CN101218316B - 涂漆组合物及上漆物品 - Google Patents
涂漆组合物及上漆物品 Download PDFInfo
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- CN101218316B CN101218316B CN2006800253418A CN200680025341A CN101218316B CN 101218316 B CN101218316 B CN 101218316B CN 2006800253418 A CN2006800253418 A CN 2006800253418A CN 200680025341 A CN200680025341 A CN 200680025341A CN 101218316 B CN101218316 B CN 101218316B
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- paint film
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- paint
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- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
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- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
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- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 1
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
- C08G18/6233—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols the monomers or polymers being esterified with carboxylic acids or lactones
-
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Abstract
本发明提供了一种能形成具有优良的耐洗车机刮擦性、防尘-耐污性和耐候性的漆膜的涂漆组合物以及上漆物品。本发明提供了一种包含(A)组分和(B)组分的清漆组合物,其中(A)组分为包含35-50质量%(以该树脂的固体级分计)ε-己内酯结构单元的丙烯酸类共聚物(羟值为200-340毫克KOH/克,重均分子量为5000-15000),(B)组分为不泛黄型多异氰酸酯化合物。组合物中包括每1当量(A)组分的羟基对应0.5-2当量的比例的(B)组分的异氰酸酯基团,由所述涂漆组合物形成的硬化漆膜的杨氏模量不高于1.5帕,固化漆膜的交联的分子量(Mc)不高于350克/摩尔,以及硬化漆膜的玻璃化转变温度(Tg)为至少65℃。
Description
技术领域
本发明涉及可用于需要形成具有优良的耐刮性、耐候性和防尘—耐污性的漆膜的领域中的涂漆组合物以及涂有所述涂漆的物品。
背景技术
需要适应于车辆(如汽车、摩托车)用的油漆,在车辆上形成的漆膜应具有优良的耐溶剂性、耐汽油性以及耐候性而又不降低涂膜的硬度或又不影响外观。具体地说,为适应自动洗车设备对漆膜耐刮性的要求,具有高耐刮性的油漆近来已变得很重要。
包含10-50质量%由异氰酸酯化合物与已内酯多羟基化合物相反应而制得的氨基甲酸酯多羟基化合物(重均分子量为1500-4000,羟值为50-180毫克KOH/克),30-80质量%氟化树脂共聚物(其中氟-烯烃作为主要原材料已经参与反应,羟值为50-150毫克KOH/克)和10-40重量%交联剂的涂漆组合物是已知为能赋予漆膜耐刮性,并能使漆膜具有初始拒水性的涂漆组合物(例如所引述专利1)。然而,这类涂漆组合物存在一个因氟化树脂共聚物的拒水性而使水基底涂层的润湿性变低的缺点。
此外,还有一种其特征为包含下列组分的油漆组合物也已知为是能形成具有优良的耐酸、耐候和耐刮性涂层的汽车涂漆用面层油漆:90-50重量%作为可硬化树脂的组分(A)-由苯乙烯单体与丙烯酸酯单体构成的丙烯酸类共聚物(羟值为60-140毫克KOH/克,重均分子量为3000-30000),其中丙烯酸酯单体包括作为含羟基基团的丙烯酸单酯单体的,丙烯酸1,4-丁二醇单酯单体和/或ε-己内酯改性的丙烯酸酯单体,以及含4-24个碳原子的伯醇的丙烯酸酯单体,所述苯乙烯单体含量为45-55重量%;和10-50重量%组分(B)-氨基树脂和/或(封端的)多异氰酸酯化合物(例如所引述专利2)。然而,这类涂漆 组合物存在一个由于丙烯酸1,4-丁二醇单酯单体的用量只是满足了耐刮性要求,而漆膜的玻璃化转变温度(Tg)低,因而使防尘-耐污性能低的缺点。
此外,还有一种包含下列组分的紫外线硬化型涂漆组合物也已知为是具有优良的耐刮性、极好的外观、优良的粘附性和耐汽油性(例如所引述专利3)的涂层的紫外线可硬化涂漆:(A)官能度为至少4、数均分子量为300-2000、一个分子中有至少4个(甲基)丙烯酰基基团的紫外线可固化的多官能(甲基)丙烯酸酯;(B)内酯改性的多元醇(甲基)丙烯酸单酯聚合物,其中含20-60质量%开环的ε-己内酯加合物(源自内酯改性的羟值为100-180毫克KOH/克);(C)不泛黄型多异氰酸酯化合物;其中相对于(A)、(B)和(C)组分的总量计,(A)组分的用量为10-50质量%,(B)+(C)组分的用量为90-50质量%,(B)组分与(C)组分的比例为(B)组分中一个当量羟基对应(C)组分中0.5-1.5当量的异氰酸酯基团;还可包含组分(D)光稳定剂和(E)光聚合引发剂,该组合物的特征在于由所述紫外线硬化型涂漆组合物形成的硬化漆膜的努氏硬度为10-18,硬化漆膜交联键间的分子量为150-300。
然而,这些涂漆组合物在进行硬化反应时存在必须采用紫外辐射照射的缺点。
此外,大家都知道,(A)由脂族二异氰酸酯或脂环族二异氰酸酯与数均分子量为500-1500的聚己内酯二醇和/或三醇相反应,然后经除去未反应的脂族二异氰酸酯或脂环族二异氰酸酯后而制得的含双官能和/或三官能端NCO基团的预聚合物和(B)羟基值为10-150毫克KOH/克(以树脂计)、玻璃化转变温度为30-100℃的丙烯酸类多羟基化合物,当NCO/OH当量比为0.5-2.0时已知能形成对丙烯酸类模制品具有优良耐刮性的双—液型聚氨酯漆膜(例如所引述专利4)。然而,这些涂漆组合物由于形成其涂膜是可延伸的,因而漆膜存在发粘的缺点。
[所引述专利1]
Japanese Unexamined Patent Application Laid Open H5-051556
[所引述专利2]
Japanese Unexamined Patent Application Laid Open H5-320562
[所引述专利3]
Japanese Unexamined Patent Application Laid Open2003-277684
[所引述专利4]
Japanese Unexamined Patent Application Laid OpenH11-042746
发明内容
本发明的目的是提供能形成具有优良的耐洗车损伤性、防尘-耐污性和耐候性的漆膜的涂漆组合物以及经涂漆的物品。
通过对上述问题的研究,本发明者业已发现,上述目的可通过采用包含具有特定量的开环ε-己内酯加合物和不泛黄型多异氰酸化合物的丙烯酸类共聚物的涂漆组合物来达到,本发明基于这些研究结果而实现。
这就是说,本发明是一种包含(A)组分和(B)组分的涂漆组合物,其中(A)组分为包含35-50质量%(以树脂的固体级分计)ε-己内酯结构单元的丙烯酸类共聚物(羟值为200-340毫克KOH/克,重均分子量为5000-15000),(B)组分为不泛黄型多异氰酸酯化合物。所形成的清漆组合物的特征在于:组合物中包括每1当量(A)组分的羟基对应0.5-2当量的比例的(B)组分的异氰酸酯基团,由所述涂漆组合物形成的硬化漆膜的杨氏模量不高于1.5帕,固化涂层的交联的分子量(Mc)不高于350克/摩尔,以及硬化漆膜的玻璃化转变温度(Tg)为至少65℃。
此外,本发明提供了用上述清漆组合物涂敷得到的上漆物品。
本发明的油漆组合物可形成具有优良的耐刮性、良好的耐候性及防尘-耐污性的漆膜。
具体实施方式
用于本发明的(A)组分丙烯酸类共聚物优选包含35-50质量%(以树脂的固体级分计)的ε-己内酯结构单元并且其羟值为200-340毫克KOH/克。在这样情况下,当ε-己内酯结构单元含量低于35质量%时,则耐刮性会变差,当ε-己内酯结构单元含量高于50质量%时,则防尘-耐污性和耐候性会变差。此外,如果(A)组分丙烯酸类共聚物的羟值低于200毫克KOH/克,则防尘-耐污性和耐候性会变差,如果羟值超过340毫克KOH/克,则耐刮性与(B)组分不泛黄型多异氰酸酯化合物的相容性会变差。
(A)组分中开环ε-己内酯加成物的含量理想地为37-47质量%,最理想地为39-45质量%。
此外,(A)组分丙烯酸类共聚物的羟值范围优选为220-320毫克KOH/克。
(A)组分丙烯酸类共聚物的重均分子量范围优选为5000-15000,较理想的为7000-13000。当重均分子量低于5000时,则防尘-耐污性和耐候性会变差,当超过15000时,则与(B)组分不泛黄型多异氰酸酯化合物的相容性会变差。
可用于(A)组分丙烯酸类共聚物中的含羟基基团的可自由基聚合的单体的实例包括(甲基)丙烯酸2-羟乙基酯、(甲基)丙烯酸2-羟丙基酯、(甲基)丙烯酸3-羟丙基酯、(甲基)丙烯酸4-羟丁基酯、(甲基)丙烯酸聚乙二醇单酯、(甲基)丙烯酸聚丙二醇单酯、(甲基)丙烯酸新戊二醇单酯以及(甲基)丙烯酸甘油单酯。所用含羟基基团的可自由基聚合的单体可以为单独一种类型,也可以两种或多种类单体混合使用。
可用于(A)组分丙烯酸类共聚物中的其它可共聚合的乙烯基单体的实例包括:(甲基)丙烯酸及它们的烷基取代形式,(甲基)丙烯酸烷基酯(如(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丁醋、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸月桂基酯以及(甲基)丙烯酸硬脂基酯),二元酸的酯(如衣康酸、马来酸及富马酸的酯),苯乙烯和环取代的苯乙烯(如乙烯基甲苯、二甲基苯乙烯及乙基苯乙 烯),(甲基)丙烯腈,(甲基)丙烯酰胺,醋酸乙烯酯以及氯乙烯。所用该其它可共聚合的乙烯基单体可以为单独一种类型,或可以两种或多种类单体混合使用。
在(A)组分丙烯酸类共聚物中实施ε-己内酯开环加成的方法的实例包括:方法(1)使ε-己内酯与上述含羟基基团的可自由基共聚合的单体经历开环加成,然后可作为己内酯改性的可进行自由基聚合的单体用于共聚合中;方法(2)在共聚合反应期间或反应后,将ε-己内酯开环加成到含羟基基团的可自由基聚合的单体与其它乙烯基单体的共聚物中;方法(3)将ε-己内酯开环加成到二羟甲基链烷酸(如2,2-二羟甲基丁酸)中,然后与含环氧基团的(甲基)丙烯酸单酯(如(甲基)丙烯酸缩水甘油酯)的均聚物进行加成反应,或该(甲基)丙烯酸单酯与其它可共聚合乙烯基单体的共聚物与其进行加成反应。
此外,Praxel FA-1(商品名,由1摩尔ε-己内酯与1摩尔丙烯酸2-羟乙基酯开环加成的单体,Daicel Chemical Industries Co.制造),Praxel FM-1D,Praxel FM-2D,Praxel FM-3和Praxel FM-4(都是商品名,分别为由1、2、3或4摩尔ε-己内酯与1摩尔甲基丙烯酸2-羟乙基酯开环加成的单体,Daicel Chemical Industries Co.制造),都可用作可自由基聚合单体,它们都是可商购作为可自由基聚合单体,其中ε-己内酯已与含羟基基团的甲基丙烯酸酯开环加成。
在由上述单体制备(A)组分丙烯酸类共聚物的共聚反应中通常采用聚合引发剂。聚合引发剂的实例包括基于有机过氧化物的聚合引发剂和偶氮基聚合引发剂。对聚合引发剂的使用量没有特别的限制,但0.5-15质量%(相对于单体的总量)是优选的。
此外,适用于制备本发明(A)组分的有机溶剂的实例包括:脂环烃(如环己烷和乙基环己烷),芳烃溶剂(如甲苯、二甲苯、乙基苯和芳烃油),酮基溶剂(如丙酮、甲乙酮、甲基异丁酮、环己酮和异佛尔酮),酯基溶剂(如乙酸乙酯、乙酸正丁酯、乙酸异丁酯、乙酸3-甲氧基丁酯和己二酸双(2-乙基己酯)),醚基溶剂(如二丁基醚、四氢呋喃、1,4-二烷和1,3,5-三烷),以及含氮溶剂(如乙腈、戊腈、N,N-二甲基甲酰胺和N,N-二乙基甲酰胺)。有机溶剂可以为单独一种类型或可以是包含两种或两种以上类型的混合溶剂。在这种情况下,含羟基基团的树脂的固含量可在不影响树脂分散液稳定性的条件下任意选择,但通常为10-70重量%的固含量。
优选用作本发明(B)组分的不泛黄型多异氰酸酯化合物是脂族和脂环族多异氰酸酯化合物。其典型实例包括六亚甲基二异氰酸酯和/或异佛尔酮二异氰酸酯与多元醇和/或低分子量聚酯多羟基化合物的反应产物,异氰脲酸酯(为六亚甲基二异氰酸酯和/或异佛尔酮二异氰酸酯的聚合物)以及缩二脲化合物(由上述化合物再与氨基甲酸酯键反应得到的)。
此外,这些聚合物中的异氰酸酯基团经具有羟基基团的化合物掩蔽的封端异氰酸酯也是优选采用的。各种不泛黄型多异氰酸酯化合物如除上述以外的二异氰酸酯化合物的聚合物也可采用。所用该不泛黄型多异氰酸酯化合物可以为单独一类,或可以两种或两种以上类型混合使用。
本发明中(A)组分与(B)组分的比例是:每1当量(A)组分的羟基对应0.2-2当量,优选0.5-1.5当量,最理想0.6-1.2当量的(B)组分的异氰酸酯基团。当1当量(A)组分羟基基团所对应的(B)组分异氰酸酯基团的当量低于0.5时,则硬化性能不能令人满意,如果用量超过2当量时,则耐刮性能会下降。
本发明的清漆组合物可根据需要添加有机溶剂和各种添加剂,如紫外线吸收剂,光稳定剂,抗氧化剂,表面活性剂,表面调节剂,硬化反应催化剂,抗静电剂,香料,除水剂以及流变调节剂(如聚乙烯蜡、聚酰胺蜡)以及例如细小的内交联树脂颗粒。
可通过调整上述组分使本发明清漆组合物形成的硬化漆膜的杨氏模量不高于1.5帕,优选0.01-1.2帕,最优选0.1-1.0帕,固化涂膜的交联的分子量(Mc)不高于350克/摩尔,优选300-350克/摩尔,硬化漆膜的玻璃化转变温度(Tg)为至少65℃,优选65-90℃。在那些硬化漆膜的杨氏模量低于0.01帕的情况下,漆膜的防尘-耐污性和 耐候性很差,而在杨氏模量超过1.5帕的那些情况下,耐刮性会变差。此外,在硬化漆膜的交联间的分子量低于300的那些情况下,耐刮性很差,而分子量超过350的情况下,防尘-耐污性和耐候性会变差。此外,在玻璃化转变温度(Tg)低于65℃的情况下,防尘-耐污性和耐候性差,而玻璃化转变温度超过90℃则耐刮性会变差。
本发明中杨氏模量的测定方法是通过采用拉伸试验机(商品名为Tensilon/UTM-III-200,Toyo Baldwin Co.制造)在20℃下以每分钟10%的样品长度伸长率测定分离的漆膜试样得到的曲线算得的。这就是说,在分离的漆膜试样为40毫米的情况下,漆膜以每分钟拉伸4毫米的方式伸长。测得的模量值较大说明较硬。
固化涂膜的交联的分子量(Mc)是通过采用强迫伸缩振动型粘度测定装置(商品名为Rheovibron DDV-II-EA,Toyo Baldwin Co.制造),在110赫兹的振动频率和2℃/分钟的升温速率下,测定分离的漆膜试样在橡胶区域的动态刚性模量所得到的数值,并按下式表示:
Mc=293×ρ/(log10G′-7)
式中Mc为交联间的分子量(克/摩尔),ρ是漆膜的密度(克/立方厘米),G′为橡胶区域的动态刚性模量(E′/3(10-9牛/平方米)),E′为在橡胶区域的动态弹性模量(10-9牛/平方米)。
玻璃化转变温度(Tg)是通过采用强迫伸缩振动型粘度测定装置(商品名为Rheovibron,DDV-II-EA,Toyo Baldwin Co.制造),在110赫兹的振动频率、2℃/分钟的升温速率下,测定分离漆膜试样的Tanδ的最大点数值得到的。
适用于本发明清漆组合物的涂装方法是,例如二涂一烤涂装法,在该方法中,将着色的底涂层涂在基材上,然后将所述清漆组合物以未交联的清漆涂在该底涂层上;或是罩面涂装法,在该方法中将着色的底涂层涂在基材上,然后将未交联清漆涂敷在底涂层上,经烘烤后,其上再涂一层所述清漆组合物作为罩面清漆并烘烤;还有其它一些涂装法,其中在上述罩面涂装法中的清漆层上,涂一层透明底漆以保证与下层透明涂层的粘附性,再将所述清漆组合物作为未交联的罩面清 漆涂在该底漆上。
先根据需要,通过加热或添加有机溶剂或反应性稀释剂将上述着色的底漆、清漆、罩面清漆和透明底漆的粘度调节至指定的要求,然后采用常用类型的涂装器械(如空气喷涂器、静电空气喷涂器、辊涂机、流涂机或浸涂***)来实施涂装,或者采用刷涂、线绕棒刮涂器或涂膜器进行涂装。这些方法中喷涂是优选的。
此外,其上涂敷本发明清漆组合物的基材的实例包括有机材料和无机材料如木材,玻璃,金属,布料,塑料,泡沫材料,弹性体,纸,陶瓷,混凝土和石膏板。这些基材可以是预先经表面处理过的材料,或者表面上预先已形成有漆膜的材料。
上面已经提出了一些涂装方法的实例,但涂装本发明清漆组合物的方法不仅限于这些方法。
对本发明清漆组合物涂敷的漆膜厚度没有特别的限制,但是,通常干燥后的漆膜厚度优选为10-150微米,更理想为10-100微米。
可采用本发明清漆组合物进行涂敷得到涂敷物品的实例包括:结构,木制品,金属制品,塑料制品,橡胶制品,加工纸,陶瓷制品及玻璃制品。实际上,这类物品包括:汽车,汽车部件(例如车体、保险杠、阻流板、后视镜、车轮、内装饰件及各种材料制的部件),金属板材如钢板,自行车,自行车部件,道路设施(例如护栏、交通信号和消声墙),隧道设施(例如侧壁板材),船舶,铁路车辆,飞机,家具,乐器,家具电器,建筑材料,容器,办公设备,运动器具以及玩具等。
说明性实施例
下面将通过说明性实施例对本发明作更实用性的说明,但本发明不限于这些说明性实施例。此外,由本发明清漆组合物形成的漆膜的性能是通过下述方法测定的。
(1)对汽车清洗机的耐刮性
耐刮性:用刷子将泥浆水(JIS Z-8901-84,以10/99/1的8型尘土/水/中性洗涤剂的混合物)刷涂在试片上,然后用自动汽车清洗机 中的洗车刷以150rpm转速转动洗刷10秒钟,其后用流动水漂洗试片。对以上步骤重复10次,然后用色差计(CR-331,Minolta Camera Co.制造)通过测量L*值来测定试片表面的刮擦程度。所测数值低的为好。
(2)防尘-耐污性
将尘土水(JIS Z-8901-84,以1.3/98/0.5/0.2的8型尘土/水/炭黑/赫黄颜料)涂敷在试片上,然后在50℃下干燥10分钟,经这样八次反复处理后,用抛光布以固定用力清洁漆膜,同时用水冲洗,并用目视评定污斑,按下列标准作出评价:
○:无污斑
△:部分保留沾污物质
×:全部表面上保留有沾污物质
(3)耐候性
采用日光型碳弧灯加速耐候试验机(JIS K-5400(1990)9.8.1)对漆膜照射3000小时,以目视评定漆膜的状况。
制备实施例1和3-6
含羟基基团涂漆的树脂溶液A-1和A-3-A-6的制备
将表1所列组合物中的二甲苯导入装置有温度计、回流冷凝器、搅拌器和滴液漏斗的四颈烧瓶中,同时在氮气流下搅拌并加热,使温度保持在140℃。接着,将表1中所列的组合物的单体混合物和聚合引发剂(滴加的成分)从滴液漏斗于140℃温度下在2小时内匀速滴加。滴完后继续保持140℃温度1小时,然后将反应温度降至110℃。随后加入表1所列组合物的聚合引发剂溶液(辅助催化剂),在110℃保温2小时后,导入表1所列用量的ε-己内酯,于150℃下保温3小时以完成反应,于是制得了含羟基基团油漆的树脂溶液A-1。此外,含羟基基团油漆的树脂溶液A3-A6的制备,除按表1所列加入的原材料数量不同外,A3-A6的制备步骤与A-1相同。
表1
制备实施例 | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | |
含羟基树脂溶液 | A-1 | A-2 | A-3 | A-4 | A-5 | A-6 | A-7 | A-8 | |
最先导入 | 二甲苯 | 36.8 | 36.6 | 36.7 | 36.7 | 33.0 | 37.3 | 36.4 | 36.2 |
2,2-二羟甲基丁 酸 | - | 16.5 | - | - | - | - | 12.8 | 20.1 | |
单体 | 丙烯酸丁酯 | 2.7 | 3.3 | 11.0 | 8.7 | 2.7 | 2.7 | 1.4 | - |
甲基丙烯酸2-羟 乙酯 | 33.3 | - | 25.0 | 33.3 | 33.3 | 33.3 | - | - | |
甲基丙烯酸缩水 甘油酯 | - | 16.2 | - | - | - | - | 12.8 | 20.1 | |
叔丁基过氧-2-乙 基己酸酯 | 1.2 | 1.4 | 1.2 | 1.2 | 5.0 | 0.7 | 1.5 | 1.5 | |
辅助催化剂 | 叔丁基过氧-2-乙 基己酸酯 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
二甲苯 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | |
辅助组分 | ε-己内酯 | 24.0 | 24.0 | 24.0 | 18.0 | 24.0 | 24.0 | 33.0 | 33.0 |
二甲苯 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | |
总计 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | |
树脂的羟值(mgKOH/g) | 240 | 310 | 180 | 240 | 240 | 240 | 240 | 369 | |
非挥发性物质(质量%) | 61 | 61 | 61 | 61 | 65 | 61 | 62 | 62 | |
重均分子量 | 9.100 | 9.300 | 8.900 | 9.000 | 3.200 | 17,10 0 | 9,100 | 9,300 | |
在树脂的固体部分中ε-己内酯含 量(质量%) | 39.3 | 39.3 | 39.3 | 29.5 | 36.9 | 39.3 | 53.2 | 32.3 |
制备实施例2、7和8
含羟基基团涂漆的树脂溶液A-2、A-7和A-8的制备
将表1所列组合物中的二甲苯和2,2-二羟甲基丁酸导入装置有温度计、回流冷凝器、搅拌器和滴液漏斗的四颈烧瓶中,同时在氮气 流下搅拌并加热,使温度保持在140℃。接着,将表1中所列组合物的单体混合物和聚合引发剂(滴加的组分)从滴液漏斗在140℃温度下在2小时内匀速滴加。滴完后继续在140℃温度下保温1小时,然后将反应温度降至110℃。随后加入表1所列组合物的聚合引发剂溶液(辅助催化剂),在110℃保温2小时后,导入表1所列的ε-己内酯,于150℃下保温3小时以完成反应,于是制得了含羟基基团涂漆的树脂溶液A-2、A-7和A-8。
制备实施例9-20
清漆CC-1-CC-12的制备
依次将表2和表3中原材料进行混合并搅拌以得到均匀的混合物,制成清漆。
表2
制备实施例 | 9 | 10 | 11 | 12 | |
清漆 | CC-1 | CC-2 | CC-3 | CC-4 | |
含羟基基团的丙烯酸类树脂 | A-1 | 35.4 | - | 44.2 | 25.0 |
A-2 | - | 30.7 | - | - | |
A-3 | - | - | - | - | |
A-4 | - | - | - | - | |
A-5 | - | - | - | - | |
A-6 | - | - | - | - | |
A-7 | - | - | - | - | |
A-8 | - | - | - | - | |
交联剂(Sumidure HT-1) | 29.3 | 33.1 | 22.0 | 37.3 | |
紫外光吸收剂溶液2) | 1.5 | 1.5 | 1.5 | 1.5 | |
光稳定剂溶液3) | 1 | 1 | 1 | 1 | |
表面调节剂溶液4) | 0.4 | 0.4 | 0.4 | 0.43 | |
Solvesso 1005) | 32.4 | 33.3 | 30.9 | 34.8 | |
总计 | 100.0 | 100.0 | 100.0 | 100.0 | |
(B)组分的NCO基团与(A)组分的羟基基团的 当量比 | 1.0 | 1.0 | 0.6 | 1.8 |
表3
制备实施例 | 13 | 14 | 15 | 16 | 17 | 18 | 19 | 20 | |
清漆 | CC-5 | CC-6 | CC-7 | CC-8 | CC-9 | CC-10 | CC-11 | CC-12 | |
含羟基基团的丙烯酸类 树脂 | A-1 | - | - | - | - | - | - | 54.7 | 20.0 |
A-2 | - | - | - | - | - | - | - | - | |
A-3 | 40.0 | - | - | - | - | - | - | - | |
A-4 | - | 35.4 | - | - | - | - | - | - | |
A-5 | - | - | 35.4 | - | - | - | - | - | |
A-6 | - | - | - | 35.4 | - | - | - | - | |
A-7 | - | - | - | - | 35.3 | - | - | - | |
A-8 | - | - | - | - | - | 28.6 | - | - | |
交联剂HT 1) | 24.8 | 29.3 | 29.3 | 29.3 | 29.5 | 34.8 | 13.6 | 41.4 | |
紫外光吸收剂溶液2) | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 | |
光稳定剂溶液3) | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | |
表面调节剂溶液4) | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | |
Solvesso 1005) | 32.3 | 32.4 | 32.4 | 32.4 | 32.3 | 33.7 | 28.8 | 35.7 | |
总计 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | 100.0 | |
(B)组分的NCO基团与(A) 组分的羟基基团的当量比 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 0.3 | 2.5 |
上表的附注
1)Sumidure HT:商品名,液态HDI的缩二脲型树脂(不挥发馏分75质量%,NCO含量为13质量%),由Sumika Beyer Urethane Co.制造
2)Tinuvin 900:商品名,20质量%二甲苯溶液,Ciba SpecialtyChemicals Co.制造
3)Tinuvin 292:商品名,20质量%二甲苯溶液,Ciba SpecialtyChemicals Co.制造
4)BYK-300:商品名,10质量%二甲苯溶液,Bikkukemi Co.制造
5)Solvesso 100:商品名,芳烃油,Esso Co.制造
实施例1-4
试样的制备和漆膜性能的研究
将阳离子电沉积漆Aqua No.4200(商品名,BASF Coatings JapanCo.制造)以电沉积法涂敷在经磷酸锌处理过的中碳钢板上,使经175℃烘烤25分钟后的干膜厚度为20微米,然后以空气喷涂法涂敷中间涂层漆HS-H300(商品名,BASF Coatings Japan Co.制造),使经140℃烘烤30分钟后的干膜厚度为30微米。然后,用空气喷涂法涂敷溶剂基底漆Belcoat No.6000黑(商品名,BASF Coatings Japan Co.制造,涂漆颜色:黑),以使干膜厚度为15微米,在20℃下固定3分钟后,用Sorbesso 100(商品名,Esso Co.制造,芳烃油)将清漆CC-1或CC-2稀释至涂敷粘度(No.4 Ford杯,20℃下25秒),用具有湿碰湿体系的空气喷涂法进行涂敷使干膜厚度为40微米,并经140℃烘烤30分钟制得试样。
然而,实施例1-实施例4的耐污试验的试片中以Belcoat No.6000白(商品名,BASF Coatings Japan Co.制造,涂漆颜色:白)代替底漆。
漆膜性能列于表4中,在所有情况中都没有产生涂漆浊度,得到的漆膜具有均匀光泽,这些漆膜具有优良的耐洗车损伤性、耐污性和耐候性。
对照实施例1-8
试样的制备和漆膜性能的研究
除清漆是CC-5-CC-12外,其余按照与实施例1相同的方法制备试样。漆膜性能列于表5中,对照实施例1、3和5的耐污性和耐候性较差,而对照实施例2的耐洗车损伤性很差。此外,对照实施例4和6中A和B组分的相容性很差。
此外,在异氰酸酯含量低的对照实施例7中,防尘-耐污性和耐候性很差,异氰酸酯含量过量的对照实施例8中,耐刮性降低。
表4
实施例1 | 实施例2 | 实施例3 | 实施例4 | ||
清漆 | CC-1 | CC-2 | CC-3 | CC-4 | |
(B)组分的NCO基团与(A)组分的羟基基团的当 量比 | 1.0 | 1.0 | 0.6 | 1.8 | |
树脂的羟值(mgKOH/g) | 240 | 310 | 240 | 240 | |
ε-己内酯含量(质量%) | 39 | 39 | 39 | 39 | |
(A)组分重均分子量 | 9100 | 9300 | 9100 | 9100 | |
A组分与B组分的相容性 | ○ | ○ | ○ | ○ | |
硬化的漆膜性能 | 杨氏膜量 | 0.43 | 0.5 | 0.3 | 1.3 |
固化漆膜的交联的分子量 | 316 | 311 | 340 | 320 | |
漆膜Tg | 66.2 | 76.2 | 66 | 75 | |
对汽车清洗机的耐刮擦性 | 0.2 | 0.8 | 0.3 | 1.2 | |
防尘-耐污性 | ○ | ○ | ○ | ○ | |
耐候性 | 正常 | 正常 | 正常 | 正常 |
表5
对照实施例 1 | 对照实施例 2 | 对照实施例 3 | 对照实施例 4 | 对照实施例 5 | 对照实施例 6 | 对照实施例 7 | 对照实施例 8 | ||
清漆 | CC-5 | CC-6 | CC-7 | CC-8 | CC-9 | CC-10 | CC-11 | CC-12 | |
(B)组分的NCO基团与(A)组分的羟基 基团的当量比 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 | 0.3 | 2.5 |
树脂的羟值(mgKOH/g) | 180 | 240 | 240 | 240 | 240 | 350 | 240 | 240 | |
ε-己内酯含量(质量%) | 39 | 30 | 37 | 39 | 53 | 32 | 39 | 39 | |
(A)组分重均分子量 | 8900 | 9000 | 3200 | 17100 | 9100 | 9300 | 9100 | 9100 | |
A组分与B组分的相容性 | ○ | ○ | ○ | × | ○ | × | ○ | ○ | |
硬化的漆 膜性能 | 杨氏模量 | 0.45 | 7.5 | 0.43 | - | 0.32 | - | 0.1 | 2 |
固化漆膜的交联的分子量 | 389 | 313 | 335 | - | 346 | - | 400 | 370 | |
漆膜Tg | 60.1 | 68.5 | 62.3 | - | 58.6 | - | 55 | 95 | |
对汽车清洗机的耐刮擦性 | 0.2 | 7.5 | 0.1 | - | 0.1 | - | 1.3 | 8 | |
防尘-耐污性 | × | ○ | × | - | × | - | × | ○ | |
耐候性 | 水斑 | 正常 | 水斑 | - | 水斑 | - | 水斑 | 正常 |
工业应用前景
本发明的清漆组合物可用于各种领域中,具体地说,可用作车辆如汽车、摩托车用涂漆。
Claims (2)
1.一种包含(A)组分和(B)组分的清漆组合物,其中(A)组分为包含以树脂的固体级分计35-50质量%的ε-己内酯结构单元的丙烯酸类共聚物,该丙烯酸类共聚物的羟值为200-340毫克KOH/克和重均分子量为5000-15000,(B)组分为不泛黄型多异氰酸酯化合物,该组合物的特征在于:组合物中包括每1当量(A)组分的羟基对应0.5-2当量的比例的(B)组分的异氰酸酯基团,由所述漆组合物形成的硬化漆膜的杨氏模量不高于1.5帕,固化漆膜的交联的分子量(Mc)不高于350克/摩尔,以及硬化的漆膜的玻璃化转变温度(Tg)为至少65℃。
2.用权利要求1公开的漆组合物涂漆得到的上漆物品。
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JPH06220397A (ja) * | 1993-01-25 | 1994-08-09 | Mazda Motor Corp | 二液型ウレタン塗料組成物 |
JP3329049B2 (ja) * | 1994-01-24 | 2002-09-30 | 日本油脂ビーエーエスエフコーティングス株式会社 | 自動車用上塗塗料のクリヤーコート用熱硬化被覆組成物 |
US6436531B1 (en) * | 1998-07-20 | 2002-08-20 | 3M Innovative Properties Company | Polymer blends and tapes therefrom |
US6652971B1 (en) * | 2000-10-30 | 2003-11-25 | E. I. Du Pont De Nemours And Company | Hydroxy-functional (meth)acrylic copolymers and coating composition |
US6894124B2 (en) * | 2000-11-01 | 2005-05-17 | Kansai Paint Co., Ltd. | High solid paint compositions |
US6605669B2 (en) * | 2001-04-03 | 2003-08-12 | E. I. Du Pont De Nemours And Company | Radiation-curable coating compounds |
JP2003119410A (ja) * | 2001-10-10 | 2003-04-23 | Kansai Paint Co Ltd | 塗料組成物及びそれを用いた塗膜形成方法 |
JP2003181368A (ja) * | 2001-12-13 | 2003-07-02 | Kansai Paint Co Ltd | 複層塗膜形成方法 |
ES2403529T3 (es) * | 2002-03-22 | 2013-05-20 | Basf Japan Ltd. | Composición de recubrimiento curable por UV y artículos recubiertos |
JP2003313493A (ja) * | 2002-04-23 | 2003-11-06 | Nippon Yushi Basf Coatings Kk | 上塗り塗料組成物、塗装仕上げ方法及び塗装物品 |
US7019082B2 (en) * | 2002-08-09 | 2006-03-28 | Carnegie Mellon University | Polymers, supersoft elastomers and methods for preparing the same |
JP2004256679A (ja) * | 2003-02-26 | 2004-09-16 | Dainippon Ink & Chem Inc | ウレタン系塗料およびウレタン系塗料用硬化剤組成物 |
JP4259278B2 (ja) * | 2003-10-27 | 2009-04-30 | Basfコーティングスジャパン株式会社 | 熱硬化性塗料組成物 |
US7288290B2 (en) * | 2004-05-26 | 2007-10-30 | Ppg Industries Ohio, Inc. | Process for applying multi-component composite coatings to substrates to provide sound damping and print-through resistance |
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- 2006-07-03 CN CN2006800253418A patent/CN101218316B/zh active Active
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CN1542068A (zh) * | 2003-03-28 | 2004-11-03 | ������������ʽ���� | 涂膜的形成方法 |
CN1572856A (zh) * | 2003-05-20 | 2005-02-02 | 拜尔材料科学股份公司 | 用于抗划伤面漆的高固含量粘合剂组合物 |
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EP1907493B1 (en) | 2010-06-30 |
WO2007007146A3 (en) | 2007-05-18 |
ATE472581T1 (de) | 2010-07-15 |
WO2007007146A2 (en) | 2007-01-18 |
JP2007023069A (ja) | 2007-02-01 |
DE602006015196D1 (de) | 2010-08-12 |
CN101218316A (zh) | 2008-07-09 |
US8536274B2 (en) | 2013-09-17 |
JP5279984B2 (ja) | 2013-09-04 |
EP1907493A2 (en) | 2008-04-09 |
US20080227915A1 (en) | 2008-09-18 |
KR20080027796A (ko) | 2008-03-28 |
KR101284204B1 (ko) | 2013-07-09 |
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