CN109306630A - 一种水性丙烯酸粘合剂用交联剂及所得的粘合剂 - Google Patents
一种水性丙烯酸粘合剂用交联剂及所得的粘合剂 Download PDFInfo
- Publication number
- CN109306630A CN109306630A CN201811150706.0A CN201811150706A CN109306630A CN 109306630 A CN109306630 A CN 109306630A CN 201811150706 A CN201811150706 A CN 201811150706A CN 109306630 A CN109306630 A CN 109306630A
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- Prior art keywords
- crosslinking agent
- acid
- acryloid cement
- substance
- ether
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title abstract description 24
- -1 aldehyde compound Chemical class 0.000 claims abstract description 25
- 239000004568 cement Substances 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000004593 Epoxy Substances 0.000 claims abstract description 9
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
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Classifications
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
- D06P1/651—Compounds without nitrogen
- D06P1/65106—Oxygen-containing compounds
- D06P1/65112—Compounds containing aldehyde or ketone groups
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
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Abstract
本发明公开了一种丙烯酸粘合剂用交联剂,以重量百分计,该交联剂包含:5~30%的醛类化合物、1~20%的缩水甘油醚类化合物、2~10%环氧基化合物、1~10%的有机酸、10~30%的有机醇溶剂以及1~5%金属盐,余量为水;其中,本发明的交联剂可通过将上述各组分按比例称取混合均匀而制得。本发明的交联剂具有用量少,可有效提高丙烯酸类粘合剂粘接强度,而且不含毒性高的成分。
Description
技术领域
本发明涉及一种纺织印染用的助剂,更具体地讲,本发明涉及一种印染用水性丙烯酸粘合剂的交联剂以及所得的粘合剂。
背景技术
水性丙烯酸粘合剂广泛用于纤维的印花、染色。与染料印花、染色工艺相比,具有节水,节能,环保。但水性丙烯酸粘合剂通常采用乳液聚合法,成膜后的交联密度不高,粘接力不够,造成这类织物的皂洗牢度、摩擦牢度差。虽然可通过聚合时加入内交联剂改善这些缺陷,但还是难以满足市场的要求。
中国专利申请CN 200680000574.2公开了一种具有优异的抗冲击性的丙烯酸粘合剂组合物,其起到增强用于增大图像显示器的光学膜对外抗冲击性能的作用,并起到在热和湿热条件下增加光学膜的耐久性的作用。根据该发明,该具有优异抗冲击性能的丙烯酸粘合剂组合物包括:(a)100重量份丙烯酸共聚物、(b)0.01~10重量份交联剂和(c)0.5~20重量份含有氨基的聚合物;其中,丙烯酸共聚物通过:(1)0.5~10wt%的不含羧基的乙烯型单体、(2)0.5~20wt%的含有羧基的乙烯型单体和(3)余量的含有C1~C12烷基基团的(甲基)丙烯酸酯单体共聚合而获得;其中,所采用的交联剂选自由异氰酸酯交联剂、环氧交联剂、氨基树脂交联剂、氮杂环丙烷交联剂和金属鳌合物交联剂组成的组,例如选自如下一组的至少一种:甲苯二异氰酸酯、1,6-己二异氰酸酯、乙二醇二缩水甘油醚、丙二醇二缩水甘油醚、四缩水甘油基二甲苯二胺和三聚氰胺化合物。
中国专利申请CN 201710599814.5公开了一种丙烯酸粘合剂组合物及包含其的保护膜和显示装置,该丙烯酸粘合剂组合物包含通过使约120重量份至约250重量份的丙烯酸单体的混合物聚合而获得的丙烯酸聚合物与约0.1重量份至约1重量份的偶氮引发剂、约0.5重量份至约1重量份的填充剂、约1.5重量份至约2.5重量份的交联剂和约0.5重量份至约1重量份的抗静电剂,其中,交联剂可以是氮丙啶或异氰酸酯交联剂。例如,交联剂可以是1,1’-间苯二甲酰基-二(2-甲基氮丙啶)、三亚甲基二异氰酸酯、四亚甲基二异氰酸酯、六亚甲基二异氰酸酯、五亚甲基二异氰酸酯、1,2-亚丙基二异氰酸酯、1,3-亚丁基二异氰酸酯、十二亚甲基二异氰酸酯、2,4,4-三甲基六亚甲基二异氰酸酯、1,3-环戊烷二异氰酸酯、1,3-环己烷二异氰酸酯、1,4-环己烷二异氰酸酯、异佛尔酮二异氰酸酯、加氢的二苯基甲烷二异氰酸酯、加氢的亚二甲苯基二异氰酸酯、加氢的甲代亚苯基二异氰酸酯、加氢的四甲基亚二甲苯基二异氰酸酯、亚苯基二异氰酸酯、2,4-甲代亚苯基二异氰酸酯、2,2’-二苯基甲烷二异氰酸酯、4,4’-二苯基甲烷二异氰酸酯、4,4’-甲苯胺二异氰酸酯、4,4’-二苯基醚二异氰酸酯、4,4’-二苯基二异氰酸酯、1,5-亚萘基二异氰酸酯和亚二甲苯基二异氰酸酯中的任一个。
中国专利CN 200910265532.7公开了一种抗静电粘合剂组合物,该抗静电粘合剂组合物包括:(a)100重量份的(甲基)丙烯酸粘合剂树脂,该(甲基)丙烯酸粘合剂树脂具有能够与交联剂结合的官能团,(b)0.01至15重量份的交联剂,和(c)0.1至10重量份的季铵盐,其中,季铵盐通过将具有两个或更多个末端羟烷基的胺与有机酸或无机酸反应获得。其中,交联剂(b)包括:异氰酸酯化合物、环氧化合物、氮杂环丙烷化合物、金属螯合物和它们的混合物中的至少一种。
然而,上述用于丙烯酸粘合剂的交联剂适用于显示器的光学膜,并不适用于印染工业,因为这种交联剂含有异氰酸酯,而异氰酸酯是一种毒性较强、且有致癌嫌疑的物质,印染之后的织物具有较高的接触人体的几率,残存的异氰酸酯是巨大的健康问题。
为提高色牢度,中国专利申请CN 201710437595.0公开了一种使用改性丙烯酰胺提高色牢度的方法,其方法在于:在预乳化阶段,加入适量的这种改性丙烯酰胺,可以使丙烯酸酯粘合剂的附着力及色牢度有着明显地改善提高。其中,在丙烯酸乳液的反应体系中包含:A.单体:丙烯酸丁酯25~30%,苯乙烯8~15%;B.酸:丙烯酸0.2~1%,衣康酸0.2~1%;C.交联剂:改性丙烯酰胺IBMA0.2~2%;D.乳化剂:十二烷基硫酸钠0.1~1%,非离子乳化剂0.5~1.5%;E.功能单体:乙烯基硅油;F.引发剂:过硫酸铵0.04%;G.水:40~60%。其制备工艺过程如下:先把预乳液各组分加入到分散机中分散30min,待反应釜温度达到75摄氏度后,开始初加引发剂和初加5~10%的预乳液,待反应稳定后开始滴加预乳液以及滴加引发剂。2.5~3小时滴完,滴加过程中控制温度保持在85摄氏度左右,滴加结束后在原温度上保温1小时,然后降温后处理,后处理过后需保温20min,之后即可将温度降至45摄氏度以下,然后用氨水调节PH=7.0左右,最后出料包装。其中,其预乳液包括:110克苯乙烯、270克丙烯酸丁酯、3克丙烯酸、10克改性丙烯酰胺IBMA、2.5克十二烷基硫酸钠等。
不过,丙烯酰胺属于一种中等毒性的物质,其可通过消化道、呼吸道、皮肤粘膜等而被人体吸收。已知丙烯酰胺具有生殖发育毒性、遗传毒性以及致癌性等,进一步的描述可参阅百度百科等。另外,上述的专利申请所涉及的交联剂属于内交联剂,即其为聚合时所加入的交联剂,应用较为不便
因而,有必要提供一种全新的丙烯酸用交联剂,该交联剂可有效提高丙烯酸类粘合剂粘接强度,从而提高织物的皂洗牢度、摩擦牢度等,而且该交联剂应当使用方便,具有较低毒性,利于环保、印染工人的健康和织物使用者的健康。
发明内容
本发明的目的是提供一种新型的丙烯酸粘合剂用交联剂以及所得的粘合剂,该交联剂能显著提高丙烯酸类粘合剂粘接强度,从而能显著提高粘合剂皂洗牢度以及干、湿摩擦牢度,而且该交联剂使用方便,可在使用时加入到水性丙烯酸粘合剂中(所谓的外交联剂),同时基本上没有毒性或者毒性很低。
为实现本发明的发明目的,一方面,本发明提供了一种丙烯酸粘合剂用交联剂,以重量百分计,该交联剂包含:5~30%的醛类化合物、1~20%的缩水甘油醚类化合物、2~10%环氧基化合物、1~10%的有机酸、10~30%的有机醇溶剂以及1~5%金属盐,余量为水;其中,该交联剂可通过将上述各组分按比例称取混合均匀而制得的。
优选地,上述的交联剂包含:10~30%的C2-C5醛类化合物、5~20%的缩水甘油醚类化合物、2~8%环氧基化合物、2~6%的C2-C6有机酸、15~30%的C1-C3有机醇溶剂以及1~5%金属氯化物。
在上述本发明的丙烯酸粘合剂用交联剂中,所使用的醛类化合物可以为选自于如下一组物质中的一种或一种以上:乙醛、丙醛、丁醛、乙二醛和戊二醛,这些醛类化合物均为低毒性物质,虽然某些醛有一定刺激性,但并无遗传毒性以及致癌性方面的报道。优选地,在本发明的丙烯酸粘合剂用交联剂中,所使用的醛类化合物为乙二醛和/或戊二醛。
在上述本发明的丙烯酸粘合剂用交联剂中,所使用的缩水甘油醚类化合物可以为选自于如下一组物质中的一种或一种以上:三羟甲基丙烷三缩水甘油醚、乙二醇二缩水甘油醚、烯丙基缩水甘油醚和缩水甘油醚。本发明所使用的这些缩水甘油醚类化合物均为低毒性物质,且无遗传毒性以及致癌性方面的报道。
优选地,在本发明的丙烯酸粘合剂用交联剂中,所使用的缩水甘油醚类化合物可以为选自于如下一组物质中的一种或一种以上:三羟甲基丙烷三缩水甘油醚、氧丙基三甲氧基硅烷缩水甘油醚和甲基丙烯酸缩水甘油醚。
在上述本发明的丙烯酸粘合剂用交联剂中,所使用的环氧基化合物可以为环氧氯丙烷。
在上述本发明的丙烯酸粘合剂用交联剂中,所使用的有机酸可以为选自于如下一组物质中的一种或一种以上:乙二酸、羟基乙酸、丁二酸、苹果酸、和柠檬酸,优选为柠檬酸。这些酸基本上是无毒的,有些甚至可以食用。
在上述本发明的丙烯酸粘合剂用交联剂中,所使用的有机醇溶剂可以为选自于如下一组物质中的一种或一种以上:甲醇、乙醇、异丙醇和丙二醇,优选为异丙醇和/或丙二醇。除甲醇外,其它的有机醇溶剂都是无毒的,本发明优选不使用甲醇。
在上述本发明的丙烯酸粘合剂用交联剂中,所采用的金属盐可以为选自于如下一组物质中的一种或一种以上:氯化镁、氯化锌、氯化铝和氯化锆,优选氯化铝和/或氯化锆。
另一方面,为了实现本发明的发明目的,本发明还提供了一种印染用的丙烯酸粘合剂,其中,该丙烯酸粘合剂含有如上所述的本发明的交联剂。
本发明的交联剂时一种外交联剂,在使用时加入到水性丙烯酸粘合剂中,在常温不产生反应,在高温烘干定型时(≧100℃)与粘合剂迅速发生交联反应,而能显著地提高粘合剂皂洗牢度以及干、湿摩擦牢度。从本发明交联剂所使用的成分上可以看到,本发明的交联剂是基本上没有毒性或毒性很低的。
下面结合具体实施方式来进一步地说明本发明;但是可以理解,这些具体的实施方式只是用于说明本发明,而不是对本发明的限制。本领域的普通技术人员完全可以在本发明的启示下,对本发明的具体实施方式进行改进,或对某些技术特征进行等同替换,但这些经过改进或替换后的技术方案,仍属于本发明的保护范围。
具体实施方式
实施例1:
称取10%乙二醛,10%三羟甲基丙烷三缩水甘油醚,3%环氧氯丙烷,5%乙二酸,2%氯化镁,30%异丙醇,40%的水。依次将称量好的原料加入反应釜中,室温搅拌30min,得到均一透明的交联剂Ⅰ。称取市售印花水性丙烯酸粘合剂100g,交联剂Ⅰ4g加入到1000ml水中,配制成工作液,在室温下,将已染色棉布通过工作液二浸二轧,160℃定型30秒。上述布样的湿摩擦牢度,水洗牢度达到3~4级,而未加交联剂Ⅰ,只加粘合剂处理的布样,湿摩擦牢度2级,水洗牢度2级。
实施例2:
称取20%乙二醛,10%甲基丙烯酸缩水甘油醚,3%环氧氯丙烷,5%柠檬酸,3%氯化铝,20%乙醇,39%的水。依次将称量好的原料加入反应釜中,室温搅拌30min,得到均一透明的交联剂Ⅱ。称取市售印花水性丙烯酸粘合剂100g,交联剂Ⅱ4g加入到1000ml水中,配制成工作液,在室温下,将已染色棉布通过工作液二浸二轧,160℃定型30秒。上述布样的水洗牢度,湿摩擦牢度达到4~5级,而只有粘合剂处理的布样,水洗牢度、湿摩擦牢度仅为2级。
实施例3:
称取20%乙二醛,15%烯丙基缩水甘油醚,5%环氧氯丙烷,5%羟基乙酸,5%氯化锌,10%丙二醇,20%乙醇,20%的水。依次将称量好的原料加入反应釜中,室温搅拌30min,得到均一透明的交联剂Ⅲ。称取市售印花水性丙烯酸粘合剂100g,交联剂Ⅲ4g加入到1000ml水中,配制成工作液,在室温下,将已染色棉布通过工作液二浸二轧,160℃定型30秒。上述布样的水洗牢度,湿摩擦牢度达到4~5级,而只有粘合剂处理的布样,水洗牢度、湿摩擦牢度仅为2级。
实施例4:
称取30%乙二醛,20%氧丙基三甲基硅烷缩水甘油醚,5%环氧氯丙烷,5%丁二酸,3%氯化镁,2%氯化锌,10%乙醇,10%异丙醇,15%的水。依次将称量好的原料加入反应釜中,室温搅拌30min,得到均一透明的交联剂Ⅳ。称取市售印花水性丙烯酸粘合剂100g,交联剂Ⅳ4g加入到1000ml水中,配制成工作液,在室温下,将已染色棉布通过工作液二浸二轧,160℃定型30秒。上述布样的水洗牢度,湿摩擦牢度达到4~5级,而只有粘合剂处理的布样,水洗牢度、湿摩擦牢度仅为2级。
实施例5:
称取25%乙二醛,15%乙二醇二缩水甘油醚,5%环氧氯丙烷,5%苹果酸,3%氯化镁,2%氯化铝,10%甲醇,20%异丙醇,15%的水。依次将称量好的原料加入反应釜中,室温搅拌30min,得到均一透明的交联剂Ⅴ。称取市售印花水性丙烯酸粘合剂100g,交联剂Ⅴ4g加入到1000ml水中,配制成工作液,在室温下,将已染色棉布通过工作液二浸二轧,160℃定型30秒。上述布样的水洗牢度,湿摩擦牢度达到4~5级,而只有粘合剂处理的布样,水洗牢度、湿摩擦牢度仅为2级。
实施例6:
称取25%戊二醛,15%三羟甲基丙烷缩水甘油醚,5%环氧氯丙烷,5%柠檬酸,5%氯化镁,10%乙醇,20%异丙醇,15%的水。依次将称量好的原料加入反应釜中,室温搅拌30min,得到均一透明的交联剂Ⅵ。称取市售印花水性丙烯酸粘合剂100g,交联剂Ⅵ4g加入到1000ml水中,配制成工作液,在室温下,将已染色棉布通过工作液二浸二轧,160℃定型30秒。上述布样的水洗牢度,湿摩擦牢度达到5级,而只有粘合剂处理的布样,水洗牢度、湿摩擦牢度仅为2级。
实施例7:
称取10%丙醛,5%三羟甲基丙烷缩水甘油醚,2%环氧氯丙烷,2%柠檬酸,1.5%氯化镁,5%乙醇,5%异丙醇,69.5%的水。依次将称量好的原料加入反应釜中,室温搅拌30min,得到均一透明的交联剂ⅤⅡ。称取市售印花水性丙烯酸粘合剂100g,交联剂ⅤⅡ10g加入到1000ml水中,配制成工作液,在室温下,将已染色棉布通过工作液二浸二轧,160℃定型30秒。上述布样的水洗牢度,湿摩擦牢度达到3-4级,而只有粘合剂处理的布样,水洗牢度、湿摩擦牢度仅为2级。
Claims (10)
1.一种丙烯酸粘合剂用交联剂,以重量百分计,该交联剂包含:5~30%的醛类化合物、1~20%的缩水甘油醚类化合物、2~10%环氧基化合物、1~10%的有机酸、10~30%的有机醇溶剂以及1~5%金属盐,余量为水;其中,所述的交联剂是通过将上述各组分按比例称取混合均匀而制得的。
2.如权利要求1所述的丙烯酸粘合剂用交联剂,其中,所述的交联剂包含:10~30%的C2-C5醛类化合物、5~20%的缩水甘油醚类化合物、2~8%环氧基化合物、2~6%的C2-C6有机酸、15~30%的C1-C3有机醇溶剂以及1~5%金属氯化物。
3.如权利要求1或2所述的丙烯酸粘合剂用交联剂,其中,所述的醛类化合物为选自于如下一组物质中的一种或一种以上:乙醛、丙醛、丁醛、乙二醛和戊二醛,优选为乙二醛和/或戊二醛。
4.如权利要求1或2所述的丙烯酸粘合剂用交联剂,其中,所述的缩水甘油醚类化合物为选自于如下一组物质中的一种或一种以上:三羟甲基丙烷三缩水甘油醚、乙二醇二缩水甘油醚、烯丙基缩水甘油醚和缩水甘油醚。
5.如权利要求4所述的丙烯酸粘合剂用交联剂,其中,所述的缩水甘油醚类化合物为选自于如下一组物质中的一种或一种以上:三羟甲基丙烷三缩水甘油醚、氧丙基三甲氧基硅烷缩水甘油醚和甲基丙烯酸缩水甘油醚。
6.如权利要求1或2所述的丙烯酸粘合剂用交联剂,其中,所述的环氧基化合物为环氧氯丙烷。
7.如权利要求1或2所述的丙烯酸粘合剂用交联剂,其中,所述的有机酸为选自于如下一组物质中的一种或一种以上:乙二酸、羟基乙酸、丁二酸、苹果酸、和柠檬酸,优选为柠檬酸。
8.如权利要求1或2所述的丙烯酸粘合剂用交联剂,其中,所述的有机醇溶剂为选自于如下一组物质中的一种或一种以上:甲醇、乙醇、异丙醇和丙二醇,优选为异丙醇和/或丙二醇。
9.如权利要求1或2所述的丙烯酸粘合剂用交联剂,其中,所述金属盐为选自于如下一组物质中的一种或一种以上:氯化镁、氯化锌、氯化铝和氯化锆,优选氯化铝和/或氯化锆。
10.一种印染用的丙烯酸粘合剂,其中,所述的丙烯酸粘合剂含有如权利要求1-9之一所述的交联剂。
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