CN106893063B - 一种无溶剂型镜面革及其制备方法 - Google Patents

一种无溶剂型镜面革及其制备方法 Download PDF

Info

Publication number
CN106893063B
CN106893063B CN201710308159.3A CN201710308159A CN106893063B CN 106893063 B CN106893063 B CN 106893063B CN 201710308159 A CN201710308159 A CN 201710308159A CN 106893063 B CN106893063 B CN 106893063B
Authority
CN
China
Prior art keywords
resin
parts
solvent
leather
content
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.)
Active
Application number
CN201710308159.3A
Other languages
English (en)
Other versions
CN106893063A (zh
Inventor
周其平
丛小雨
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wuxi Wanli Adhesion Materials Co ltd
Original Assignee
Wuxi Wanli Adhesion Materials Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Wuxi Wanli Adhesion Materials Co ltd filed Critical Wuxi Wanli Adhesion Materials Co ltd
Priority to CN201710308159.3A priority Critical patent/CN106893063B/zh
Publication of CN106893063A publication Critical patent/CN106893063A/zh
Application granted granted Critical
Publication of CN106893063B publication Critical patent/CN106893063B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6204—Polymers of olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/69—Polymers of conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)

Abstract

一种无溶剂型镜面革的制备方法，具体步骤如下：(1)将乙烯、丙烯、马来酸酐、羟基丙烯酸共聚树脂共10‑30份，多元醇树脂50‑60份，120～140℃真空度0～‑0.1MPa下脱水120～150min，降温至70～75℃；(2)异氰酸酯10～40份加入，常压氮气保护反应40～45min，反应温度控制在70～95℃，然后置入‑0.1～0MPa真空中继续反应50～55min，反应温度控制在90～115℃，反应结束后将产品装入由铝、锡或其复合膜制成的容器中，即得到产品无溶剂镜面革树脂。本发明制备得到的镜面革表面高光，颜色靓丽，光泽耐久不褪色变黄，柔韧性好，抗弯折、抗裂性能高，具有广阔的应用前景。

Description

一种无溶剂型镜面革及其制备方法
技术领域
本发明涉及人造革技术领域，尤其是涉及一种无溶剂树脂镜面人造革的制备方法。
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。人造革按使用的合成树脂分类：
(1)聚氯乙烯人造革：它是用聚氯乙烯树脂、增塑别和其他配合剂组成的混合物，涂覆或贴合在织物，经一定的加工工艺过程而制成的醒料制品。另外，也有基材两面均为塑料层的双面聚氯乙烯人造革。
(2)聚酰胺人造革：它是以尼龙6或尼龙66溶液徐覆在织物上、膜的方法制成具有连续泡孔性结构的塑料制品。
(3)聚烯烃人造革：聚乙烯人造革是一种泡沫人造革，它是以低密度聚乙烯树脂为主要原材料，掺以改性树脂、交联剂、润滑剂、发泡剂等组分而制成的制品。
(4)聚氨酯人造革：聚氨酯人造革又分为干法聚氨酯人造革和湿法聚氨酯人造革。所谓干法聚氨酯人造革，是指将溶剂型聚氨酯树脂的溶液挥发掉溶剂后、得到的多层薄膜加上底布而构成的多层结构体。而湿法聚氨酯人造革，是将溶剂型聚氨酯树脂、采用水中成膜法而得到的具有良好透气性和透湿性，同时又具有连续多孔层的多层结构体。
镜面革是类似于镜面的人造革，一般是以湿气固化型聚氨酯涂饰，使涂层光亮如镜。目前常用的镜面革是溶剂型树脂制备而成，有气味，保光保色性差，易变黄，耐久性不高，有毒性和污染，使用范围狭窄。
发明内容
针对现有技术存在的上述问题，本申请提供了一种无溶剂型镜面革及其制备方法。本发明制备得到的镜面革表面高光，颜色靓丽，光泽耐久不褪色变黄，柔韧性好，抗弯折、抗裂性能高，具有广阔的应用前景。
本发明的技术方案如下：
一种无溶剂型镜面革的制备方法，具体步骤如下：
(1)将乙烯、丙烯、马来酸酐、羟基丙烯酸共聚树脂一共10-30份，以及多元醇树脂50-60份，在120～140℃下在真空度0～-0.1MPa下脱水120～150min，降温至70～75℃；其中乙烯含量为3-8份，丙烯含量为4-7份，马来酸酐含量为1-4份，羟基丙烯酸含量为2-11份；
(2)取异氰酸酯10～40份加入到步骤(1)得到的混合物中，常压下在氮气保护下反应40～45min，反应温度控制在70～95℃，然后置入-0.1～0MPa真空中继续反应50～55min，反应温度控制在90～115℃，反应结束后将产品装入由铝、锡或其复合膜制成的容器中，即得到产品无溶剂镜面革树脂。
优选的，所述多元醇为聚丁二烯多元醇或二聚酸型聚酯多元醇。
优选的，所述聚丁二烯多元醇为羟基封端的聚丁二烯树脂。
优选的，所述羟基封端的聚丁二烯树脂为Cray Valley公司生产的krasol LBH-2000或LBH-3000型号的产品。
优选的，所述异氰酸酯为MDI或IPDI。
本发明有益的技术效果在于：
本发明用于人造革的表面，表面光滑。本发明树脂中不含溶剂，采用的是热熔型树脂。本发明树脂为单组份树脂，避免了双组份在混合过程中的误差造成产品质量问题。乙烯、丙烯、马来酸酐、丙烯酸共聚树脂能提供本发明树脂的初期强度。异氰酸酯树脂主要是和多元醇树脂反应。乙烯，丙烯，马来酸酐，丙烯酸共聚树脂是透明色树脂，有较好的耐磨性，多元醇树脂与异氰酸酯树脂反应形成的异氰酸酯封端物湿气固化完后比较柔软，提供树脂耐折痕性。形成的异氰酸酯封端物湿气固化后是透明的，适合做镜面革。此异氰酸酯封端物的NCO含量为小于1.5％，可以保证此树脂湿气固化以后没有气泡。
目前市面上的溶剂型产品不能使人造革成品表面这层镜面革的柔软性较好，本发明提供的这种无溶剂产品由于较高的切断伸长率和材料较低的硬度使得材料柔软性好。
具体实施方式
下面结合实施例，对本发明进行具体描述。以下实施例中乙烯，丙烯，马来酸酐，羟基丙烯酸共聚树脂可以从陶氏化学购得。
实施例1：
乙烯，丙烯，马来酸酐，羟基丙烯酸共聚树脂一共12份(其中乙烯含量为3份，丙烯含量为5份，马来酸酐含量为1份，羟基丙烯酸含量为4份)，多元醇树脂krasol LBH-2000，50份，在120℃下在真空度-0.1MPa下脱水150min，降温至70℃；取异氰酸酯MDI 12份加入到上述混合物中，常压下在氮气保护下反应45min，反应温度控制在70℃，将混合物置入-0.1MPa真空中继续反应50min，反应温度控制在90℃，反应结束后将产品装入由铝、锡或其复合膜制成的容器中，即得到产品无溶剂镜面革树脂。其粘度为8500mpa.s(110℃)，异氰酸酯的含量为1.5％。
实施例2：
乙烯，丙烯，马来酸酐，羟基丙烯酸共聚树脂一共18份(其中乙烯含量为5份，丙烯含量为6份，马来酸酐含量为2份，羟基丙烯酸含量为5份)，多元醇树脂krasol LBH-3000，60份，在130℃下将定量的树脂在真空度-0.05MPa下脱水140min，降温至75℃；取异氰酸酯MDI30份加入到上述混合物中，常压下在氮气保护下反应45min，反应温度控制在85℃，将混合物置入-0.05MPa真空中继续反应52min，反应温度控制在100℃，反应结束后将产品装入由铝、锡或其复合膜制成的容器中，即得到产品无溶剂镜面革树脂。其粘度为13000mpa.s(130℃)，异氰酸酯的含量为1.3％。
实施例3：
乙烯，丙烯，马来酸酐，羟基丙烯酸共聚树脂一共30份(其中乙烯含量为8份，丙烯含量为7份，马来酸酐含量为4份，羟基丙烯酸含量为11份)，多元醇树脂krasol LBH-3000，54份，在140℃下将定量的树脂在真空度0MPa下脱水120min，降温至75℃；取异氰酸酯IPDI40份加入到上述混合物中，常压下在氮气保护下反应40min，反应温度控制在95℃，将混合物置入0MPa真空中继续反应55min，反应温度控制在115℃，反应结束后将产品装入由铝、锡或其复合膜制成的容器中，即得到产品无溶剂镜面革树脂。其粘度为5000mpa.s(130℃)，异氰酸酯的含量为1.4％。
测试例：将实施例1-3制备的无溶剂镜面革树脂进行性能测试，结果如表1所示。
表1
实施例1 实施例2 实施例3
切断伸长率 720％ 650％ 1100％
拉伸强度 3.5Mpa 8.9Mpa 5.2Mpa
耐折性测试 100000次以上 100000次以上 100000次以上
耐高温测试 250度 250度 250度
铅笔硬度 H 2H 2H
其中耐折性测试方法：将涂布为5mm厚固化完全的树脂，180度弯曲后观察弯曲处是否有不可逆转的折痕。无任何不可逆转的折痕认定此次弯曲试验是有效的，同时记录180度弯曲的次数。
耐高温测试方法：将涂布为5mm厚固化完全的树脂，放入一定温度的恒温烘箱中60min后取出，若树脂无流淌，无发粘即认定此树脂是可以耐此高温的。

Claims (1)

1.一种无溶剂镜面革树脂的制备方法，其特征在于具体步骤如下：
(1)将乙烯、丙烯、马来酸酐、羟基丙烯酸共聚树脂一共10-30份，以及多元醇树脂50-60份，在120～140℃下在真空度0～-0.1MPa下脱水120～150min，降温至70～75℃；其中乙烯含量为3-8份，丙烯含量为4-7份，马来酸酐含量为1-4份，羟基丙烯酸含量为2-11份；
(2)取异氰酸酯10～40份加入到步骤(1)得到的混合物中，常压下在氮气保护下反应40～45min，反应温度控制在70～95℃，然后置入-0.1～0MPa真空中继续反应50～55min，反应温度控制在90～115℃，反应结束后将产品装入由铝、锡或其复合膜制成的容器中，即得到产品无溶剂镜面革树脂；所述多元醇树脂为聚丁二烯多元醇或二聚酸型聚酯多元醇；所述聚丁二烯多元醇为羟基封端的聚丁二烯树脂；所述羟基封端的聚丁二烯树脂为CrayValley公司生产的krasol LBH-2000或LBH-3000型号的产品；所述异氰酸酯为MDI或IPDI。
CN201710308159.3A 2017-05-04 2017-05-04 一种无溶剂型镜面革及其制备方法 Active CN106893063B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710308159.3A CN106893063B (zh) 2017-05-04 2017-05-04 一种无溶剂型镜面革及其制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710308159.3A CN106893063B (zh) 2017-05-04 2017-05-04 一种无溶剂型镜面革及其制备方法

Publications (2)

Publication Number Publication Date
CN106893063A CN106893063A (zh) 2017-06-27
CN106893063B true CN106893063B (zh) 2020-04-03

Family

ID=59197138

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710308159.3A Active CN106893063B (zh) 2017-05-04 2017-05-04 一种无溶剂型镜面革及其制备方法

Country Status (1)

Country Link
CN (1) CN106893063B (zh)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109467666B (zh) * 2018-09-30 2020-11-20 浙江禾欣科技有限公司 一种表面滑爽的聚氨酯的制备方法
CN110330628A (zh) * 2019-07-10 2019-10-15 福建元发树脂有限公司 无溶剂单组份聚氨酯镜面树脂

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102796485A (zh) * 2012-09-11 2012-11-28 无锡市万力粘合材料有限公司 反应性聚氨酯热熔胶及其制备方法
CN103045154A (zh) * 2013-01-21 2013-04-17 无锡市万力粘合材料有限公司 木工包覆用聚氨酯热熔胶及其制备方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102796485A (zh) * 2012-09-11 2012-11-28 无锡市万力粘合材料有限公司 反应性聚氨酯热熔胶及其制备方法
CN103045154A (zh) * 2013-01-21 2013-04-17 无锡市万力粘合材料有限公司 木工包覆用聚氨酯热熔胶及其制备方法

Also Published As

Publication number Publication date
CN106893063A (zh) 2017-06-27

Similar Documents

Publication Publication Date Title
CN103437195B (zh) 一种免车缝的热熔胶tpu-pu皮革及其制备方法
CN103437194A (zh) 一种免车缝的热熔胶tpu皮革及其制备方法
CN103409101B (zh) 聚丁二烯橡胶改性水性聚氨酯胶粘剂及其制备方法
CN105801808A (zh) 一种可剥离革用水性聚氨酯的合成与制备方法
CN105111399B (zh) 一种耐水压水性聚氨酯树脂
CN106893063B (zh) 一种无溶剂型镜面革及其制备方法
CN103805122A (zh) 一种水性聚氨酯贴布胶及其制备方法
JP2016084400A (ja) 水性樹脂組成物、水性表面処理剤及びそれを用いた物品
TW202003614A (zh) 聚胺酯預聚物、接著劑、及合成人造皮
CN107794777B (zh) 一种透气吸湿pu革的制备方法
CN106397678A (zh) 一种丙烯酸改性的水性聚氨酯及其制备方法和用途
CN111909348B (zh) 反应型聚氨酯热熔胶组合物及其制备和用途
CN103254399A (zh) 一种高耐水压耐寒聚氨酯树脂及其制备方法
CN104358131A (zh) 一种合成革用高温细羊巴树脂及其制备方法
CN113584898A (zh) 一种汽车座椅用硅胶皮革及其制备方法
CN105131565A (zh) 一种高色牢度热塑性聚氨酯、热塑性聚氨酯合成革及其制备方法
CN105482765A (zh) 一种水性聚氨酯胶粘剂组合物及其制备方法
CN105694698A (zh) 用于一涂一烘涂层的具有平滑结构的涂覆组合物
KR102428612B1 (ko) 합성 피혁의 제조 방법
CN111705522A (zh) 一种泼水型聚氯乙烯人造革及其制备方法
CN106118577A (zh) 一种鞋用双组份高固含量聚氨酯胶粘剂及其制备方法
CN107761404B (zh) 一种高耐磨pu合成革面料的制备方法
CN112745795B (zh) 一种注塑用水性聚氨酯静电植绒胶及制备方法
CN114507989A (zh) 一种防白化pu合成革及其制备方法
EP3908461A2 (de) Verfahren zur folienbeschichtung mit gravurwalzensystem

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant