CN108049196A - 一种阻燃抗菌墙纸 - Google Patents
一种阻燃抗菌墙纸 Download PDFInfo
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- 230000003115 biocidal effect Effects 0.000 title claims abstract description 34
- 238000000576 coating method Methods 0.000 claims abstract description 39
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- 238000007639 printing Methods 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 5
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 18
- -1 methyl methacrylates Ester Chemical class 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
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- 238000006243 chemical reaction Methods 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 11
- 239000003995 emulsifying agent Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical group [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 9
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- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
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- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 4
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- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 4
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-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 abstract description 2
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- 230000003373 anti-fouling effect Effects 0.000 abstract description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 7
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- 230000000845 anti-microbial effect Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
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- OOFAEFCMEHZNGP-UHFFFAOYSA-N 1-n',1-n'-dimethylpropane-1,1-diamine Chemical compound CCC(N)N(C)C OOFAEFCMEHZNGP-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical class ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000010538 cationic polymerization reaction Methods 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 238000003854 Surface Print Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
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- 238000011156 evaluation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
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Abstract
本发明公开了一种阻燃抗菌墙纸,包括无纺布基纸、基纸表面的涂料印刷层及附着在涂料印刷层上表面的阻燃抗菌涂层;本发明阻燃抗菌墙纸的阻燃抗菌涂层整理剂由丙烯酸酯、含氟丙烯酸酯、阻燃单体、有机季铵盐接枝纳米二氧化钛反应而成,形成了无机‑有机抗菌复合物,具有防水、抗菌、阻燃等功能,增强了墙纸的防霉、抗菌、防污、防水、阻燃等性能。
Description
技术领域
本发明涉及一种阻燃抗菌墙纸,属于墙纸领域。
背景技术
墙纸,以纯无纺布为基材,表面采用涂料印刷后涂上特殊材料,经特殊加工而成,具有吸音、不变形等优点,并且有强大的呼吸性能。
无纺布基材墙纸其材质是由天然纤维或合成纤维经过无纺形成,为墙纸中较环保的一种。
然而,该类墙纸在使用过程中易发霉、沾污。
发明内容
本发明的目的是提供一种阻燃抗菌墙纸,通过在基材纸的表面印制涂料及涂覆抗菌阻燃整理剂,使墙纸具备良好的抗菌、防水、阻燃等功能。
为实现上述目的,本发明采用的技术方案为:
一种阻燃抗菌墙纸,包括无纺布基纸、基纸表面的涂料印刷层及附着在涂料印刷层上表面的阻燃抗菌涂层;
所述的阻燃抗菌涂层由以下方法制备:
a、搅拌釜中加入200mL无水乙醇,纳米二氧化钛20份、3-丙烯酰胺丙基二甲基丙基三甲氧基硅烷氯化铵6份,40℃条件下搅拌反应24h,将混合液离心,用甲醇洗涤2次,在70℃烘干,得表面改性纳米二氧化钛,备用;
b、将12份表面改性的纳米二氧化钛、21份3-丙烯酰胺丙基二甲基丙基三甲氧基硅烷氯化铵、15份2-乙基(甲基丙烯酰氧甲基)膦酸酯、12份丙烯酸六氟丁酯、11份甲基丙烯酸甲酯、23份丙烯酸丁酯组成的混合物在高速均质分散机的作用下加入到乳化剂水溶液中,得到纳米二氧化钛与单体分散液;
c、将分散液转移到反应釜中,在一定搅拌速度下,快速升温到68℃,加入10份水与0.2份引发剂的水溶液,反应0.5h后,同步缓慢滴加入由14份甲基丙烯酸甲酯、25份丙烯酸丁酯、0.7份引发剂与20份水的溶液,滴加时间为2h;滴完后升温至80℃保温2h;反应完成后,降温出料,制得阻燃抗菌涂层整理剂。
所述3-丙烯酰胺丙基二甲基丙基三甲氧基硅烷氯化铵由N,N二甲基丙二胺、丙烯酰氯、γ-氯丙基三甲氧基硅烷制成,具体制备方法为:
在250mL的三口瓶中加入82mL二氯甲烷,25mL6mol/L氢氧化钠,0.1molN,N二甲基丙二胺,N2保护、冰水浴,在N2保护下,磁力均匀搅拌。将25mL溶有0.104mol丙烯酰氯的二氯甲烷溶液用恒压漏斗缓慢加入,保持反应温度不超过5℃。滴加完毕后,继续搅拌30min。取出有几层用水洗两次,饱和氯化钠溶液洗两次,再用无水硫酸钠干燥,然后用旋转蒸发仪蒸去溶剂,得到浅黄色油状物,再减压蒸馏,得到N.N-二甲基丙基丙烯酰胺;
取5gN.N-二甲基丙基丙烯酰胺于烧瓶中,加入10gγ-氯丙基三甲氧基硅烷,在N2保护下,磁力搅拌均匀,室温反应48h后,将未反应的γ-氯丙基三甲氧基硅烷,经液氮冷却,得白色固体,用2倍质量的乙醚洗涤两次,真空干燥,再以1:1丙酮及乙醚的混合溶剂洗涤,5℃以下重结晶,真空干燥,得白色固体,即为3-丙烯酰胺丙基二甲基丙基三甲氧基硅烷氯化铵。具体反应式如下:
所述的乳化剂水溶液由12份十六烷基三甲基氯化铵、5份AEO-9、4份聚乙二醇、3份十二烷基硫酸钠、132份水组成。
所述的引发剂为过硫酸钠。
本发明阻燃抗菌墙纸,阻燃抗菌涂层整理剂由丙烯酸酯、含氟丙烯酸酯、阻燃单体、有机季铵盐接枝纳米二氧化钛反应而成,形成了无机-有机抗菌复合物,具有防水、抗菌、阻燃等功能,增强了墙纸的防霉、抗菌、防污、防水、阻燃等性能。
具体实施方式
本发明公开了一种阻燃抗菌墙纸,包括无纺布基纸、基纸表面的涂料印刷层及附着在涂料印刷层上表面的阻燃抗菌涂层。
无纺布基纸,原料包括天然纤维、化学纤维、合成纤维,经非织方式形成,厚度约150-250um,150-250g/m2。
墙纸表面的图案通过涂料印刷方式形成,按图案的色彩分色,分别对图案制作印刷凹辊,由浅色至深色顺序分别印刷涂料,再经烘干,完成图案的印制。印刷的涂料层的厚度一般为1-5um。
为了增强墙纸的耐污、抗菌、阻燃等性能,在涂料印刷层的表面可以涂覆功能性涂层,该功能性涂层同常采用功能性的乳液,可直接对墙纸进行单面涂层,经高温干燥即可。
本发明使用的功能性涂层整理剂为阻燃抗菌涂层整理剂。
一种阻燃抗菌涂层整理剂,由12份表面改性纳米二氧化钛、21份阳离子聚合弹体、15份可聚合膦酸酯、12份含氟丙烯酸酯以及48份丙烯酸丁酯、25份甲基丙烯酸甲酯在0.9份引发剂、24份乳化剂、162份水存在下,经乳液聚合制成,
所述的阳离子聚合弹体为3-丙烯酰胺丙基二甲基丙基三甲氧基硅烷氯化铵。
所述3-丙烯酰胺丙基二甲基丙基三甲氧基硅烷氯化铵由N,N二甲基丙二胺、丙烯酰氯、γ-氯丙基三甲氧基硅烷制成,具体制备方法为:
在250mL的三口瓶中加入82mL二氯甲烷,25mL6mol/L氢氧化钠,0.1molN,N二甲基丙二胺,N2保护、冰水浴,在N2保护下,磁力均匀搅拌。将25mL溶有0.104mol丙烯酰氯的二氯甲烷溶液用恒压漏斗缓慢加入,保持反应温度不超过5℃。滴加完毕后,继续搅拌30min。取出有几层用水洗两次,饱和氯化钠溶液洗两次,再用无水硫酸钠干燥,然后用旋转蒸发仪蒸去溶剂,得到浅黄色油状物,再减压蒸馏,得到N.N-二甲基丙基丙烯酰胺;
取5gN.N-二甲基丙基丙烯酰胺于烧瓶中,加入10gγ-氯丙基三甲氧基硅烷,在N2保护下,磁力搅拌均匀,室温反应48h后,将未反应的γ-氯丙基三甲氧基硅烷,经液氮冷却,得白色固体,用2倍质量的乙醚洗涤两次,真空干燥,再以1:1丙酮及乙醚的混合溶剂洗涤,5℃以下重结晶,真空干燥,得白色固体,即为3-丙烯酰胺丙基二甲基丙基三甲氧基硅烷氯化铵。
所述的可聚合膦酸酯为2-乙基(甲基丙烯酰氧甲基)膦酸酯。
所述的含氟丙烯酸酯为丙烯酸六氟丁酯。
所述的引发剂为过硫酸钠。
所述的阻燃抗菌涂层由以下方法制备:
a、搅拌釜中加入200mL无水乙醇,纳米二氧化钛20份、3-丙烯酰胺丙基二甲基丙基三甲氧基硅烷氯化铵6份,40℃条件下搅拌反应24h,将混合液离心,用甲醇洗涤2次,在70℃烘干,得表面改性纳米二氧化钛,备用;
b、将12份表面改性的纳米二氧化钛、21份3-丙烯酰胺丙基二甲基丙基三甲氧基硅烷氯化铵、15份2-乙基(甲基丙烯酰氧甲基)膦酸酯、12份丙烯酸六氟丁酯、11份甲基丙烯酸甲酯、23份丙烯酸丁酯组成的混合物在高速均质分散机的作用下加入到乳化剂水溶液中,得到纳米二氧化钛与单体分散液;所述的乳化剂水溶液由12份十六烷基三甲基氯化铵、5份AEO-9、4份聚乙二醇、3份十二烷基硫酸钠、132份水组成;
c、将分散液转移到反应釜中,在一定搅拌速度下,快速升温到68℃,加入10份水与0.2份引发剂的水溶液,反应0.5h后,同步缓慢滴加入由14份甲基丙烯酸甲酯、25份丙烯酸丁酯、0.7份引发剂与20份水的溶液,滴加时间为2h;滴完后升温至80℃保温2h;反应完成后,降温出料,制得阻燃抗菌涂层整理剂。
实施例1:
丙烯酰氧乙基-丙基三甲氧基硅烷-二甲基氯化铵的制备:
在单口烧瓶中加入1mol N,N-二甲基乙醇胺、1.05molγ-氯丙基三甲氧基硅烷、200mL乙腈,搅拌,缓慢加热至70℃左右,回流反应36h后,将反应液置于冰浴中冷却,待结晶析出,抽滤,干燥,得白色粉末固体,即丙基三甲氧基硅烷-乙醇基-二甲基氯化铵;
在单口烧瓶中加入1mol丙基三甲氧基硅烷-乙醇基-二甲基氯化铵、1.1mol丙烯酰氯及少量对苯二酚,150mL乙醚,控制反应温度5℃,反应4h,反应完毕后,将瓶中的混合液过滤,减压蒸馏除去未反应物,得丙烯酰氧乙基-丙基三甲氧基硅烷-二甲基氯化铵。
实施例2:
一种阻燃抗菌涂层整理剂,由12份表面改性纳米二氧化钛、21份3-丙烯酰胺丙基二甲基丙基三甲氧基硅烷氯化铵、15份2-乙基(甲基丙烯酰氧甲基)膦酸酯、12份丙烯酸六氟丁酯以及48份丙烯酸丁酯、25份甲基丙烯酸甲酯在0.9份引发剂、24份乳化剂、162份水存在下,经乳液聚合制成,
所述的阻燃抗菌涂层由以下方法制备:
a、搅拌釜中加入200mL无水乙醇,纳米二氧化钛20份、3-丙烯酰胺丙基二甲基丙基三甲氧基硅烷氯化铵6份,40℃条件下搅拌反应24h,将混合液离心,用甲醇洗涤2次,在70℃烘干,得表面改性纳米二氧化钛,备用;
b、将12份表面改性的纳米二氧化钛、21份3-丙烯酰胺丙基二甲基丙基三甲氧基硅烷氯化铵、15份2-乙基(甲基丙烯酰氧甲基)膦酸酯、12份丙烯酸六氟丁酯、11份甲基丙烯酸甲酯、23份丙烯酸丁酯组成的混合物在高速均质分散机的作用下加入到乳化剂水溶液中,得到纳米二氧化钛与单体分散液;所述的乳化剂水溶液由12份十六烷基三甲基氯化铵、5份AEO-9、4份聚乙二醇、3份十二烷基硫酸钠、132份水组成;
c、将分散液转移到反应釜中,在一定搅拌速度下,快速升温到68℃,加入10份水与0.2份过硫酸钠的水溶液,反应0.5h后,同步缓慢滴加入由14份甲基丙烯酸甲酯、25份丙烯酸丁酯、0.7份过硫酸钠与20份水的溶液,滴加时间为2h;滴完后升温至80℃保温2h;反应完成后,降温出料,制得阻燃抗菌涂层整理剂。
实施例3:
一种阻燃抗菌墙纸,包括无纺布基纸、基纸表面的涂料印刷层及附着在涂料印刷层上表面的阻燃抗菌涂层;阻燃抗菌涂层由实施例2方法制备。
墙纸的制备:
a、查验无纺布基纸,
b、基纸表面印制涂料,花型、颜色根据需要设定,
c、烘干,
d、在涂料层表面进行阻燃抗菌涂层,
e、烘干
f、收卷。
应用例:
抗菌性能按《GB/T 20944.3-2008纺织品抗菌性能的评价第3部分:振荡法》测试。
阻燃性能按《GB/T 5455-2014纺织品燃烧性能垂直方向损毁长度、阴燃和续燃时间的测定》测试。
表1墙纸的抗菌性能
表2墙纸的阻燃性能
由表1、2可知,墙纸具有良好的阻燃、抗菌性能。
Claims (3)
1.一种阻燃抗菌墙纸,包括无纺布基纸、基纸表面的涂料印刷层及附着在涂料印刷层上表面的阻燃抗菌涂层;
所述的阻燃抗菌涂层由以下方法制备:
a、搅拌釜中加入200mL无水乙醇,纳米二氧化钛20份、3-丙烯酰胺丙基二甲基丙基三甲氧基硅烷氯化铵6份,40℃条件下搅拌反应24h,将混合液离心,用甲醇洗涤2次,在70℃烘干,得表面改性纳米二氧化钛,备用;
b、将12份表面改性的纳米二氧化钛、21份3-丙烯酰胺丙基二甲基丙基三甲氧基硅烷氯化铵、15份2-乙基(甲基丙烯酰氧甲基)膦酸酯、12份丙烯酸六氟丁酯、11份甲基丙烯酸甲酯、23份丙烯酸丁酯组成的混合物在高速均质分散机的作用下加入到乳化剂水溶液中,得到纳米二氧化钛与单体分散液;
c、将分散液转移到反应釜中,在一定搅拌速度下,快速升温到68℃,加入10份水与0.2份引发剂的水溶液,反应0.5h后,同步缓慢滴加入由14份甲基丙烯酸甲酯、25份丙烯酸丁酯、0.7份引发剂与20份水的溶液,滴加时间为2h;滴完后升温至80℃保温2h;反应完成后,降温出料,制得阻燃抗菌涂层整理剂。
2.根据权利要求1所述的一种阻燃抗菌墙纸,其特征在于:所述的乳化剂水溶液由12份十六烷基三甲基氯化铵、5份AEO-9、4份聚乙二醇、3份十二烷基硫酸钠、132份水组成。
3.根据权利要求1所述的一种阻燃抗菌墙纸,其特征在于:所述的引发剂为过硫酸钠。
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