CN115387130A - 一种人造革用uv涂料及其应用 - Google Patents
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- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 3
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- 230000001376 precipitating effect Effects 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
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- ZDHCZVWCTKTBRY-UHFFFAOYSA-N omega-Hydroxydodecanoic acid Natural products OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 claims description 2
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
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- MJIHNNLFOKEZEW-UHFFFAOYSA-N lansoprazole Chemical compound CC1=C(OCC(F)(F)F)C=CN=C1CS(=O)C1=NC2=CC=CC=C2N1 MJIHNNLFOKEZEW-UHFFFAOYSA-N 0.000 description 1
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- D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- 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
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- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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Abstract
本发明涉及涂料技术领域,具体涉及一种人造革用UV涂料及其应用。光固化涂料中的热膨胀微球在光固化过程中受热微膨胀的同时,会显著降低光固化涂层与人造革之间的附着力,使得光固化涂层容易从人造革表面脱落。针对上述问题,本发明提供一种人造革用UV涂料,其成分中添加有自制长氟碳链改性的热膨胀微球,长氟碳链的存在赋予改性热膨胀微球低表面能,使得改性热膨胀微球具有上浮的特性,将本发明所获光固化涂料涂覆在人造革的表面,红外流平过程中涂料中的改性热膨胀微球倾向于集中分布在涂层的表面,光固化过程中,通过控制控制光照时间,使得光固化涂料中的改性热膨胀微球受热后发生微膨胀,最终获得表面富有细腻弹性触感的人造皮革。
Description
技术领域
本发明涉及涂料技术领域,具体涉及一种人造革用UV涂料及其应用。
背景技术
人造革是一种外观、手感似皮革并可代替其使用的塑料制品。通常以织物为底基,涂覆合成树脂及各种塑料添加制成。主要有PVC人造革、PU合成革两类。人造革的花色品种繁多、防水性能好、边幅整齐、利用率高和价格相对真皮便宜的特点。
市面上,绝大多数人造革,其手感和弹性无法达到真皮的细腻弹性触感。针对上述问题,有研究将含有热膨胀微球的光固化涂料涂覆在人造革表面形成光固化涂层,热膨胀微球在光固化过程中发生微膨胀,试验发现,这种方法确实可以赋予人造革具有较好的弹性,但是,热膨胀微球在发生微膨胀的同时,会显著降低光固化涂层与人造革之间的附着力,使得涂层容易从人造革表面脱落。
本发明提供一种UV涂料,其涂料体系中添加有自制长氟碳链改性的热膨胀微球,长氟碳链的存在赋予改性热膨胀微球低表面能,使得改性热膨胀微球具有上浮的特性,在涂料红外流平过程中倾向于集中分布在涂层的表面,光固化过程中,通过控制控制光照时间,使得改性热膨胀微球发生微膨胀,最终获得表面富有细腻弹性触感的人造皮革。
发明内容
现有技术中存在的问题是:光固化涂料中的热膨胀微球在光固化过程中受热微膨胀的同时,会显著降低光固化涂层与人造革之间的附着力,使得光固化涂层容易从人造革表面脱落。针对上述问题,本发明提供一种人造革用UV涂料,以重量份数计,包括以下成分:
具体地,所述丙烯酸树脂为环氧丙烯酸树脂、聚氨酯丙烯酸树脂、聚酯丙烯酸树脂中的至少一种。
具体地,改性热膨胀微球按照以下步骤制备:
(1)取600重量份蒸馏水加入到烧杯中,再依次添加150重量份氯化钠、16重量份纳米二氧化硅、2.4重量份聚乙烯吡咯烷酮,搅拌均匀后,滴加硫酸调节溶液pH=3,得水相悬浮液;
(2)将150重量份丙烯酸、50重量份甲基丙烯酸、60重量份甲基丙烯羟乙酯、40重量份甲基丙烯酸甲酯加入到烧杯中,滴加1.88重量份甲基丙烯酸羟丙酯,2.5重量份二乙二醇二丙烯酸酯,然后再添加2重量份偶氮二异丁腈、30重量份戊烷、30重量份异己烷,搅拌均匀后得油相;
(3)将步骤(2)得到的油相加入到步骤(1)得到的水相悬浮液中,水相与油相悬浮液的质量比是1:1,在高速均质机中20000rpm下搅拌20min,分散成油相小液滴悬浮液后,转移至带搅拌的反应釜中,65℃下搅拌反应22h,过滤干燥得到表面富含羧基的热膨胀微球;
(4)在三孔圆底烧瓶中加入步骤(3)得到的热膨胀微球、对甲苯磺酸、对苯二酚、二甲苯,所述热膨胀微球与对甲苯磺酸、对苯二酚的质量比为7.04:0.01:0.001,所述热膨胀微球在所述二甲苯中的体积浓度为0.2g/mL,搅拌分散均匀后,将圆底烧瓶的温度升至70℃,持续搅拌下,在反应体系中持续滴加PETA,通过FTIR测量监测反应,待反应体系中羧基的吸收峰消失,羧基峰不在减少,反应结束后,正己烷洗涤沉淀,得产物b;
(5)在三孔圆底烧瓶中加入50g产物b、0.1g光引发剂、100mL甲苯,然后将圆底烧瓶的温度升至50℃,氮气保护下,将全氟烷基硫醇(CAS号:34451-28-0)持续滴加到烧瓶中,边搅拌边用波长为365nm的LED灯照射,通过FTIR测量监测反应,待反应体系中的双键吸收峰消失,反应结束,之后将反应液离心分离、水洗、干燥后,即得到表面接枝有长氟碳链的改性热膨胀微球。
具体地,所述活性单体包括HDDA、PET3A、TMP9EOTA中的至少一种。
具体地,所述光引发剂包括TPO、819、1173、184、ITX、907中的至少一种。
具体地,所述流平剂为有机硅类流平剂。
具体地,所述有机硅类流平剂包括BYK333、迪高450中的至少一种。
具体地,所述分散剂为高分子类分散剂。
具体地,所述高分子类分散剂包括BYK163。
具体地,所述消泡剂为有机硅类消泡剂。
具体地,所述有机硅类消泡剂包括迪高815N。
具体地,所述的人造革用UV涂料,其应用如下:
将其涂覆在人造皮革的表面,50℃下红外流平1min,然后将其置于紫外灯下光照,光照时间10-30s,光固化过程中,涂料体系中的改性热膨胀微球发生微膨胀,即得到表面富有细腻弹性触感的人造皮革。
有益效果
本发明涂料体系中添加有自制长氟碳链改性的热膨胀微球,长氟碳链的存在赋予改性热膨胀微球低表面能,使得改性热膨胀微球具有上浮的特性,将本发明所获光固化涂料涂覆在人造革的表面,红外流平过程中涂料中的改性热膨胀微球倾向于集中分布在涂层的表面,光固化过程中,通过控制控制光照时间,使得光固化涂料中的改性热膨胀微球受热后发生微膨胀,最终获得表面富有细腻弹性触感的人造皮革。
具体实施方式
本发明以下实施例中的改性热膨胀微球按照以下步骤制备:
(1)取600重量份蒸馏水加入到烧杯中,再依次添加150重量份氯化钠、16重量份纳米二氧化硅、2.4重量份聚乙烯吡咯烷酮,搅拌均匀后,滴加硫酸调节溶液pH=3,得水相悬浮液;
(2)将150重量份丙烯酸、50重量份甲基丙烯酸、60重量份甲基丙烯羟乙酯、40重量份甲基丙烯酸甲酯加入到烧杯中,滴加1.88重量份甲基丙烯酸羟丙酯,2.5重量份二乙二醇二丙烯酸酯,然后再添加2重量份偶氮二异丁腈、30重量份戊烷、30重量份异己烷,搅拌均匀后得油相;
(3)将步骤(2)得到的油相加入到步骤(1)得到的水相悬浮液中,水相与油相悬浮液的质量比是1:1,在高速均质机中20000rpm下搅拌20min,分散成油相小液滴悬浮液后,转移至带搅拌的反应釜中,65℃下搅拌反应22h,过滤干燥得到表面富含羧基的热膨胀微球;
(4)在三孔圆底烧瓶中加入步骤(3)得到的热膨胀微球、对甲苯磺酸、对苯二酚、二甲苯,所述热膨胀微球与对甲苯磺酸、对苯二酚的质量比为7.04:0.01:0.001,所述热膨胀微球在所述二甲苯中的体积浓度为0.2g/mL,搅拌分散均匀后,将圆底烧瓶的温度升至70℃,持续搅拌下,在反应体系中持续滴加PETA,通过FTIR测量监测反应,待反应体系中羧基的吸收峰消失,羧基峰不在减少,反应结束后,正己烷洗涤沉淀,得产物b;
(5)在三孔圆底烧瓶中加入50g产物b、0.1g光引发剂、100mL甲苯,然后将圆底烧瓶的温度升至50℃,氮气保护下,将全氟烷基硫醇(CAS号:34451-28-0)持续滴加到烧瓶中,边搅拌边用波长为365nm的LED灯照射,通过FTIR测量监测反应,待反应体系中的双键吸收峰消失,反应结束,之后将反应液离心分离、水洗、干燥后,即得到表面接枝有长氟碳链的改性热膨胀微球。
本发明以下实施例所采用的环氧丙烯酸树脂为长兴UV环氧低聚物6210G。
本发明以下实施例所采用的聚氨酯丙烯酸树脂为脂肪族聚氨酯丙烯酸酯HM-2527,购自江西坤隆新材料有限公司。
本发明以下实施例所采用的聚酯丙烯酸树脂为中山科田聚酯丙烯酸酯2101UV树脂。
本发明采用的热膨胀微球F-48D购自北京森昌泰和科技有限责任公司。
实施例1
一种人造革用UV涂料,以重量份数计,组成如下:
实施例2
一种人造革用UV涂料,以重量份数计,组成如下:
实施例3
一种人造革用UV涂料,以重量份数计,组成如下:
实施例4
一种人造革用UV涂料,以重量份数计,组成如下:
实施例5
一种人造革用UV涂料,以重量份数计,组成如下:
对比例1同实施例1,不同之处在于,对比例1采用舜泰科技生产的微球发泡剂ST13替换本发明自制的改性热膨胀微球。
对比例2同实施例1,不同之处在于,对比例2采用美国POLYCHEM公司生产的热膨胀发泡微球180DU25替换本发明自制的改性热膨胀微球。
应用:
将本发明实施例1-5以及对比例1-2所获人造革用UV涂料分别涂覆在相同的人造革表面,50℃下红外流平1min,20-30μm,然后将其置于紫外灯下光照,光照时间30s,使得涂料体系中的改性热膨胀微球发生微膨胀,最终获得表面富有细腻弹性触感的人造皮革。
对本发明实施例1-5以及对比例1-2所获表面富有细腻弹性触感的人造皮革进行相关性能测试,具体测试如下:
弹性:拇指按压(一公斤力)人造革表面,观察是否回弹。
光固化涂层与人造革之间的附着力:按照GB/T9286-1998进行测试。
触感:用手触摸,与真皮的触感相比较。
耐污性:用油性笔涂鸦漆膜表面,用干纸巾擦拭观察是否有残留。
测试结果如表1所示:
表1
测试项 | 有无弹性 | 附着力(级) | 触感 | 耐污性 |
实施例1 | 有 | 0 | 真皮触感 | 无残留 |
实施例2 | 有 | 0 | 真皮触感 | 无残留 |
实施例3 | 有 | 0 | 真皮触感 | 无残留 |
实施例4 | 有 | 0 | 真皮触感 | 无残留 |
实施例5 | 有 | 0 | 真皮触感 | 无残留 |
对比例1 | 有 | 3 | 真皮触感 | 有残留 |
对比例2 | 有 | 4 | 真皮触感 | 有残留 |
对比例3 | 有 | 2 | 真皮触感 | 有残留 |
对比例3同实施例1,不同之处在于,对比例3涂覆在人造革表面后,未在50℃下红外流平1min。
以上所述,仅是本发明的较佳实施例而已,并非对本发明作任何形式上的限制,虽然本发明已以较佳实施例揭示如上,然而并非用以限定本发明,任何本领域技术人员,在不脱离本发明技术方案范围内,当可利用上述揭示的技术内容做出些许更动或修饰为等同变化的等效实施例,但凡是未脱离本发明技术方案内容,依据本发明的技术实质对以上实施例所作的任何简介修改、等同变化与修饰,均仍属于本发明技术方案的范围内。
Claims (9)
2.根据权利要求1所述的一种人造革用UV涂料,其特征在于,所述丙烯酸树脂为环氧丙烯酸树脂、聚氨酯丙烯酸树脂、聚酯丙烯酸树脂中的至少一种。
3.根据权利要求1所述的一种人造革用UV涂料,其特征在于,改性热膨胀微球按照以下步骤制备:
(1)取600重量份蒸馏水加入到烧杯中,再依次添加150重量份氯化钠、16重量份纳米二氧化硅、2.4重量份聚乙烯吡咯烷酮,搅拌均匀后,滴加硫酸调节溶液pH=3,得水相悬浮液;
(2)将150重量份丙烯酸、50重量份甲基丙烯酸、60重量份甲基丙烯羟乙酯、40重量份甲基丙烯酸甲酯加入到烧杯中,滴加1.88重量份甲基丙烯酸羟丙酯,2.5重量份二乙二醇二丙烯酸酯,然后再添加2重量份偶氮二异丁腈、30重量份戊烷、30重量份异己烷,搅拌均匀后得油相;
(3)将步骤(2)得到的油相加入到步骤(1)得到的水相悬浮液中,水相与油相悬浮液的质量比是1:1,在高速均质机中20000rpm下搅拌20min,分散成油相小液滴悬浮液后,转移至带搅拌的反应釜中,65℃下搅拌反应22h,过滤干燥得到表面富含羧基的热膨胀微球;
(4)在三孔圆底烧瓶中加入步骤(3)得到的热膨胀微球、对甲苯磺酸、对苯二酚、二甲苯,所述热膨胀微球与对甲苯磺酸、对苯二酚的质量比为7.04:0.01:0.001,所述热膨胀微球在所述二甲苯中的体积浓度为0.2g/mL,搅拌分散均匀后,将圆底烧瓶的温度升至70℃,持续搅拌下,在反应体系中持续滴加PETA,通过FTIR测量监测反应,待反应体系中羧基的吸收峰消失,羧基峰不在减少,反应结束后,正己烷洗涤沉淀,得产物b;
(5)在三孔圆底烧瓶中加入50g产物b、0.1g光引发剂、100mL甲苯,然后将圆底烧瓶的温度升至50℃,氮气保护下,将全氟烷基硫醇持续滴加到烧瓶中,边搅拌边用波长为365nm的LED灯照射,通过FTIR测量监测反应,待反应体系中的双键吸收峰消失,反应结束,之后将反应液离心分离、水洗、干燥后,即得到表面接枝有长氟碳链的改性热膨胀微球。
4.根据权利要求1所述的一种人造革用UV涂料,其特征在于,所述活性单体包括HDDA、PET3A、TMP9EOTA中的至少一种。
5.根据权利要求1所述的一种人造革用UV涂料,其特征在于,所述光引发剂包括TPO、819、1173、184、ITX、907中的至少一种。
6.根据权利要求1所述的一种人造革用UV涂料,其特征在于,所述流平剂为有机硅类流平剂。
7.根据权利要求1所述的一种人造革用UV涂料,其特征在于,所述分散剂为高分子类分散剂。
8.根据权利要求1所述的一种人造革用UV涂料,其特征在于,所述消泡剂为有机硅类消泡剂。
9.根据权利要求1-8任一项所述的人造革用UV涂料,其特征在于,其应用如下:
将其涂覆在人造皮革的表面,50℃下红外流平1min,然后将其置于紫外灯下光照,光照时间10-30s,光固化过程中,涂料体系中的改性热膨胀微球发生微膨胀,即得到表面富有细腻弹性触感的人造皮革。
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