烷、仲丁醇铝和表面活性剂组分的混合物,其中混合物基本上不含大于大约11μm的微粒。
另一方面,公开的用于制造混合式涂料的方法可包括下述步骤:使有机硅烷、金属醇盐和表面活性剂组合以形成混合物;加热混合物;并在加热步骤后过滤混合物。
另一方面,公开的用于涂覆基底的方法可包括下述步骤:清洁基底表面;用氧等离子体处理表面;将粘合增进剂施加到表面;将混合式涂料施加到表面,所述混合式涂料包括有机硅烷组分、金属醇盐组分和表面活性剂组分;和固化混合式涂料。
根据下面的说明书、附图和所附的权利要求书,公开的混合式涂料和相关的施加方法的其它方面将变得明显。
附图简述
图1是图解了施加公开的混合式涂料的一个示例性方法的流程图;
图2是在未处理的基底(“裸露的亚克力(裸露的丙烯酸树脂,BareAcrylic)”)、用现有技术涂料(“聚硅氧烷”)处理的基底和用一方面公开的混合式涂料(“混合式涂料”)处理的基底上经过100个周期的Taber磨损后获得的雾度百分比的图形说明;
图3是裸露的亚克力基底和用公开的混合式涂料涂覆的亚克力基底的雾度百分比对Taber磨损周期数的图形说明;
图4是用公开的混合式涂料弥补的磨损亚克力基底的雾度百分比对Taber磨损周期数的图形说明;
图5是用公开的混合式涂料涂覆、遭受磨损、用公开的混合式涂料弥补、接着再遭受磨损的亚克力基底的雾度百分比对Taber磨损周期数的图解说明;
图6是用现有技术涂料涂覆、遭受磨损、用公开的混合式涂料弥补、接着再遭受磨损的亚克力基底的雾度百分比对Taber磨损周期数的图形说明;
图7是开始用双层涂料(即,现有技术涂料的第一层和公开的混合式涂料的面漆)涂覆、遭受磨损、用公开的混合式涂料弥补,接着再遭受磨损的亚克力基底的雾度百分比对Taber磨损周期数的图形说明;和
图8是图解了用于制造公开的混合式涂料的一种示例性方法的流程图。
发明详述
一方面,公开的混合式涂料可包括有机硅烷组分、金属醇盐组分和表面活性剂组分。例如,可以加入水以调节混合物的固体含量和/或粘度。例如,具有各种功能的附加组分,诸如染料、光清除剂、流变改性剂和抗微生物剂,可加入到公开的混合式涂料中,而没有偏离本公开的范围。
有机硅烷组分可以是公开的混合式涂料的有机部分。在一个示例性方面,有机硅烷组分可以是(3-环氧丙氧丙基)三甲氧基硅烷。但是,可用作有机硅烷组分的化合物的可选例子包括3-环氧丙氧丙基三乙氧基硅烷、对-氨基苯基硅烷、烯丙基三甲氧基硅烷、n-(2-氨乙基)-3-氨丙基三甲氧基硅烷、3-氨丙基三乙氧基硅烷、3-氨丙基三甲氧基硅烷、3-环氧丙氧丙基二异丙基乙氧基硅烷、(3-环氧丙氧丙基)甲基二乙氧基硅烷、3-巯基丙基三甲氧基硅烷、3-巯基丙基三乙氧基硅烷、3-甲基丙烯酰氧丙基甲基二乙氧基硅烷、3-甲基丙烯酰氧丙基甲基二甲氧基硅烷、3-甲基丙烯酰氧丙基三甲氧基硅烷、n-苯基氨基丙基三甲氧基硅烷、乙烯基甲基二乙氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷和原硅酸四乙酯,及其组合。本领域技术人员将明白其他化合物可用作公开的混合式涂料的有机硅烷组分,而没有偏离本公开的范围。
金属醇盐组分可以是公开的混合式涂料的无机部分。在一个示例性方面,金属醇盐组分可以是烷醇铝,例如仲丁醇铝、正丁醇铝和叔丁醇铝。在第二示例性方面,金属醇盐组分可以是烷醇铈,例如异丙醇铈IV,甲氧基乙醇铈IV和2,4-乙酰丙酮铈III。本领域技术人员将明白其他金属醇盐可用作公开的混合式涂料的金属醇盐组分,而没有偏离本公开的范围。
因此,公开的混合式涂料可以是包括有机组分和无机组分二者的混合式材料。
不限制于任何具体的理论,公开的混合式涂料的表面活性剂组分可通过减小涂料的表面张力改进涂料的湿粘合(wet adhesion)。在一个示例性方面,表面活性剂组分可以是液体、非离子表面活性剂,例如直链伯脂肪烷氧基化醇(primary aliphatic alkoxylated alcohol)。此类表面活性剂的具体例子是可以从法国的Rhodia Operations of Aubervilliers获得的ANTAROXBL-240(CAS# 68603-25-8)。但是,本领域的技术人员将明白其它表面活性剂可用作公开的混合式涂料的表面活性剂组分,而没有偏离本公开的范围。
可选择有机硅烷、金属醇盐和表面活性剂组分的相对量,以优化公开的混合式涂料的耐磨性、透明度、表面润湿、可固化性或其他物理性质。在一个示例性方面,在公开的涂料中,金属醇盐和有机硅烷组分可以以大约2∶1(2摩尔的金属醇盐组分对1摩尔的有机硅烷组分)的摩尔比存在,且表面活性剂组分可以以相对于金属醇盐组分75∶1的摩尔比(75摩尔的金属醇盐组分对1摩尔的表面活性剂组分)存在。但是,本领域技术人员将明白所述的量(或摩尔比)可根据成分、被优化的物理性质或使用者的具体需求而改变。
一方面,通过在混合容器中组合适量的有机硅烷、金属醇盐和表面活性剂组分以及任选的足够量的水制备公开的混合式涂料。加热组合物,同时连续地搅拌,直到溶液变得透明(澄清)。将透明的溶液冷却至室温(例如,大约25℃),然后过滤。在一个具体的方面,可进行过滤步骤以去除大于大约10μm的颗粒。例如,可使用具有制造商规定的11μm颗粒保留级别的Whatman #1定性滤纸。
对此,本领域的技术人员将明白所得到的透明、冷却的过滤液体可以是溶胶凝胶。
实施例1(混合式涂料)
通过在耐热容器中组合11.7毫升的仲丁醇中的75%的仲丁醇铝、15.1毫升的(3-环氧丙氧丙基)三甲氧基硅烷、0.5毫升10wt%的ANTAROXBL-240和22.7毫升去离子水,制备混合式涂料。加热混合物至90℃的温度同时搅拌。继续搅拌额外的120分钟或直到混合物透明。然后,将混合物从热源移开并使其冷却到25℃。然后,使冷却的混合物通过Whatman #1定性滤纸,丢弃滤渣(filtrand)。将滤液储存在密闭容器中。
如下论述,公开的混合式涂料可作为初始涂料或弥补涂料,用于涂覆各种基底,例如亚克力(例如,拉伸的亚克力)和玻璃。本领域技术人员将明白可用公开的混合式涂料涂覆除亚克力和玻璃外的其它基底,而没有偏离本公开的范围。
参看图1,通常指定为10的一种施加混合式涂料的方法可通过制备公开的混合式涂料开始,如方块12中所示。公开的混合式涂料的制备已在上文中详细描述。
如方块14中所示,可制备粘合增进剂。粘合增进剂可以是可促进公开的混合式涂料粘合到下面的基底上的任何材料。一种示例性粘合增进剂包括在水中按重量计2.5%的3-氨丙基三乙氧基硅烷。但是,本领域技术人员将明白可以使用各种粘合增进组合物。
如方块16中所示,可对将接受涂料的基底表面适当清洁。用于清洁将接受涂料的表面的各种技术在本领域中是公知的。例如,当基底是拉伸的亚克力时,基底的表面可用异丙醇擦拭。
此外,如方块18中所示,清洁的基底表面可用氧等离子体处理,但是其他的处理方式例如电晕处理也可使用,而没有偏离本公开的范围。可用户外空气等离子处理***产生氧等离子体,并且氧等离子体可具有如此前部(head),其在距离基底表面大约0.75英寸的距离处,每秒移动大约0.1英寸。举例来说,可使用从Structure Probe,Inc.of WestChester,Pennsylvania可获得的SPI Plasma-PrepTM等离子体蚀刻机,产生氧等离子体。不限制于任何具体的理论,相信在公开的混合式涂料中的氧等离子体和表面活性剂都利于改进混合式涂料对基底的润湿性和粘合。
在清洁(方块16)和等离子体处理(方块18)步骤后,可将粘合增进剂可施加到基底的表面,如方块20中所示。尽管可使用各种技术施加粘合增进剂,但是喷雾是一个示例性技术。然后,如方块22中所示,如果需要,可使粘合增进剂固化。例如,当使用按重量计2.5%的3-氨丙基三乙氧基硅烷水溶液作为粘合增进剂时,粘合增进剂可在80℃下固化10分钟,之后,可使基底冷却(方块24)。
在这点上,本领域技术人员将明白,根据需要,方块14到24中所示的步骤可被省略。尤其是,当使用公开的混合式涂料作为弥补涂料时,粘合增进剂的使用(即方块14,20,22和24中示出的步骤)可被任选地省略。同样地,当使用公开的混合式涂料作为弥补涂料时,氧等离子体处理(方块18)可被任选地省略。
如方块26中所示,混合式涂料可被施加到清洁的且处理过的基底表面。尽管将混合式涂料喷雾到基底上是一种合适的施加技术,但是本领域技术人员将明白可使用各种施加技术,例如绘涂(drawing)、刮涂和涂抹,而没有偏离本公开的范围。
如方块28中所示,施加到基底上的混合式涂料可在进入使用(service)之前被固化。尽管包括固化时间和固化温度在内的固化技术可根据混合式涂料的具体组成而改变,但是如果使用在上面实施例1中描述的混合式涂料,那么通过在室温下静置大约16个小时,然后在80℃下固化大约2个小时,可获得合适的固化。固化之后,可使涂覆的基底冷却,如方块30中所示。
按照BSS7225,Class5(粘合7是最低要求,粘合10是完美粘合),在拉伸亚克力上测试混合式涂料(“混合式涂料”)的湿的和干的粘合。仲丁醇铝用作金属醇盐组分(“无机的”),(3-环氧丙氧丙基)三甲氧基硅烷用作有机硅烷组分(“有机的”)和ANTAROXBL-240用作表面活性剂组分。由指示时使用氧等离子体(“等离子体”)、电晕处理(“电晕”)和粘合增进剂(“AP”)。结果示于表1中。
表1
因此,公开的混合式涂料产生良好的干和湿粘合,特别是当使用公开的方法施加时。
表2
因此,公开的混合式涂料产生低的初始雾度和高的初始透明度。
使用ASTM D 1044,在拉伸的亚克力上评估公开的混合式涂料的耐磨性,其通常称为Taber磨损试验。结果在图2-7中示出。
图2显示了在裸露的亚克力、仅用聚硅氧烷处理(现有技术)的亚克力和用公开的混合式涂料处理的亚克力上,经过100个磨损周期后获得的雾度百分比。图3显示了对于裸露的亚克力基底和涂覆有公开的混合式涂料的亚克力基底,雾度百分比对磨损周期。图4显示了对于用公开的混合式涂料弥补的磨损亚克力基底,雾度百分比对磨损周期。图5显示了对于用公开的混合式涂料涂覆,遭受大约1600次磨损周期,用公开的混合式涂料弥补,然后再遭受磨损的亚克力基底,雾度百分比对磨损周期。图6显示了对于用现有技术的涂料涂覆,遭受大约100次磨损周期,用公开的混合式涂料弥补,然后再遭受磨损的亚克力基底,雾度百分比对磨损周期。图7显示了对于起始用双层涂料(即现有技术涂料的第一层和公开的混合式涂料的面漆)涂覆,遭受大约2500个磨损周期,用公开的混合式涂料弥补,然后再遭受磨损的亚克力基底,雾度百分比对磨损周期。
因此,不管用作初始涂料还是用作为弥补涂料,公开的混合式涂料提供充分改进的耐磨性。
因此,公开的混合式涂料产生低的初始雾度和高的初始透明度,良好的干和湿粘合(尤其对拉伸的亚克力)和极好的耐磨性。此外,无论基底先前是否已被涂覆,公开的混合式涂料可用作弥补涂料以修复磨损的基底的透明度和耐磨性。此外,公开的混合式涂料可被制备为水性溶胶-凝胶材料,且因此是环境友好的。
尽管公开的混合式涂料和相关的施加方法的多个方面已被示出并被描述,但本领域技术人员在阅读说明书后可想到多种改进。本申请包括这类改进,并仅由权利要求的范围所限制。
Claims (20)
1.混合式涂料,其包括有机硅烷组分、金属醇盐组分和表面活性剂组分的混合物。
2.根据权利要求1所述的混合式涂料,其中所述混合物基本上不含大于大约11μm的颗粒。
3.根据权利要求1所述的混合式涂料,其中所述有机硅烷组分选自(3-环氧丙氧丙基)三甲基氧硅烷、3-环氧丙氧丙基三乙氧基硅烷、对-氨基苯基硅烷、烯丙基三甲氧基硅烷、n-(2-氨乙基)-3-氨丙基三甲氧基硅烷、3-氨丙基三乙氧基硅烷、3-氨丙基三甲氧基硅烷、3-环氧丙氧丙基二异丙基乙氧基硅烷、(3-环氧丙氧丙基)甲基二乙氧基硅烷、3-巯基丙基三甲氧基硅烷、3-巯基丙基三乙氧基硅烷、3-甲基丙烯酰氧丙基甲基二乙氧基硅烷、3-甲基丙烯酰氧丙基甲基二甲氧基硅烷、3-甲基丙烯酰氧丙基三甲氧基硅烷、n-苯基氨基丙基三甲氧基硅烷、乙烯基甲基二乙氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三甲氧基硅烷、原硅酸四乙酯及其组合。
4.根据权利要求1所述的混合式涂料,其中所述金属醇盐选自仲丁醇铝、正丁醇铝和叔丁醇铝。
5.根据权利要求1所述的混合式涂料,其中所述金属醇盐选自异丙醇铈IV、甲氧基乙醇铈IV和2,4-乙酰丙酮铈III。
6.根据权利要求1所述的混合式涂料,其中所述表面活性剂组分包括直链伯脂肪烷氧基化醇。
7.根据权利要求1所述的混合式涂料,其中所述金属醇盐组分相对于所述有机硅烷组分以大约2∶1的摩尔比存在于所述混合物中。
8.根据权利要求1所述的混合式涂料,其中所述金属醇盐组分相对于所述表面活性剂组分以大约75∶1的摩尔比存在于所述混合物中。
9.用于涂覆基底的方法(10),其包括下述步骤:
清洁所述基底的表面(16);
用氧等离子体处理所述表面(18);
在所述处理步骤之后,施加粘合增进剂到所述表面(20);
在所述施加粘合增进剂的步骤(20)之后,将混合式涂料施加到所述表面(26),所述混合式涂料包括有机硅烷组分、金属醇盐组分和表面活性剂组分;和
固化所述混合式涂料(28)。
10.根据权利要求9所述的方法,其中所述基底是拉伸的亚克力。
11.根据权利要求9所述的方法,其中所述氧等离子体的前部在距离所述表面大约0.75英寸的距离处,每秒移动大约0.1英寸。
12.根据权利要求9所述的方法,其中所述粘合增进剂包括3-氨丙基三乙氧基硅烷的水溶液。
13.根据权利要求9所述的方法,还包括固化所述粘合增进剂的步骤(22)。
14.根据权利要求9所述的方法,还包括在施加之前过滤所述混合式涂料的步骤(108)。
15.根据权利要求14所述的方法,其中在所述过滤步骤(108)之前,所述混合式涂料被加热(104)。
16.根据权利要求9所述的方法,其中所述有机硅烷组分包括(3-环氧丙氧丙基)三甲氧基硅烷并且所述金属醇盐组分包括仲丁醇铝。
17.用于制造混合式涂料的方法(100),包括下述步骤:
制备包含有机硅烷、金属醇盐和表面活性剂的混合物(102);
加热所述混合物(104);和
在所述加热步骤(104)之后,过滤所述混合物(108)。
18.根据权利要求17所述的方法,其中在所述加热步骤(104)期间,搅拌所述混合物。
19.根据权利要求17所述的方法,还包括在所述过滤步骤(108)之前和所述加热步骤(104)之后冷却所述混合物的步骤(106)。
20.根据权利要求17所述的方法,其中所述加热步骤(104)包括加热所述混合物直到所述混合物透明。
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CN102300945B (zh) | 2016-01-06 |
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JP6357407B2 (ja) | 2018-07-11 |
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EP3415575A1 (en) | 2018-12-19 |
JP5646510B2 (ja) | 2014-12-24 |
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EP3415575B1 (en) | 2020-10-07 |
US8962753B2 (en) | 2015-02-24 |
WO2010087887A1 (en) | 2010-08-05 |
CN105315886B (zh) | 2018-12-07 |
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US20100196621A1 (en) | 2010-08-05 |
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