CN109468050B - 一种水性柔性手感涂料及其制备方法 - Google Patents
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Abstract
本发明涉及一种水性柔性手感涂料及其制备方法,所述涂料包括水和树脂组分,所述树脂组分包括以下重量百分含量的各组分:脂肪族二异氰酸酯:10~20%;HDI二聚体:15~30%;聚四氢呋喃二元醇:30~50%;亲水扩链剂:6~9%;多官扩链剂:3~6%;中和剂;3~6%;后扩链剂:2~6%。本发明制备的树脂有出色的机械性能,包括耐磨性、耐擦性好等,且涂料为水性产品,VOC≤150g/L,绿色环保,可作为高回弹漆,用于更广泛的领域;而涂料合成过程中不含金属类催化剂,无需阻燃,更加安全。
Description
技术领域
本发明涉及包装涂料技术领域,具体地说,涉及一种水性柔性手感涂料及其制备方法。
背景技术
目前市场上应用于包装行业(包括软性基材和硬性基材)的传统柔性手感涂料均为油性产品,其配方全部采用含溶剂的原材料,VOC含量高达600-1000g/L,远超国家涂料消费税免征点420g/L。因此,在本领域开发低VOC含量的水性柔性手感涂料具有很大意义。
由于水性合成工艺、稳定性与成膜机理与油性产品的不同,已有的水性聚氨酯乳液很难满足柔性手感,抗指纹性,耐候性等要求,因此传统水性聚氨酯成膜后不具备细腻的手感,一般为涩感。
现有的文献资料关于水性柔性手感涂料的研究,局限于聚碳酸酯改性,硅氟改性,添加消光剂等,多具有合成难度高与成本高等劣势,而通过树脂微观结构调整增强柔性手感的性能则鲜有报道。
发明内容
针对现有技术的缺陷,本发明的目的是提供一种水性柔性手感涂料及其制备方法。
本发明的目的是通过以下技术方案实现的:
本发明提供了一种水性柔性手感涂料,包括水和树脂组分,所述树脂组分包括以下重量百分含量的各组分:
所述脂肪族二异氰酸酯的加入量的质量百分数若高于这个范围,会造成最终分子量过小,乳液各方面性能不足;若低于这个范围,又会导致合成粘度过大易凝结。所述HDI二聚体加入量的质量百分数若高于这个范围会导致合成不稳定,极易凝胶;若低于这个范围,又无法满足性能要求。所述亲水扩链剂的含量若高于此范围会导致合成粘度大,乳液固含低;若低于此范围会导致乳液稳定性差,流平变差。所述扩链剂的含量若高于此范围会导致合成粘度大,易凝胶;若低于此范围会导致分子量过低,涂层性能下降。所述后扩链剂的含量若高于此范围会导致乳化困难;若低于此范围会导致涂层的手感性能不足。
优选地,所述脂肪族二异氰酸酯选自4,4'-二环己基甲烷二异氰酸酯(HMDI)、异佛尔酮二异氰酸酯(IPDI)中的一种或两种。
优选地,所述HDI二聚体,其生产厂商万华,商品名HT-100。
优选地,所述聚四氢呋喃二元醇的数均分子量Mn≤3000,分子量分布PDI<1.5。所述的数均分子量和分子量分布若高于此范围,都会造成最终涂层的手感性能不足。
优选地,所述亲水扩链剂为二羟甲基丙酸或二羟甲基丁酸其中的一种。
优选地,所述多官扩链剂为三羟甲基丙烷或三羟甲基乙烷其中的一种。
优选地,所述中和剂为N,N-二甲基乙醇胺、N,N-二异丙基乙胺、三乙胺其中的一种。
优选地,所述后扩链剂为四乙烯基五胺、五乙烯基六胺其中的一种。
优选地,所述水和树脂组分的质量比为6-8:2-4。
本发明还提供了一种水性柔性手感涂料的制备方法,包括以下步骤:
S1、将聚四氢呋喃二元醇搅拌脱水后加入HDI二聚体和脂肪族二异氰酸酯,保温;
S2、在步骤S1的混合物中加入亲水扩链剂反应;
S3、经步骤S2反应后加入多官扩链剂反应;
S4、将步骤S3反应后降温,然后加入中和剂调节pH值和粘度,并反应;
S5、经步骤S4反应后进行乳化分散,乳化分散的同时加入水和后扩链剂;
S6、经步骤S5处理后,抽真空旋蒸除去丙酮,即得。
优选地,步骤S1中,所述聚四氢呋喃二元醇进行搅拌脱水的条件为:温度为80-90℃、搅拌速度为100-200rpm;所述脱水后的聚酯多元醇含水量小于200ppm;所述保温温度为75-85℃、时间为2-4小时;
步骤S2中,所述反应温度为80-90℃、时间为1-3小时;
步骤S3中,所述反应温度为70-80℃、时间为1-3小时;
步骤S4中,所述降温至50-60℃,所述调节pH值为6.5-7.5,粘度为200~1000cp,所述反应时间为20-40min;
步骤S5中,所述乳化分散采用的转速为1000-1500rpm,乳化分散时间为20-40min。
步骤S6中,所述加热温度为50-60℃。
与现有技术相比,本发明具有如下的有益效果:
1、本发明选用柔性手感能力较强的聚四氢呋喃二元醇和HDI二聚体搭配使用,提供涂层细腻而柔软的手感,且具备较好的回弹性,使得手感涂层的抗指纹性更具优势。加入脂肪族二异氰酸酯,主要是降低HDI二聚体的反应密度,降低体系凝胶的风险。后扩链剂方面采用四乙烯基五胺和五乙烯基六胺,大幅增强主链的分子量,使得涂层的手感性、抗指纹性、回弹性均大幅提升。
2、本发明制备的涂料有出色的机械性能,包括耐磨性、耐擦性好等;
3、本发明制备的涂料为水性产品,VOC≤150g/L,绿色环保。在施工过程中,无任何刺激性气味,对施工人员伤害小;
4、本发明制备的涂料可作为高回弹漆,用于更广泛的领域;
5、本发明的涂料合成过程中不含金属类催化剂,无需阻燃,更加安全。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明,但不以任何形式限制本发明。应当指出的是,对本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进。这些都属于本发明的保护范围。
实施例1
本实施例的水性柔性手感涂料采用以下组分及含量的原料进行制备:
上述水性柔性手感涂料按以下工艺步骤制备:
组分a在85℃,真空条件下搅拌脱水,搅拌速度为200rpm。直到组分a中的含水量小于200ppm后,结束抽真空恢复常压。保持搅拌并加入组分b和c,保持85℃反应2h。保持搅拌并加入组分d,保持85℃反应2h,粘度太大加入组分h。降温至75℃,保持搅拌并加入组分e,保持75℃继续反应2h,粘度太大时加入组分h。冷却至50℃,加入组分f,继续搅拌30min后出料。将合成的树脂在1200rpm转速下高速分散,加入组分i,待完全搅拌开成乳液,加入组分g,随后保持30min。将合成的乳液倒入旋转蒸发釜中,50℃抽真空下进行旋蒸脱除丙酮,待固含≥31%后结束,得到成品乳液。
实施例2
本实施例的水性柔性手感涂料采用以下组分及含量的原料进行制备:
a | 聚四氢呋喃二元醇(Mn=3000,PDI=1.30) | 150g | 41.23% |
b | HT-100 | 104.2g | 28.65% |
c | 4,4'-二环己基甲烷二异氰酸酯 | 39.3g | 10.80% |
d | 二羟甲基丙酸 | 24.1g | 6.63% |
e | 三羟甲基丙烷 | 20.1g | 5.53% |
f | N,N’-二甲基乙醇胺 | 14.7g | 4.04% |
g | 四乙烯基五胺 | 11.3g | 3.12% |
h | 丙酮 | 170g | - |
i | 去离子水 | 760g | - |
上述水性柔性手感涂料按以下工艺步骤制备:
组分a在85℃,真空条件下搅拌脱水,搅拌速度为200rpm。直到组分a中的含水量小于200ppm后,结束抽真空恢复常压。保持搅拌并加入组分b和c,保持85℃反应2h。保持搅拌并加入组分d,保持85℃反应2h,粘度太大加入组分h。降温至75℃,保持搅拌并加入组分e,保持75℃继续反应2h,粘度太大时加入组分h。冷却至50℃,加入组分f,继续搅拌30min后出料。将合成的树脂在1200rpm转速下高速分散,加入组分i,待完全搅拌开成乳液,加入组分g,随后保持30min。将合成的乳液倒入旋转蒸发釜中,50℃抽真空下进行旋蒸脱除丙酮,待固含≥31%后结束,得到成品乳液。
实施例3
本实施例的水性柔性手感涂料采用以下组分及含量的原料进行制备:
a | 聚四氢呋喃二元醇(Mn=2000,PDI=1.23) | 130g | 35.19% |
b | HT-100 | 104.2g | 28.21% |
c | 4,4'-二环己基甲烷二异氰酸酯 | 52.4g | 14.19% |
d | 二羟甲基丁酸 | 28.8g | 7.80% |
e | 三羟甲基丙烷 | 22.1g | 6.00% |
f | N,N’-二甲基乙醇胺 | 16.3g | 4.42% |
g | 五乙烯基六胺 | 14.3g | 4.02% |
h | 丙酮 | 180g | - |
i | 去离子水 | 770g | - |
上述水性柔性手感涂料按以下工艺步骤制备:
组分a在85℃,真空条件下搅拌脱水,搅拌速度为200rpm。直到组分a中的含水量小于200ppm后,结束抽真空恢复常压。保持搅拌并加入组分b和c,保持85℃反应2h。保持搅拌并加入组分d,保持85℃反应2h,粘度太大加入组分h。降温至75℃,保持搅拌并加入组分e,保持75℃继续反应2h,粘度太大时加入组分h。冷却至50℃,加入组分f,继续搅拌30min后出料。将合成的树脂在1200rpm转速下高速分散,加入组分i,待完全搅拌开成乳液,加入组分g,随后保持30min。将合成的乳液倒入旋转蒸发釜中,50℃抽真空下进行旋蒸脱除丙酮,待固含≥31%后结束,得到成品乳液。
实施例4-6
本实施例4-6的水性柔性手感涂料采用以下组分及百分含量的原料进行制备:
上述水性柔性手感涂料的制备方法包括以下步骤:
S1、将聚四氢呋喃二元醇搅拌脱水后加入HDI二聚体和脂肪族二异氰酸酯,保温;
S2、在步骤S1的混合物中加入亲水扩链剂反应;
S3、经步骤S2反应后加入多官扩链剂反应;
S4、将步骤S3反应后降温,然后加入中和剂调节pH值和粘度,并反应;
S5、经步骤S4反应后进行乳化分散,乳化分散的同时加入水和后扩链剂;
S6、经步骤S5处理后,抽真空旋蒸除去丙酮,即得。
步骤S1中,所述聚四氢呋喃二元醇进行搅拌脱水的条件为:温度为80-90℃、搅拌速度为100-200rpm;所述脱水后的聚酯多元醇含水量小于200ppm;所述保温温度为75-85℃、时间为2-4小时;
步骤S2中,所述反应温度为80-90℃、时间为1-3小时;
步骤S3中,所述反应温度为70-80℃、时间为1-3小时;
步骤S4中,所述降温至50-60℃,所述调节pH值为6.5-7.5,粘度为200~1000cp,所述反应时间为20-40min;
步骤S5中,所述乳化分散采用的转速为1000-1500rpm,乳化分散时间为20-40min。
步骤S6中,所述加热温度为50-60℃。
对比例1
本对比例的水性涂料采用以下组分及含量的原料进行制备:
上述水性柔性手感涂料按以下工艺步骤制备:
组分a在85℃,真空条件下搅拌脱水,搅拌速度为200rpm。直到组分a中的含水量小于200ppm后,结束抽真空恢复常压。保持搅拌并加入组分b和c,保持85℃反应2h。保持搅拌并加入组分d,保持85℃反应2h,粘度太大加入组分h。降温至75℃,保持搅拌并加入组分e,保持75℃继续反应2h,粘度太大时加入组分h。冷却至50℃,加入组分f,继续搅拌30min后出料。将合成的树脂在1200rpm转速下高速分散,加入组分i,待完全搅拌开成乳液,加入组分g,随后保持30min。将合成的乳液倒入旋转蒸发釜中,50℃抽真空下进行旋蒸脱除丙酮,待固含≥31%后结束,得到成品乳液。
对比例2
本对比例的水性涂料采用以下组分及含量的原料进行制备:
a | 聚四氢呋喃二元醇(Mn=2000,PDI=1.23) | 200g | 45.56% |
b | HT-100 | 96.5g | 21.98% |
c | 异佛尔酮二异氰酸酯 | 55.5g | 12.64% |
d | 二羟甲基丙酸 | 37.5g | 8.55% |
e | 三羟甲基丙烷 | 13.4g | 3.05% |
f | N,N’-二甲基乙醇胺(中和剂) | 22.9g | 5.21% |
g | 二乙烯三胺 | 13.2g | 3.01% |
h | 丙酮 | 200g | - |
i | 去离子水 | 900g | - |
上述聚氨酯乳液按以下工艺步骤制备:
组分a在85℃,真空条件下搅拌脱水,搅拌速度为200rpm。直到组分a中的含水量小于200ppm后,结束抽真空恢复常压。保持搅拌并加入组分b和c,保持85℃反应2h。保持搅拌并加入组分d,保持85℃反应2h,粘度太大加入组分h。降温至75℃,保持搅拌并加入组分e,保持75℃继续反应2h,粘度太大时加入组分h。冷却至50℃,加入组分f,继续搅拌30min后出料。将合成的树脂在1200rpm转速下高速分散,加入组分i,待完全搅拌开成乳液,加入组分g,随后保持30min。将合成的乳液倒入旋转蒸发釜中,50℃抽真空下进行旋蒸脱除丙酮,待固含≥31%后结束,得到成品乳液。
对比例3
本对比例的水性涂料采用以下组分及含量的原料进行制备:
a | 聚四氢呋喃二元醇(Mn=2000,PDI=1.23) | 200g | 45.56% |
b | 六次亚甲基二异氰酸酯 | 96.5g | 21.98% |
c | 异佛尔酮二异氰酸酯 | 55.5g | 12.64% |
d | 二羟甲基丙酸 | 37.5g | 8.55% |
e | 三羟甲基丙烷 | 13.4g | 3.05% |
f | N,N’-二甲基乙醇胺(中和剂) | 22.9g | 5.21% |
g | 四乙烯基五胺 | 13.2g | 3.01% |
h | 丙酮 | 200g | - |
i | 去离子水 | 900g | - |
上述水性柔性手感涂料按以下工艺步骤制备:
组分a在85℃,真空条件下搅拌脱水,搅拌速度为200rpm。直到组分a中的含水量小于200ppm后,结束抽真空恢复常压。保持搅拌并加入组分b和c,保持85℃反应2h。保持搅拌并加入组分d,保持85℃反应2h,粘度太大加入组分h。降温至75℃,保持搅拌并加入组分e,保持75℃继续反应2h,粘度太大时加入组分h。冷却至50℃,加入组分f,继续搅拌30min后出料。将合成的树脂在1200rpm转速下高速分散,加入组分i,待完全搅拌开成乳液,加入组分g,随后保持30min。将合成的乳液倒入旋转蒸发釜中,50℃抽真空下进行旋蒸脱除丙酮,待固含≥31%后结束,得到成品乳液。
对实施例1~3和对比例1~3制备的乳液,进行各项性能测试,结果如下:
表1
由对比例1可以看出,采用普通的聚己二酸新戊二醇型二元醇搭配六次亚甲基二异氰酸酯合成的水性聚氨酯,涂膜后并不具备柔性的手感,这是因为普通的聚己二酸新戊二醇型二元醇本身具备一定的涩感。从对比例2可以看出,当后扩链剂采用二乙烯基三胺,其最终涂层的耐磨性和耐指纹性无法达到要求,这是因为二乙烯基三胺官能度较低,无法在后扩链过程中让聚氨酯主链达到足够的分子量,从而导致性能不足。从对比例3可以看出,当采用普通的六次亚甲基二异氰酸酯代替HDI二聚体后,涂层不具备耐磨性以及抗指纹性,这是由于普通的六次亚甲基二异氰酸酯性能偏软,回弹性不足。
本发明具体应用途径很多,以上所述仅是本发明的优选实施方式。应当指出,以上实施例仅用于说明本发明,而并不用于限制本发明的保护范围。对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进,这些改进也应视为本发明的保护范围。
Claims (4)
1.一种水性柔性手感涂料,包括水和树脂组分,其特征在于,所述树脂组分包括以下重量百分含量的各组分:
二异氰酸酯: 10~ 20%;
HDI二聚体: 15~ 30%;
聚四氢呋喃二元醇: 30~50%;
亲水扩链剂: 6~ 9%;
多官扩链剂: 3~ 6%;
中和剂; 3~ 6%;
后扩链剂: 2~ 6%;
所述多官扩链剂为三羟甲基丙烷或三羟甲基乙烷其中的一种;
所述后扩链剂为四乙烯基五胺、五乙烯基六胺其中的一种;
所述聚四氢呋喃二元醇的数均分子量Mn≤3000,分子量分布PDI<1.5;
所述亲水扩链剂为二羟甲基丙酸或二羟甲基丁酸其中的一种;
所述水和树脂组分的质量比为6-8:2-4;
所述二异氰酸酯选自4,4'-二环己基甲烷二异氰酸酯、异佛尔酮二异氰酸酯中的一种或两种。
2.根据权利要求1所述的水性柔性手感涂料,其特征在于,所述中和剂为N,N-二甲基乙醇胺、N,N-二异丙基乙胺、三乙胺其中的一种。
3.一种根据权利要求1-2任一项所述的水性柔性手感涂料的制备方法,其特征在于,包括以下步骤:S1、将聚四氢呋喃二元醇搅拌脱水后加入HDI二聚体和二异氰酸酯,保温;
S2、在步骤S1的混合物中加入亲水扩链剂反应;
S3、经步骤S2反应后加入多官扩链剂反应;
S4、将步骤S3反应后降温,然后加入中和剂调节pH值和粘度,并反应;
S5、经步骤S4反应后进行乳化分散,乳化分散的同时加入水和后扩链剂;
S6、经步骤S5处理后,抽真空加热除去丙酮,即得。
4.根据权利要求3所述的水性柔性手感涂料的制备方法,其特征在于,步骤S1中,所述聚四氢呋喃二元醇进行搅拌脱水的条件为:温度为80-90℃、搅拌速度为100-200rpm;所述脱水后的聚四氢呋喃二元醇含水量小于200ppm;所述保温温度为75-85℃、时间为2-4小时;
步骤S2中,所述反应温度为80-90℃、时间为1-3小时;
步骤S3中,所述反应温度为70-80℃、时间为1-3小时;
步骤S4中,所述降温至50-60℃,所述调节pH值为6.5-7.5,粘度为200~1000 cp,所述反应时间为20-40min;
步骤S5中,所述乳化分散采用的转速为1000-1500rpm,乳化分散时间为20-40min;
步骤S6中,所述加热温度为50-60℃。
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