CN111285997A - 树脂与热熔胶 - Google Patents
树脂与热熔胶 Download PDFInfo
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- CN111285997A CN111285997A CN201910055644.3A CN201910055644A CN111285997A CN 111285997 A CN111285997 A CN 111285997A CN 201910055644 A CN201910055644 A CN 201910055644A CN 111285997 A CN111285997 A CN 111285997A
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- 239000011347 resin Substances 0.000 title claims abstract description 72
- 229920005989 resin Polymers 0.000 title claims abstract description 72
- 239000004831 Hot glue Substances 0.000 title claims description 12
- 150000002009 diols Chemical class 0.000 claims abstract description 58
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 49
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 46
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 46
- 239000013067 intermediate product Substances 0.000 claims abstract description 33
- 229920005862 polyol Polymers 0.000 claims abstract description 16
- 150000003077 polyols Chemical class 0.000 claims abstract description 16
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 229920000728 polyester Polymers 0.000 claims description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 10
- 229920000570 polyether Polymers 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 22
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 22
- 125000000217 alkyl group Chemical group 0.000 description 21
- 239000000203 mixture Substances 0.000 description 16
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- DFPJRUKWEPYFJT-UHFFFAOYSA-N 1,5-diisocyanatopentane Chemical compound O=C=NCCCCCN=C=O DFPJRUKWEPYFJT-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 125000005119 alkyl cycloalkyl group Chemical group 0.000 description 3
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 3
- 239000012943 hotmelt Substances 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005580 one pot reaction Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000004386 Erythritol Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- -1 PDI Chemical compound 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种树脂，为由1摩尔份的多异氰酸酯基的核心与3至4.5摩尔份的二醇反应形成中间产物后，中间产物再与3至4.5摩尔份的第一二异氰酸酯反应而成。多异氰酸酯基的核心可为多异氰酸酯，其具有超过两个异氰酸酯基。另一方面，多异氰酸酯基的核心可由第二二异氰酸酯与多羟基化合物反应而成，且多羟基化合物具有超过两个羟基。
Description
技术领域
本发明涉及热熔胶与其树脂组成。
背景技术
在所有制鞋所使用的原材料中，连结各个零部元件、组装成为鞋子产品的关键是粘合剂。近年来各种商品皆以人类生存环境可持续性为要求，世界各国均积极推动环保法规，以限制产业生产工艺中的VOC排放，即在制鞋过程中不得使用或减少使用有机溶剂。制鞋业发展已经明确走向需要环保工艺、快速加工的材料，才能满足市场快速变化及自动化生产要求。鞋用粘合剂主要的技术发展方向为低污染及高功能化，低污染的粘合剂以水性化树脂及无溶剂化树脂为主，后者发展出热熔树脂、粉体树脂及UV树脂等系统，其中PU(polyurethane，聚氨酯)热熔胶具有加快产速、降低成本的优势。世界各鞋用树脂特化品厂如Bayer、Henkel、Bostik等公司皆开发不含有机溶剂的高功能鞋用室温交联PU树脂，初期强度达到3kgf/cm2以上，成功地应用在高功能鞋材的贴合，将有机溶剂含量降低到接近零VOC的程度。但目前室温交联PU树脂存在粘度高(100,000cps以上@120℃)与流动性差的问题。综上所述，目前亟需新的粘合剂以同时符合无溶剂、高粘合强度、与低粘度等特性。
发明内容
本发明一实施例提供的树脂，为由1摩尔份的多异氰酸酯基的核心与3至4.5摩尔份的二醇反应形成中间产物后，中间产物再与3至4.5摩尔份的第一二异氰酸酯反应而成。
本发明一实施例公开的热熔胶包括树脂，且树脂为由1摩尔份的多异氰酸酯基的核心与3至4.5摩尔份的二醇反应形成中间产物后，中间产物再与3至4.5摩尔份的第一二异氰酸酯反应而成。
具体实施方式
本发明一实施例提供树脂的形成方法如下。首先，取3至4.5摩尔份的第二二异氰酸酯与1摩尔份的多羟基化合物在60℃至90℃之间的温度下反应形成1摩尔份的多异氰酸酯基的核心，其具有超过两个异氰酸酯基。若形成多异氰酸酯基的核心的反应温度过低，则造成多异氰酸基核心反应不完全。若形成多异氰酸酯基的核心的反应温度过高，则造成多异氰酸基核心乱序架接造成树脂粘度剧烈爬升。举例来说，多羟基化合物的结构可为
n大于2，且R1为C1-21的直链或支链的烷基，或C3-12的环烷基或烷基环烷基，且烷基环烷基上的烷基可为直链或支链的烷基。在一实施例中，R1为C6-18的直链或支链的烷基，或C6-12的环烷基或烷基环烷基，且烷基环烷基上的烷基可为直链或支链的烷基。在一实施例中，R1为C9-12的直链或支链的烷基。在一实施例中，多羟基化合物不具有芳基，其可为三羟甲基丙烷(TMP)、三羟丙烷、甘油、季戊四醇、丁四醇、类似物或上述的组合。举例来说，第二二异氰酸酯的结构可为
其中R2可为C3-8的烷撑基或C3-17的环烷撑基或烷基环烷撑基，且烷基环烷撑基上的烷基可为直链或支链的烷基。在一实施例中，第二二异氰酸酯不具有芳基，其可为异佛尔酮二异氰酸酯(isophoronediisocyanate，IPDI)、五亚甲基二异氰酸酯(pentamethylenediisocyanate，PDI)、六亚甲基二异氰酸酯(hexamethylenediisocyanate，HDI)、双(异氰酸4-环己酯)甲烷(Dicyclohexylmethane 4，4′-diisocyanate，H12MDI)、类似物或上述的组合。若第二二异氰酸酯的用量过低，则多羟基化合物的羟基无法完全反应，即减少多异氰酸酯基的核心的异氰酸酯基，使最终形成的树脂粘度过高。上述多异氰酸酯基的核心的形成反应如下：
接着取1摩尔份的多异氰酸酯基的核心与3至4.5摩尔份的二醇反应形成中间产物。若二醇的用量过低，则会使树脂分子间形成网状结构，造成粘度剧烈爬升。若二醇的用量过高，则需额外步骤去除未与多异氰酸酯基的核心反应的二醇，以避免稀释树脂的浓度。上述形成中间产物的反应温度介于约90℃至120℃之间。若反应温度过低，则造成多异氰酸基核心反应不完全。若反应温度过高，则造成多异氰酸基核心乱序架接造成树脂粘度剧烈爬升。在一实施例中，二醇可为聚酯二醇、聚醚二醇、类似物或上述的组合。上述二醇的重均分子量可介于2000至4000之间，例如大于2000且小于或等于4000。若二醇的重均分子量过低，则形成的树脂产物的初期强度不足。若二醇的重均分子量过高，则造成树脂整体粘度过高无法操作。在一实施例中，二醇可为结晶性二醇。在一实施例中，二醇可为高结晶性二醇。举例来说，聚酯二醇不具有芳基，其结构可为
其中x为重复单元的数目，x可为3至25，R3为C2-8的烷撑基或C3-8的环烷撑基或烷基环烷撑基，且烷基环烷撑基上的烷基可为直链或支链的烷基。R4为C3-8的烷撑基或C3-8的环烷撑基或烷基环烷撑基，且烷基环烷撑基上的烷基可为直链或支链的烷基。当二醇为聚酯二醇时，形成中间产物的反应如下：
另一方面，当二醇为聚醚二醇，其不具有芳基，且结构可为
其中y为重复单元的数目，y可为8至75，而R6为C3-8的直链或支链烷撑基或C3-8的环烷撑基或烷基环烷撑基，且烷基环烷撑基上的烷基可为直链或支链的烷基。当二醇为聚醚二醇时，形成中间产物的反应如下：
接着取中间产物与3至4.5摩尔份的第一二异氰酸酯反应形成树脂，可使所形成的树脂的分子末端具有异氰酸反应官能基。若第一二异氰酸酯的比例过低，则会使树脂分子间形成网状结构，造成粘度剧烈爬升。若第一二异氰酸酯的比例过高，则需额外步骤去除未与中间产物反应的第一二异氰酸酯，以避免稀释树脂的浓度。在一实施例中，上述形成树脂的反应温度介于90℃至120℃之间。若反应温度过低，则造成多异氰酸基核心反应不完全。若反应温度过高，则造成多异氰酸基核心乱序架接造成树脂粘度剧烈爬升。第一二异氰酸酯的结构可为
其中R5可为C3-8的烷撑基或C3-8的环烷撑基或烷基环烷撑基，且烷基环烷撑基上的烷基可为直链或支链的烷基。在一实施例中，第一二异氰酸酯不具有芳基，其可为IPDI、PDI、HDI、双(异氰酸-4-环己酯)甲烷(DICYCLOHEXYLMETHANE 4，4’-DIISOCYANATE，H12MDI)、类似物或上述的组合。第一二异氰酸酯与前述的第二二异氰酸酯可相同或不同。换言之，上述的树脂为由1摩尔份的多异氰酸酯基的核心与3至4.5摩尔份的二醇反应形成中间产物后，中间产物再与3至4.5摩尔份的第一二异氰酸酯反应而成，且多异氰酸酯基的核心可由多羟基化合物与第二二异氰酸酯反应而成。当用以形成前述中间产物的二醇为聚酯二醇时，形成树脂的反应示例如下：
当用以形成前述中间产物的二醇为聚醚二醇时，形成树脂的反应示例如下：
在一实施例中，可依序进行下述步骤：(1)取第二二异氰酸酯与多羟基化合物反应形成多异氰酸酯基的核心，(2)取多异氰酸酯基的核心与二醇反应形成中间产物，再(3)取中间产物与第一二异氰酸酯反应形成树脂。在另一实施例中，可直接将二异氰酸酯(作为第一二异氰酸酯与第二二异氰酸酯)、多羟基化合物与二醇直接混合(一锅法)，再经由调整混合物的温度变化以确保依序进行上述反应。二异氰酸酯、多羟基化合物与二醇的具体材料种类同前述，在此不另赘述。在一锅法中，第一异氰酸酯与第二异氰酸酯的种类相同。在一锅法中，前述“二异氰酸酯的摩尔数”与“多羟基化合物与二醇的摩尔数合计”的比例可为1.3∶1至1.7∶1，通过摩尔数的比例控制，可制得末端具有异氰酸反应官能基的树脂。
在另一实施例中，多异氰酸酯基的核心为多异氰酸酯，其具有超过两个异氰酸酯基。举例来说，多异氰酸酯的结构可为
n大于2，R1为C1-10的直链或支链烷基或C3-18的环烷基或烷基环烷基，且烷基环烷基上的烷基可为直链或支链的烷基。在一实施例中，多异氰酸酯不具有芳基，其可为异佛尔酮二异氰酸酯(isophoronediisocyanate，IPDI)、五亚甲基二异氰酸酯(pentamethylenediisocyanate)、六亚甲基二异氰酸酯(hexamethylenediisocyanate，HDI)、双(异氰酸4-环己酯)甲烷(DICYCLOHEXYLMETHANE 4，4’-DIISOCYANATE，H12MDI)、类似物或上述的组合。在一实施例中，以多异氰酸酯作为多异氰酸酯基的核心，二醇为聚酯二醇，形成中间产物的反应示例如下：
在此实施例中，中间产物与第一二异氰酸酯形成树脂的反应如下：
在一实施例中，上述树脂的结晶度大于70％，可有效提升树脂的机械强度。一般而言，聚异氰酸酯系的树脂结晶度小于70％，而树脂无法在施工初期快速固化，使贴合后无法展现机械强度。
值得注意的是，本发明通过前述的方法所制得的树脂的分子结构为树枝状结构，可降低树脂的粘度。此外，通过将高结晶性的二醇导入树脂的分子结构中，可提升热熔胶的初期粘合强度。
本发明一实施例提供的热熔胶包括上述树脂。在一些实施例中，热熔胶不含溶剂，即树脂可直接作为热熔胶。在一些实施例中，树脂在120℃下的粘度介于6000cps至15000cps之间。若树脂的粘度过高，可能在涂布于对象上之前即部分硬化。若树脂的粘度过低，可能在硬化前流动至不需涂布树脂的部分而劣化产品。在一些实施例中，热熔胶于20％至80％的相对湿度与10℃至30℃的温度下硬化。举例来说，可在常温(如25℃)与一般湿度(RH＝75％)下快速硬化上述热熔胶。
为了让本发明的上述和其他目的、特征、和优点能更明显易懂，下文特别列举多个实施例，作详细说明如下：
实施例
实施例1
取3摩尔份的聚酯二醇7330(EvonikDynacoll 7330，重均分子量3500)作为二醇、1摩尔份的三羟甲基丙烷(TMP)作为多羟基化合物、以及7摩尔份的六亚甲基二异氰酸酯(HDI)作为第一二异氰酸酯与第二二异氰酸酯混合。加热上述混合物至80℃并反应1小时，使TMP与部分的HDI(第二二异氰酸酯)反应形成多异氰酸酯基的核心。接着加热上述混合物至110℃并反应1小时，使多异氰酸酯基的核心与聚酯二醇7330反应形成中间产物。接着调整上述混合物至100℃并反应1小时，使中间产物与其余部分的HDI(第一二异氰酸酯)反应形成树脂。上述树脂在120℃的粘度为14650cps(测量标准为ASTM-D3236)。以ASTM-D1876测量树脂的初期粘合强度与末期粘合强度，分别为1.19kgf/cm2与12.25kgf/cm2。上述树脂的结晶度为77.5％。
实施例2
取3摩尔份的聚醚二醇5602(长兴ETEROL-5602，重均分子量为3750)作为二醇、1摩尔份的TMP作为多羟基化合物、以及7摩尔份的HDI作为第一二异氰酸酯与第二二异氰酸酯混合。加热上述混合物至80℃并反应1小时，使TMP与部分的HDI(第二二异氰酸酯)反应形成多异氰酸酯基的核心。接着加热上述混合物至110℃并反应1小时，使多异氰酸酯基的核心与聚醚二醇5602反应形成中间产物。接着调整上述混合物至100℃并反应1小时，使中间产物与其余部分的HDI(第一二异氰酸酯)反应形成树脂。上述树脂在120℃的粘度为32710cps(测量标准为ASTM-D3236)。以ASTM-D1876测量树脂的初期粘合强度与末期粘合强度，分别为4.22kgf/cm2与14.08kgf/cm2。上述树脂的结晶度为70.5％。
实施例3
取3摩尔份的聚酯二醇PBA3000(永纯化学，重均分子量为3000)作为二醇、1摩尔份的三聚HDI(科思创Desmodur N3300)作为多异氰酸酯基的核心、以及3摩尔份的HDI作为第一二异氰酸酯混合。加热上述混合物至100℃并反应1小时，使多异氰酸酯基的核心与聚酯二醇PBA3000反应形成中间产物。接着加热上述混合物至110℃并反应1小时，使中间产物与HDI(第一二异氰酸酯)反应形成树脂。
比较例1
取3摩尔份的聚酯二醇PBA(永纯化学PBA，重均分子量为2000)作为二醇、1摩尔份的TMP作为多羟基化合物、以及7摩尔份的HDI作为第一二异氰酸酯与第二二异氰酸酯混合。加热上述混合物至80℃并反应1小时，使TMP与部分的HDI(第二二异氰酸酯)反应形成多异氰酸酯基的核心。接着加热上述混合物至80℃并反应1小时，使多异氰酸酯基的核心与聚酯二醇PBA反应形成中间产物。接着加热上述混合物至110℃并反应1小时，使中间产物与其余部分的HDI(第一二异氰酸酯)反应形成树脂。上述树脂在120℃的粘度为14650cps(测量标准为ASTM D3236)。以ASTM-D1876测量树脂的初期粘合强度与末期粘合强度，分别为0kgf/cm2与8.13kgf/cm2。上述树脂的结晶度为56.0％。由比较例1可知，若二醇的重均分子量过低，则树脂的初期粘合强度不足。
比较例2
取2摩尔份的聚醚二醇5602(长兴ETEROL-5602)作为二醇、1摩尔份的1，4-丁二醇作为二羟基化合物、以及2摩尔份的六亚甲基二异氰酸酯(HDI)作为第一二异氰酸酯与第二二异氰酸酯混合。加热上述混合物至80℃并反应1小时，使1，4-丁二醇(二羟基化合物)与部分的HDI(第二二异氰酸酯)反应形成二异氰酸酯基的核心。接着加热上述混合物至100℃并反应1.5小时，使二异氰酸酯基的核心与聚醚二醇5602反应形成中间产物。接着加热上述混合物至110℃并反应1小时，使中间产物与其余部分的HDI(第一二异氰酸酯)反应形成树脂。上述树脂在120℃的粘度为86900cps(测量标准为ASTM-D3236)。以ASTM-D1876测量树脂的初期粘合强度与末期粘合强度，分别为7.15kgf/cm2与7.22kgf/cm2。上述树脂的结晶度为51.8％。由比较例2可知，若树脂的核心具有二异氰酸酯基而非多异氰酸酯基，则粘度过高而难以施加至欲粘合的对象。
以上所述仅为本发明的具体实施例而已，并不用于限制本发明，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (8)
1.一种树脂，为由：
1摩尔份的一多异氰酸酯基的核心与3至4.5摩尔份的一二醇反应形成一中间产物后，该中间产物再与3至4.5摩尔份的一第一二异氰酸酯反应而成。
2.如权利要求1所述的树脂，其中该多异氰酸酯基的核心为一多异氰酸酯，其具有超过两个异氰酸酯基。
3.如权利要求1所述的树脂，其中该多异氰酸酯基的核心为由3至4.5摩尔份的一第二二异氰酸酯与1摩尔份的一多羟基化合物反应而成，且该多羟基化合物具有超过两个羟基。
4.如权利要求1所述的树脂，其中该二醇为聚醚二醇或聚酯二醇。
5.如权利要求1所述的树脂，其中该二醇的重均分子量介于2000至4000之间。
6.一种热熔胶，包括一树脂，且该树脂为由1摩尔份的一多异氰酸酯基的核心与3至4.5摩尔份的一二醇反应形成一中间产物后，该中间产物再与3至4.5摩尔份的一第一二异氰酸酯反应而成。
7.如权利要求6所述的热熔胶，其不含溶剂。
8.如权利要求6所述的热熔胶，其在20％至80％的相对湿度的硬化温度介于10℃至30℃之间。
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| CN103305174B (zh) * | 2013-05-24 | 2015-01-21 | 南京林业大学 | 一种光/湿双固化聚氨酯热熔胶的制备方法 |
| CN108559437B (zh) * | 2018-02-28 | 2020-12-08 | 广州市白云化工实业有限公司 | 反应型聚氨酯热熔胶及其制备方法 |
| CN108659775A (zh) * | 2018-04-10 | 2018-10-16 | 广东中粘新材料科技有限公司 | 一种应用于电子家电行业的双组分无溶剂反应型聚氨酯热熔胶及其使用方法 |
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| Publication number | Publication date |
|---|---|
| US20200181466A1 (en) | 2020-06-11 |
| TWI696638B (zh) | 2020-06-21 |
| TW202022003A (zh) | 2020-06-16 |
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