CN114941245A - 一种合成革用水性粘合剂及其制备方法 - Google Patents
一种合成革用水性粘合剂及其制备方法 Download PDFInfo
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- CN114941245A CN114941245A CN202210390865.8A CN202210390865A CN114941245A CN 114941245 A CN114941245 A CN 114941245A CN 202210390865 A CN202210390865 A CN 202210390865A CN 114941245 A CN114941245 A CN 114941245A
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- emulsion
- water
- agent
- aqueous
- combination
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Classifications
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—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 otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
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- D06N3/145—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 otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes two or more layers of polyurethanes
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
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- D06N3/0086—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the application technique
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—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 otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—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 otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
- D06N3/142—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 otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes mixture of polyurethanes with other resins in the same layer
- D06N3/144—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 otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes mixture of polyurethanes with other resins in the same layer with polyurethane and polymerisation products, e.g. acrylics, PVC
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
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Abstract
本发明涉及一种合成革用水性粘合剂及其制备方法,水性粘合剂主要包含水性聚氨酯乳液、水性丙烯酸乳液、水性氯丁乳液和增粘乳液,制备水性聚氨酯乳液的多元醇包含选自聚己二酸‑2‑丁基‑2‑乙基‑1,3‑丙二醇、聚己二酸‑1,6‑己二醇和聚氧化丙烯二醇;水性丙烯酸乳液为具有压敏性的水性丙烯酸乳液。本发明采用特定多元醇制备的水性聚氨酯乳液配合一定量的水性氯丁乳液和水性丙烯酸乳液、增粘乳液及其它助剂的使用,制备的水性粘合剂具有更加优异的剥离负荷强度,用于合成革上,能实现更加宽泛的施工工艺,可以不用烘干立即进行贴合工序,或者在烘箱将全部或者部分水烘掉进行贴合工序即可,同时制备的合成革具有优异的耐老化性能和耐折性。
Description
技术领域
本发明属于粘合剂技术领域,具体涉及一种合成革用水性粘合剂及其制备方法。
背景技术
溶剂型聚氨酯合成革在生产和使用过程中,会对环境造成严重的污染、有很大的燃烧、爆炸的风险及对人类健康产生危害。作为一种重要的环保合成革,水性合成革可以从根本上解决这些问题。
据了解,目前国内聚氨酯革用树脂年消耗量大约140万吨,溶剂型聚氨酯革用树脂产量占比约95%,水性等环保型聚氨酯革用树脂产量仅占比约5%。
水性环保型合成革的占比较小主要受限于基础原材料的性能及其使用工艺的苛刻要求。水性粘合剂是生产水性环保型合成革的重要原料之一,水性环保合成革对水性粘合剂的性能和使用工艺要求较高。
在传统的溶剂型干法制革中一般采用干贴、半干贴及湿贴均可。合成革厂对水性粘合剂存在同样的要求,目的是保证合成革的生产稳定性。同时,合成革厂要求水性粘合剂的各项性能(如粘接强度、耐老化性)达到或优于溶剂型粘合剂的性能。
近年来随着国际和国家更严格的环保法规的出台及环保政策的趋严,以及消费者消费观念的变化,水性环保合成革得到前所未有的重视。然而目前的革用水性粘合剂大多采用水性聚氨酯粘合剂,其更适用湿贴和半干贴。湿贴和半干贴对生产控制要求很高,否则水性粘合剂容易渗透到基布里面,导致合成革手感明显变硬,而干贴时由于初期粘力低导致终粘力低,工艺宽泛性较差,达不到溶剂型的工艺宽泛性。所以,目前合成革市场亟需一种工艺宽泛性强及综合性能优异的水性粘合剂。
发明内容
本发明目的是为了克服现有技术的不足而提供一种工艺宽泛性强及综合性能更优异的合成革用水性粘合剂及其制备方法。
为达到上述目的,本发明所采用的技术方案为:
一种合成革用水性粘合剂,按重量份计,所述水性粘合剂包含以下组分:
其中,制备所述水性聚氨酯乳液的多元醇包含聚己二酸-2-丁基-2-乙基-1,3-丙二醇、聚己二酸-1,6-己二醇、聚氧化丙烯二醇中的一种或几种的组合;
所述水性丙烯酸乳液为具有压敏性的水性丙烯酸乳液。
本发明中,所述水性丙烯酸乳液为水性丙烯酸压敏胶,固含量为45%-60%。
所述水性聚氨酯乳液的固含量为30~45%。
所述水性氯丁乳液的固含量为50~60%。
本发明中,所述水性氯丁乳液为聚氯丁二烯的水基胶态分散体,可以是高结晶速率的水性氯丁乳液、慢结晶速率的水性氯丁乳液、化学改性的水性氯丁乳液的一种或几种的组合,优选高结晶速率的水性氯丁乳液,如科思创公司的Dispercoll C84。
在所述水性粘合剂中加入一定量的水性氯丁乳液有助于显著提高粘合剂的剥离负荷强度及耐老化性,且用于合成革上,不损坏合成革的耐折性。而若水性氯丁乳液用量过多,则显著降低合成革的耐折性。
根据本发明的一些实施方面,按重量份计,所述水性聚氨酯乳液的原料配方包括以下组分:
所述多元醇为聚己二酸-2-丁基-2-乙基-1,3-丙二醇、聚己二酸-1,6-己二醇、聚氧化丙烯二醇中的一种或几种的组合,数均分子量为2000~3000;
所述异氰酸酯为甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷二异氰酸酯、二环己基甲烷二异氰酸酯、六亚甲基二异氰酸酯中的一种或几种的组合。
优选地,所述多元醇为聚己二酸-1,6-己二醇与聚氧化丙烯二醇的组合或聚己二酸-2-丁基-2-乙基-1,3-丙二醇。
优选地,所述异氰酸酯为甲苯二异氰酸酯。
进一步地,所述亲水剂为二羟甲基丙酸、二羟甲基丁酸、胺基磺酸钠、侧基带有羧基或磺酸钠基的多元醇中的一种或几种的组合。优选地,所述亲水剂为二羟甲基丙酸、二羟甲基丁酸中的一种或几种的组合。
进一步地,所述成盐剂为三乙胺、三丁胺、三丙胺、三乙醇胺、二甲基乙醇胺中的一种或几种的组合。
进一步地,所述封端剂为甲醇、乙醇、丙醇、丙烯酸羟乙酯、二乙胺、二乙醇胺、一乙醇胺的一种或几种的组合。优选地,所述封端剂为二乙醇胺、一乙醇胺的一种或几种的组合。
进一步地,所述扩链剂为醇类扩链剂和/或胺类扩链剂,所述醇类扩链剂为乙二醇、二甘醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、2,2-二甲基-1,3-丙二醇、1,3-丙二醇、二丙二醇、三羟甲基丙烷、三羟甲基丁烷中的一种或几种,所述胺类扩链剂为水合肼、乙二胺、丙二胺、二乙烯三胺、异佛尔酮二胺、羟乙基乙二胺、氨乙基氨丙基三甲氧基硅烷、氨丙基三甲氧基硅烷中的一种或几种。优选地,所述扩链剂为羟乙基乙二胺。
本发明中,采用羟乙基乙二胺作为扩链剂结合采用二乙醇胺或一乙醇胺作为封端剂制备的水性聚氨酯乳液用于水性粘合剂有助于提高粘合剂的剥离负荷强度。
根据本发明的一些实施方面,当选用的所述亲水剂中含有二羟甲基丙酸、二羟甲基丁酸、侧基带有羧基的多元醇中的至少一种时,所述水性聚氨酯乳液的原料配方中还需用所述成盐剂进行中和,所述成盐剂为用量为5~20份;当选用的所述亲水剂仅为胺基磺酸钠、侧基带有磺酸钠基的多元醇中的一种或几种时,所述水性聚氨酯乳液的原料配方中不添加所述成盐剂。
当选用的所述亲水剂中含有二羟甲基丙酸、二羟甲基丁酸、侧基带有羧基的多元醇中的至少一种时,所述水性聚氨酯乳液的制备方法包括使多元醇和亲水剂在110~120℃下脱水,然后降温至60~90℃,加入异氰酸酯、催化剂进行反应,待NCO残留值降至5.3%以下,加入有机溶剂降粘,然后成盐剂在50~60℃反应5~20min,然后与水剪切乳化,乳化完毕,加入扩链剂和封端剂搅拌,然后减压蒸馏脱除有机溶剂,制得固含量为30~45%的水性聚氨酯乳液。
当选用的所述亲水剂仅为胺基磺酸钠、侧基带有磺酸钠基的多元醇中的一种或几种时,所述水性聚氨酯乳液的制备方法包括使多元醇在110~120℃下脱水,然后降温至60~90℃,加入异氰酸酯、扩链剂和催化剂进行反应,待NCO残留值降至5.3%以下,加入有机溶剂降粘,加入亲水剂在50~60℃下反应20~40min,然后与水剪切乳化,乳化完毕,加入封端剂搅拌,然后减压蒸馏脱除有机溶剂,制得固含量为30~45%的水性聚氨酯乳液。
进一步优选地,按重量份计,所述水性聚氨酯乳液的原料配方包括以下组分:
进一步地,所述有机溶剂为丙酮、丁酮中的一种或多种的组合。
根据本发明的一些实施方面,所述增粘乳液为水性松香增粘乳液、水性萜烯酚树脂、化学改性的水性松香乳液的一种或几种的组合。优选地,所述增粘乳液为水性萜烯酚树脂。
根据本发明的一些实施方面,所述固化剂为水性异氰酸酯固化剂、聚氮丙啶固化剂、水性碳化二亚胺类固化剂、密胺类固化剂的一种或几种的组合。优选地,所述固化剂为水性异氰酸酯固化剂,相比其它类型固化剂,更能获得更好的剥离负荷强度及耐老化性。
根据本发明的一些实施方面,所述消泡剂为聚硅氧烷类消泡剂、聚醚类消泡剂、矿物油类消泡剂的一种或几种的组合。
根据本发明的一些实施方面,所述流平润湿剂为聚醚改性硅氧烷的一种或几种的组合。
根据本发明的一些实施方面,所述增稠剂为水性丙烯酸增稠剂、水性聚氨酯增稠剂的一种或几种的组合。
在一些优选且具体实施方式中,所述水性聚氨酯乳液、水性丙烯酸乳液、水性氯丁乳液的质量比为3.5~5:1~1.5:1;
所述水性氯丁乳液为Dispercoll C84;
所述固化剂为水性异氰酸酯固化剂;
所述增粘乳液为水性萜烯酚树脂;
按重量份计,所述水性聚氨酯乳液的原料配方包括以下组分:
所述多元醇为聚己二酸-1,6-己二醇和聚氧化丙烯二醇的混合物,且所述聚己二酸-1,6-己二醇和聚氧化丙烯二醇的质量比为1~2.5:1;
所述亲水剂为二羟甲基丙酸、二羟甲基丁酸中的一种或多种的组合;
所述异氰酸酯为甲苯二异氰酸酯;
所述封端剂为二乙醇胺、一乙醇胺中的一种或多种的组合;
所述扩链剂为羟乙基乙二胺。
本发明采取的另一技术方案:一种上述所述的水性粘合剂的制备方法,所述制备方法包括使所述水性聚氨酯乳液、水性丙烯酸乳液和增粘乳液混合,调pH值至8~9,然后加入水性氯丁乳液搅拌,然后加入消泡剂、流平润湿剂、固化剂和增稠剂,将粘度增至设计值,制得所述水性粘合剂。
所述调pH值至8~9采用的物质为氨水、2-氨基-2-甲基-1-丙醇中的一种或多种的组合。
所述粘度的设定值为3000~5000mPas。
由于上述技术方案运用,本发明与现有技术相比具有下列优点:
本发明采用特定多元醇制备的水性聚氨酯乳液配合一定量的水性氯丁乳液和水性丙烯酸乳液、增粘乳液及配合其它助剂的使用,制备的水性粘合剂具有更加优异的剥离负荷强度,用于合成革上,可以实现更加宽泛的施工工艺,可以不用烘干立即进行贴合工序,或者在烘箱将全部或者部分水烘掉进行贴合工序即可,同时制备的合成革具有优异的耐老化性能和耐折性。
具体实施方式
下面结合具体实施例对本发明的具体实施作进一步详细说明,但本发明的实施和保护范围不限于此。
实施例1
本实施例提供的水性粘合剂,通过以下方法制备得到:
(1)水性聚氨酯乳液的制备
向反应器中加入295克聚己二酸-2-丁基-2-乙基-1,3-丙二醇(分子量2000)和15克二羟甲基丙酸,120℃通氮气脱水2小时。然后降温至60℃,加入90克TDI-80,并加入有机铋催化剂0.2克,75-85℃反应一定时间。待NCO残留值降低至5.3%时,降温至60℃加入100克丙酮降粘,并加入11.3克三乙胺,50-60℃反应10分钟,制得预聚体。
然后将预聚体压入高速搅拌的700克水中剪切乳化,并向其加入5.2克羟乙基乙二胺和23克二乙醇胺,搅拌1小时。减压蒸馏脱除丙酮,最终获得固含量37%的水性聚氨酯乳液。
(2)水性粘合剂的制备
向搅拌器中加入70克水性聚氨酯乳液,边搅拌边加入15克水性丙烯酸乳液(BLJ-569,上海保立佳化工股份有限公司)和5克水性萜烯酚树脂(吉田968,深圳市吉田化工有限公司)。搅拌均匀后加入氨水,调节pH至8-9。然后加入15克水性氯丁乳液C84(科思创公司生产),搅拌均匀。加入0.3克水性聚硅氧烷类消泡剂、0.3克聚醚改性硅氧烷流平润湿剂(毕克333,毕克化学)、3.5克水性异氰酸酯固化剂Desmodur DN(科思创公司生产)及0.8克水性聚氨酯增稠剂(RHEOBYK-T 1010VF,毕克化学)。将粘度增至5000mPas待用。
将本例中的水性粘合剂配合水性聚氨酯面层树脂(如选用万华公司的Leasys3250)制备水性合成革,方法如下:
在离型纸上涂刮水性聚氨酯面层树脂(0.1毫米厚),烘干(120℃、3分钟)成型获得水性聚氨酯面层;在水性聚氨酯面层上涂覆上述水性粘合剂,进行预烘(烘干温度、时间无具体要求)后获得水性粘合层,再将基布贴合,进入烘箱交联固化、定型(120℃、6分钟)、剥离离型纸后即可获得水性合成革。
对水性合成革进行性能测试,结果如表1所示。
表1为采用实施例1的水性粘合剂制备的合成革的性能测试结果
实施例2
本实施例提供的水性粘合剂,通过以下方法制备得到:
(1)水性聚氨酯乳液的制备
向反应器中加入200克聚己二酸-1,6己二醇(分子量2000)、113克聚氧化丙烯二醇(分子量2000)和15克二羟甲基丙酸,120℃通氮气脱水2小时。然后降温至60℃,加入72克TDI-80,并加入有机铋催化剂0.2克,75-85℃反应一定时间。待NCO残留值降低至3%时,降温至60℃加入150克丙酮降粘,并加入11.3克三乙胺,50-60℃反应10分钟,制得预聚体。
然后将预聚体压入高速搅拌的800克水中剪切乳化,并向其加入4.6克一乙醇胺和1.9克羟乙基乙二胺,搅拌1小时。减压蒸馏脱除丙酮,最终获得固含量33%的水性聚氨酯乳液。
(2)水性粘合剂的制备
向搅拌器中加入60克水性聚氨酯乳液,边搅拌边加入20克水性丙烯酸乳液(同实施例1)和6克水性萜烯酚树脂(同实施例1)。搅拌均匀后加入氨水,调节pH至8-9。然后加入15克水性氯丁乳液C84(科思创公司生产),搅拌均匀。加入0.3克消泡剂(同实施例1)、0.3克流平润湿剂(同实施例1)、3.5克水性异氰酸酯固化剂Desmodur DN(科思创公司生产)及0.7克水性增稠剂(同实施例1)。将粘度增至3000mPas待用。
将本例中的水性粘合剂配合水性聚氨酯面层树脂(如选用万华公司的Leasys3250)、水性聚氨酯贝斯层树脂(如选用万华公司的Leasys3233A)制备水性合成革,方法如下:
(1)在基布上涂覆水性聚氨酯贝斯浆料(0.3毫米厚),烘干定型(130℃、10分钟)获得水性聚氨酯贝斯层。
(2)在离型纸上涂刮水性聚氨酯面层树脂(0.1毫米厚),烘干成型(120℃、3分钟)获得水性聚氨酯面层。
(3)在水性聚氨酯面层上涂覆上述水性粘合剂,进行预烘(烘干温度、时间无具体要求)后获得水性粘合层,再贴合步骤(1)获得的贝斯层,进入烘箱交联固化、定型(120℃、6分钟)、剥离离型纸后即可获得水性合成革。
对水性合成革进行性能测试,结果如表2所示。
表2为采用实施例2的水性粘合剂制备的合成革的性能测试结果
对比例1
本对比例提供的水性粘合剂,通过以下方法制备得到:
(1)水性聚氨酯乳液的制备
向反应器中加入295克聚己二酸-乙二醇(分子量2000)和15克二羟甲基丙酸,120℃通氮气脱水2小时。然后降温至60℃,加入90克TDI-80,并加入有机铋催化剂0.2克,75-85℃反应一定时间。待NCO残留值降低至5.3%时,降温至60℃加入100克丙酮降粘,并加入11.3克三乙胺,50-60℃反应10分钟,制得预聚体。
然后将预聚体压入高速搅拌的700克水中剪切乳化,并向其加入3克乙二胺和16克二乙胺,搅拌1小时。减压蒸馏脱除丙酮,最终获得固含量37%的水性聚氨酯乳液。
(2)水性粘合剂的制备
向搅拌器中加入70克水性聚氨酯乳液,边搅拌边加入15克水性丙烯酸乳液(同实施例1)和5克水性松香增粘乳液(AT880,广东威斯达新材料有限公司)。搅拌均匀后加入氨水,调节pH至8-9。然后加入15克水性氯丁乳液C74(科思创公司生产),搅拌均匀。加入0.3克消泡剂(同实施例1)、0.3克流平润湿剂(同实施例1)、1克聚氮丙啶固化剂及0.8克水性增稠剂(同实施例1)。将粘度增至5000mPas待用。
将本例中的水性粘合剂配合水性聚氨酯面层树脂制备水性合成革,方法如下:
在离型纸上涂刮水性聚氨酯面层树脂(0.1毫米厚),烘干(120℃、3分钟)成型获得水性聚氨酯面层;在水性聚氨酯面层上涂覆上述水性粘合剂,进行预烘(烘干温度、时间无具体要求)后获得水性粘合层,再将基布贴合,进入烘箱交联固化、定型(120℃、6分钟)、剥离离型纸后即可获得水性合成革。
对水性合成革进行性能测试,结果如表3所示。
表3为采用对比例1的水性粘合剂制备的合成革的性能测试结果
对比例2
本对比例提供的水性粘合剂,通过以下方法制备得到:
(1)水性聚氨酯乳液的制备
向反应器中加入200克聚己二酸-1,4丁二醇(分子量2000)、113克聚氧化丙烯二醇(分子量2000)和15克二羟甲基丙酸,120℃通氮气脱水2小时。然后降温至60℃,加入72克TDI-80,并加入有机铋催化剂0.2克,75-85℃反应一定时间。待NCO残留值降低至3%时,降温至60℃加入150克丙酮降粘,并加入11.3克三乙胺,50-60℃反应10分钟,制得预聚体。
然后将预聚体压入高速搅拌的800克水中剪切乳化,并向其加入5.5克二乙胺和3.1克异佛尔酮二胺,搅拌1小时。减压蒸馏脱除丙酮,最终获得固含量33%的水性聚氨酯乳液。
(2)水性粘合剂的制备
向搅拌器中加入60克水性聚氨酯乳液,边搅拌边加入20克水性丙烯酸乳液(同实施例1)和6克水性松香增粘乳液(同对比例1)。搅拌均匀后加入氨水,调节pH至8-9。然后加入15克水性氯丁乳液C74(科思创公司生产),搅拌均匀。加入0.3克消泡剂(同实施例1)、0.3克流平润湿剂(同实施例1)、3.5克水性碳化二亚胺类固化剂及0.7克水性增稠剂(同实施例1)。将粘度增至3000mPas待用。
用上述水性粘合剂配合水性聚氨酯面层、水性聚氨酯贝斯层树脂制备水性合成革。
(1)在基布上涂覆水性聚氨酯贝斯浆料(0.3毫米厚),烘干定型(130℃、10分钟)获得水性聚氨酯贝斯层。
(2)在离型纸上涂刮水性聚氨酯面层树脂(0.1毫米厚),烘干成型(120℃、3分钟)获得水性聚氨酯面层。
(3)在水性面层上涂覆上述水性粘合剂,进行预烘(烘干温度、时间无具体要求)后获得水性粘合层,再贴合步骤(1)获得的贝斯层,进入烘箱交联固化、定型(120℃、6分钟)、剥离离型纸后即可获得水性合成革。
对水性合成革进行性能测试,结果如表4所示。
表4为采用对比例2的水性粘合剂制备的合成革的性能测试结果
上述剥离负荷、耐老化、耐折的测试方法如下:
剥离负荷:参考国家标准GB/T8949-2008,具体为:取试样三块(尺寸为150mm×30mm),用适量粘结胶将涂层与同类革涂层粘贴在一起,再将贴合好的试样置于135℃±5℃,恒温2h后对贴合处理的试样进行手剥,革样的涂层与基布分开至50mm,再将分开的两端分别夹在拉伸试验机的夹具上,以200mm/min的速度进行剥离,记录每块试样的强度并取算数平均值。
耐老化:参考行业标准QB/T4671-2014,具体为:将规定尺寸的试样吊挂于温度为70℃,相对湿度95%的恒温恒湿试验机中,放置时间为24h的整数倍,取出后评价有无光泽度、颜色、脱层等表面状态变化以及力学性能变化,以此来评价样品的耐老化程度。
耐折:GB/T8949-2008,具体为:将试样(尺寸为70mm×45mm)上部测试面向内对折,夹在可运动的夹具内,下部测试面向外对折,夹在固定的夹具内,上部运动的夹具带动试样运动。在耐折试验机运行规定的次数后,观察试样被曲挠部分的表面有无破损、裂纹等损坏现象。
上述实施例只为说明本发明的技术构思及特点,其目的在于让熟悉此项技术的人士能够了解本发明的内容并据以实施,并不能以此限制本发明的保护范围。凡根据本发明精神实质所作的等效变化或修饰,都应涵盖在本发明的保护范围之内。
在本文中所披露的范围的端点和任何值都不限于该精确的范围或值,这些范围或值应当理解为包含接近这些范围或值的值。对于数值范围来说,各个范围的端点值之间、各个范围的端点值和单独的点值之间,以及单独的点值之间可以彼此组合而得到一个或多个新的数值范围,这些数值范围应被视为在本文中具体公开。
Claims (10)
3.根据权利要求2所述的合成革用水性粘合剂,其特征在于,所述多元醇为聚己二酸-1,6-己二醇与聚氧化丙烯二醇的组合或聚己二酸-2-丁基-2-乙基-1,3-丙二醇;和/或,所述异氰酸酯为甲苯二异氰酸酯。
4.根据权利要求2所述的合成革用水性粘合剂,其特征在于,所述亲水剂为二羟甲基丙酸、二羟甲基丁酸、胺基磺酸钠、侧基带有羧基或磺酸钠基的多元醇中的一种或几种的组合;和/或,所述成盐剂为三乙胺、三丁胺、三丙胺、三乙醇胺、二甲基乙醇胺中的一种或几种的组合;和/或,所述封端剂为甲醇、乙醇、丙醇、丙烯酸羟乙酯、二乙胺、二乙醇胺、一乙醇胺的一种或几种的组合;和/或,所述扩链剂为醇类扩链剂和/或胺类扩链剂,所述醇类扩链剂为乙二醇、二甘醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、2,2-二甲基-1,3-丙二醇、1,3-丙二醇、二丙二醇、三羟甲基丙烷、三羟甲基丁烷中的一种或几种,所述胺类扩链剂为水合肼、乙二胺、丙二胺、二乙烯三胺、异佛尔酮二胺、羟乙基乙二胺、氨乙基氨丙基三甲氧基硅烷、氨丙基三甲氧基硅烷中的一种或几种。
5.根据权利要求4所述的合成革用水性粘合剂,其特征在于:当选用的所述亲水剂中含有二羟甲基丙酸、二羟甲基丁酸、侧基带有羧基的多元醇中的至少一种时,所述水性聚氨酯乳液的原料配方中还需用所述成盐剂进行中和,所述成盐剂的用量为5~20份;当选用的所述亲水剂仅为胺基磺酸钠、侧基带有磺酸钠基的多元醇中的一种或几种时,所述水性聚氨酯乳液的原料配方中不添加所述成盐剂。
6.根据权利要求5所述的合成革用水性粘合剂,其特征在于:所述亲水剂为二羟甲基丙酸、二羟甲基丁酸中的一种或多种的组合;所述扩链剂为羟乙基乙二胺;所述封端剂为二乙醇胺、一乙醇胺中的一种或多种的组合。
7.根据权利要求1所述的合成革用水性粘合剂,其特征在于:所述增粘乳液为水性松香增粘乳液、水性萜烯酚树脂、化学改性的水性松香乳液的一种或几种的组合;和/或,所述固化剂为水性异氰酸酯固化剂、聚氮丙啶固化剂、水性碳化二亚胺类固化剂、密胺类固化剂的一种或几种的组合;和/或,所述消泡剂为聚硅氧烷类消泡剂、聚醚类消泡剂、矿物油类消泡剂的一种或几种的组合;和/或,所述流平润湿剂为聚醚改性硅氧烷的一种或几种的组合;和/或,所述增稠剂为水性丙烯酸增稠剂、水性聚氨酯增稠剂的一种或几种的组合。
8.根据权利要求7所述的合成革用水性粘合剂,其特征在于:所述增粘乳液为水性萜烯酚树脂;所述固化剂为水性异氰酸酯固化剂。
9.根据权利要求1所述的合成革用水性粘合剂,其特征在于:所述水性聚氨酯乳液、水性丙烯酸乳液、水性氯丁乳液的质量比为3.5~5:1~1.5:1;
所述水性氯丁乳液为Dispercoll C84;
所述固化剂为水性异氰酸酯固化剂;
所述增粘乳液为水性萜烯酚树脂;
按重量份计,所述水性聚氨酯乳液的原料配方包括以下组分:
所述多元醇为聚己二酸-1,6-己二醇和聚氧化丙烯二醇的混合物,且所述聚己二酸-1,6-己二醇和聚氧化丙烯二醇的质量比为1~2.5:1;
所述亲水剂为二羟甲基丙酸、二羟甲基丁酸中的一种或多种的组合;
所述异氰酸酯为甲苯二异氰酸酯;
所述封端剂为二乙醇胺、一乙醇胺中的一种或多种的组合;
所述扩链剂为羟乙基乙二胺。
10.一种权利要求1~9中任一项所述的水性粘合剂的制备方法,其特征在于:所述制备方法包括使所述水性聚氨酯乳液、水性丙烯酸乳液、增粘乳液混合,调pH值至8~9,然后加入水性氯丁乳液搅拌,然后加入消泡剂、流平润湿剂、固化剂和增稠剂,将粘度增至设计值,制得所述水性粘合剂。
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KR101784727B1 (ko) * | 2016-06-28 | 2017-10-12 | 한국신발피혁연구원 | 점착력이 우수한 수성 폴리우레탄계 점착제의 제조방법 |
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CN115717325A (zh) * | 2022-09-01 | 2023-02-28 | 嘉兴博锐新材料有限公司 | 一种锦纶导电丝的加工工艺 |
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