CN111164141B - 发泡氨基甲酸酯片和合成皮革 - Google Patents

发泡氨基甲酸酯片和合成皮革 Download PDF

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Publication number
CN111164141B
CN111164141B CN201880064067.8A CN201880064067A CN111164141B CN 111164141 B CN111164141 B CN 111164141B CN 201880064067 A CN201880064067 A CN 201880064067A CN 111164141 B CN111164141 B CN 111164141B
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urethane resin
mass
parts
urethane
foamed
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CN111164141A (zh
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铁井智博
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DIC Corp
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DIC Corp
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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
    • D06N3/0043—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers
    • D06N3/0047—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by their foraminous structure; Characteristics of the foamed layer or of cellular layers obtained by incorporating air, i.e. froth
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
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    • B29C44/5627—After-treatment of articles, e.g. for altering the shape by mechanical deformation, e.g. crushing, embossing, stretching
    • B29C44/5654—Subdividing foamed articles to obtain particular surface properties, e.g. on multiple modules
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Abstract

本发明提供一种发泡氨基甲酸酯片，其特征在于，由含有氨基甲酸酯树脂(A)、水性介质(B)、及碳原子数为10以上的表面活性剂(C)的水性氨基甲酸酯树脂组合物形成，密度为200～1000kg/m3。另外，本发明提供一种合成皮革，其是上述至少具有基材(i)、及聚氨酯层(ii)的合成皮革，其特征在于，该聚氨酯层(ii)由权利要求1～4中任一项所述的发泡氨基甲酸酯片形成。上述聚氨酯层(ii)也可为实施压印加工的层。上述表面活性剂(C)，优选为硬脂酸盐，上述氨基甲酸酯树脂(A)具有阴离子性基团，且优选使用流动起始温度为80℃以上的树脂。

Description

发泡氨基甲酸酯片和合成皮革
技术领域
本发明涉及一种发泡氨基甲酸酯片。
背景技术
聚氨基甲酸酯树脂，因为具有优异的机械强度及柔软性，所以至今为止用于涂布剂、粘接剂等各种用途。其中，至今为止广泛利用含有二甲基甲酰胺(DMF)的溶剂系氨基甲酸酯树脂，但DMF的法律限制逐年趋严，亟需弱溶剂化、水系化、无溶剂化等环保对策制品的开发。
其中，将氨基甲酸酯树脂分散于水中的水系氨基甲酸酯(PUD)正被最积极地进行研究。在将该水系氨基甲酸酯应用于各式各样的用途时，为了提升手感等的目的，作为发泡体成型的需求很多。作为通过水系氨基甲酸酯将发泡体成型的方法，例如研究了配合微胶囊、使二氧化碳等气体分散于PUD配合液的机械发泡等(例如参照专利文献1)。然而，配合微胶囊的方法，所得到的发泡体的手感不良，微胶囊的膨胀所致的平滑性不良成为问题。另外，在使气体分散的方法中，在制造发泡体的过程，由于裹持于配合液的气泡消失等，因此气泡尺寸等的控制为困难，难以稳定地得到手感良好的发泡体。
现有技术文献
专利文献
专利文献1：日本特开2007-191810号公报
发明内容
要解决的技术问题
本发明要解决的课题在于，提供一种使用含有水的氨基甲酸酯树脂组合物，手感及拉伸强度优异的发泡氨基甲酸酯片。
解决的技术问题的技术手段
本发明提供一种发泡氨基甲酸酯片，其特征在于，由含有氨基甲酸酯树脂(A)、水(B)、及碳原子数为10以上的表面活性剂(C)的氨基甲酸酯树脂组合物形成，密度为200～1000kg/m3。
另外，本发明提供一种合成皮革，其是至少具有基材(i)、及聚氨酯层(ii)的合成皮革，其特征在于，上述聚氨酯层(ii)由上述发泡氨基甲酸酯片形成。
技术效果
本发明的发泡氨基甲酸酯片的手感及拉伸强度优异。
另外，在将上述发泡氨基甲酸酯片应用于合成皮革时，其进一步为剥离强度也优异、且能在其表面上均匀地制作外观设计性优异的压印加工的合成皮革。
具体实施方式
本发明的发泡氨基甲酸酯片由含有氨基甲酸酯树脂(A)、水(B)、及不具有芳香环且具有碳原子数为10以上的疏水部的表面活性剂(C)的氨基甲酸酯树脂组合物形成，其密度为200～1000kg/m3。
上述氨基甲酸酯树脂(A)为可分散于后述的水(B)中等的树脂，例如可使用：具有阴离子性基团、阳离子性基团、非离子性基团等亲水性基团的氨基甲酸酯树脂；以乳化剂强制地分散于水(B)中的氨基甲酸酯树脂等。这些氨基甲酸酯树脂(A)可单独使用，也可并用2种以上。从制造稳定性的观点出发，这些中优选使用具有亲水性基团的氨基甲酸酯树脂，更优选为具有阴离子性基团的水性氨基甲酸酯树脂。
作为得到上述具有阴离子性基团的氨基甲酸酯树脂的方法，可举出例如，使用选自由具有羧基的二醇化合物、及具有磺酰基的化合物所组成的组中的1种以上的化合物作为原料的方法。
作为上述具有羧基的二醇化合物，例如可使用：2,2-二羟甲基丙酸、2,2-二羟甲基丁酸、2,2-二羟甲基酪酸、2,2-二羟甲基丙酸、2,2-戊酸等。这些化合物可单独使用，也可并用2种以上。
作为上述具有磺酰基的化合物，例如可使用：3,4-二氨基丁烷磺酸、3,6-二氨基-2-甲苯磺酸、2,6-二氨基苯磺酸、N-(2-氨基乙基)-2-氨基乙基磺酸等。这些化合物可单独使用，也可并用2种以上。
从得到更优异的水分散稳定性的观点出发，作为使用上述为了制造具有阴离子性基团的氨基甲酸酯树脂而使用的原料时的使用量，优选为氨基甲酸酯树脂(A)的原料的合计质量中的0.1～4.8质量％的范围，更优选为0.5～4质量％的范围，进一步更优选为1～3质量％的范围。
上述羧基及磺酰基，在氨基甲酸酯树脂组合物中，也可一部分或全部被碱性化合物中和。作为上述碱性化合物，例如可使用：氨、三乙胺、吡啶、吗啉等有机胺；单乙醇胺、二甲基乙醇胺等烷醇胺；包含钠、钾、锂、钙等的金属碱化合物等。
作为得到上述具有阳离子性基团的氨基甲酸酯树脂的方法，可举出例如，使用具有氨基的化合物的1种或2种以上作为原料的方法。
作为上述具有氨基的化合物，例如可使用：三亚乙四胺、二亚乙三胺等具有伯及仲氨基的化合物；N-甲基二乙醇胺、N-乙基二乙醇胺等N-烷基二烷醇胺、N-甲基二氨基乙胺、N-乙基二氨基乙胺等N-烷基二氨基烷胺等具有叔氨基的化合物等。这些化合物可单独使用，也可并用2种以上。
作为上述氨基甲酸酯树脂(A)，具体而言，例如可使用以下反应物：即多异氰酸酯(a1)、多元醇(a2)、及上述为了制造具有亲水性基团的水性氨基甲酸酯树脂而使用的原料的反应物。
作为上述多异氰酸酯(a1)，例如可使用：苯二异氰酸酯、甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、苯二甲基二异氰酸酯、萘二异氰酸酯、聚亚甲基聚苯基多异氰酸酯、碳二亚胺化二苯基甲烷多异氰酸酯等芳香族多异氰酸酯；六亚甲基二异氰酸酯、赖氨酸二异氰酸酯、环己烷二异氰酸酯、异佛尔酮二异氰酸酯、二环己基甲烷二异氰酸酯、苯二甲基二异氰酸酯、四甲基苯二甲基二异氰酸酯、二聚酸二异氰酸酯、降冰片烯二异氰酸酯等脂肪族或脂环式多异氰酸酯等。这些多异氰酸酯可单独使用，也可并用2种以上。
从制造稳定性以及得到的被膜的机械物性的观点出发，作为上述多异氰酸酯(a1)的使用量，优选为上述氨基甲酸酯树脂(A)的原料的合计质量中5～40质量％的范围，更优选为10～30质量％的范围。
作为上述多元醇(a2)，例如可使用：聚醚多元醇、聚酯多元醇、聚丙烯酸多元醇、聚碳酸酯多元醇、聚丁二烯多元醇等。这些多元醇，可单独使用，也可并用2种以上。
从得到的被膜的机械强度的观点出发，作为上述多元醇(a2)的数均分子量，优选为500～8000的范围，更优选为800～4000的范围。需要说明的是，上述多元醇(a2)的数均分子量表示利用凝胶渗透柱色谱(GPC)法测定的数值。
上述多元醇(a2)中，根据需要，也可并用数均分子量为50～450的扩链剂(a2’)。作为上述扩链剂(a2’)，例如可使用：乙二醇、二乙二醇、三乙二醇、丙二醇、二丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、六亚甲基二醇、蔗糖、亚甲基二醇、丙三醇、山梨糖醇、双酚A、4,4’-二羟基联苯、4,4’-二羟基二苯醚、三羟甲基丙烷等具有羟基的扩链剂；乙二胺、1,2-丙二胺、1,6-六亚甲基二胺、哌嗪、2,5-二甲基哌嗪、异佛尔酮二胺、1,2-环己二胺、1,3-环己二胺、1,4-环己二胺、4,4’-二环己基甲烷二胺、3,3’-二甲基-4,4’-二环己基甲烷二胺、1,4-环己二胺、肼等具有氨基的扩链剂等。这些扩链剂，可单独使用，也可并用2种以上。
从容易调整所得到的氨基甲酸酯树脂(A)的流动起始温度，得到更优异的拉伸强度的观点出发，作为使用上述扩链剂(a2’)时的使用量，优选为氨基甲酸酯树脂(A)的原料的合计质量中0.8～4.3质量％的范围，更优选为1～3.5质量％的范围，进一步更优选为1.5～3.2质量％的范围。
作为上述氨基甲酸酯树脂(A)的制造方法，可举出例如：将上述多元醇(a2)、上述为了制造具有亲水性基团的氨基甲酸酯树脂而使用的原料、上述扩链剂(a2’)、及上述多异氰酸酯(a1)一次性投入，并进行反应的方法。这些的反应，可举出例如，在50～100℃进行3～10小时。
作为制造上述氨基甲酸酯树脂(A)时的上述多元醇(a2)所具有的羟基、上述为了制造具有亲水性基团的氨基甲酸酯树脂而使用的原料所具有的羟基及氨基、以及上述扩链剂(a2’)所具有的羟基及氨基的合计与上述多异氰酸酯(a1)具有的异氰酸酯基的摩尔比[异氰酸酯基/(羟基及氨基)]，优选为0.8～1.2的范围，更优选为0.9～1.1的范围。
在制造上述氨基甲酸酯树脂(A)时，优选使残存于上述氨基甲酸酯树脂(A)的异氰酸酯基丧失活性。在使上述异氰酸酯基丧失活性时，优选为使用甲醇等具有1个羟基的醇。作为上述醇的使用量，优选为相对于氨基甲酸酯树脂(A)100质量份为0.001～10质量份的范围。
另外，在制造上述氨基甲酸酯树脂(A)时，也可使用有机溶剂。作为上述有机溶剂，例如可使用：丙酮、甲乙酮等酮化合物；四氢呋喃、二噁烷等醚化合物；乙酸乙酯、乙酸丁酯等乙酸酯化合物；乙腈等腈化合物；二甲基甲酰胺、N-甲基吡咯烷酮等酰胺化合物等。这些有机溶剂可单独使用，也可并用2种以上。需要说明的是，上述有机溶剂，优选为在得到最后的氨基甲酸酯树脂组合物时，通过蒸馏法等去除。
从可将利用后述的起泡工序产生的气泡稳定地保持(尤其在干燥工序中)，稳定地使发泡氨基甲酸酯片的密度成为200～1000kg/m3的范围的观点出发，作为上述氨基甲酸酯树脂(A)的流动起始温度，优选为80℃以上，更优选为80～220℃的范围。
作为调整上述氨基甲酸酯树脂(A)的流动起始温度的方法，主要可举出根据后述的为氨基甲酸酯树脂(A)的原料的多元醇(a2)的种类、扩链剂(a2’)的使用量、及多异氰酸酯(a1)的种类进行调整的方法。作为提高上述流动起始温度的方法，可举出例如：使用如聚碳酸酯多元醇那样的结晶性高的多元醇作为多元醇(a2)、增加扩链剂(a2’)的使用量、及使用如二环己基甲烷二异氰酸酯或4,4’-二苯基甲烷二异氰酸酯那样的结晶性高的多异氰酸酯作为多异氰酸酯(a1)等。另外，作为使上述流动起始温度降低的方法，可举出例如：使用如聚氧丙烯二醇那样的结晶性低的多元醇作为多元醇(a2)、减少扩链剂(a2’)的使用量、及使用如异佛尔酮二异氰酸酯或甲苯二异氰酸酯那样的结晶性低的多异氰酸酯作为多异氰酸酯(a1)等。因此，通过适当选择这些方法，可调整上述氨基甲酸酯树脂(A)的流动起始温度。需要说明的是，上述氨基甲酸酯树脂(A)的流动起始温度的测定方法在后述的实施例中记载。
在使用具有阴离子性基团的氨基甲酸酯树脂作为上述氨基甲酸酯树脂(A)时，从容易调整流动起始温度，得到更优异的气泡保持性、手感、及拉伸强度的观点出发，优选使用具有阴离子性基团的氨基甲酸酯树脂(A-A-1)，该氨基甲酸酯树脂(A-A-1)为以下反应物：即，选自由4，4’-二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、环己基甲烷二异氰酸酯、及异佛尔酮二异氰酸酯所组成的组中的1种以上的多异氰酸酯；与多元醇(a2)；与具有羧基的二醇化合物；以及含有具有羟基的扩链剂(a2’)的扩链剂的反应物。
作为上述水(B)，例如可使用离子交换水、蒸馏水等。这些水可单独使用，也可使用2种以上。
从水分散稳定性和操作性的观点出发，作为上述氨基甲酸酯树脂(A)与上述水(B)的质量比[(A)/(B)]，优选为10/80～70/30的范围，更优选为20/80～60/40的范围。
上述表面活性剂(C)，为了防止利用起泡产生的泡消失，必须使用不具有芳香环且具有碳原子数为10以上的疏水部的物质。
作为上述表面活性剂(C)，例如可使用下述通式(1)所示的表面活性剂；脂肪酸盐、琥珀酸盐、磺基琥珀酸盐、十八基磺基琥珀酸盐、磺基琥珀酸酯等。这些表面活性剂可单独使用，也可并用2种以上。
RCO2 -X+ (1)
(式(1)中，R表示具有碳原子数为10～20的直链或支链结构的烷基，X表示Na、K、NH4、吗啉、乙醇胺或三乙醇胺。
从具有更优异的气泡保持性的观点出发，作为上述表面活性剂(C)，上述之中，优选为使用上述通式(1)所示的表面活性剂，更优选为使用表示碳原子数为13～19的直链的烷基的物质，进一步更优选为硬脂酸盐。
从得到更优异的气泡保持性的观点出发，作为上述表面活性剂(C)的使用量，相对于上述氨基甲酸酯树脂(A)(＝固体成分)100质量份，优选为0.01～10质量份的范围，更优选为0.1～5质量份的范围。
上述氨基甲酸酯树脂组合物含有上述氨基甲酸酯树脂(A)、水(B)、及表面活性剂(C)作为必要成分，但根据需要也可含有其它的添加剂。
作为上述其它的添加剂，例如可使用：交联剂、中和剂、增粘剂、氨基甲酸酯化催化剂、填充剂、颜料、染料、阻燃剂、流平剂、抗粘连剂等。这些添加剂可单独使用，也可并用2种以上。
作为上述交联剂，出于发泡氨基甲酸酯片的机械强度的提升等的目的而被使用，例如可使用多异氰酸酯交联剂、环氧交联剂、三聚氰胺交联剂、噁唑啉交联剂等。这些交联剂可单独使用，也可并用2种以上。作为使用上述交联剂时的使用量，例如，相对于上述氨基甲酸酯树脂(A)(＝固体成分)100质量份，优选为0.01～100质量份的范围，更优选为0.1～50质量份的范围，进一步更优选为0.5～30质量份的范围，特别优选为1～10质量份。
接下来，针对本发明的发泡氨基甲酸酯片的制造方法进行说明。
上述发泡氨基甲酸酯片通过使上述氨基甲酸酯树脂组合物起泡，得到起泡液，将该起泡液涂布于基材，并进行干燥，得到200～1000kg/m3的密度，由此制造。
作为使上述氨基甲酸酯树脂组合物起泡，得到起泡液的方法，可举出例如，利用手的搅拌、或使用机械混合机等混合机的方法。在使用混合机时，可举出例如，以500～3000rpm进行10秒钟～3分钟搅拌的方法。此时，从容易将发泡氨基甲酸酯片的密度调整为本发明所规定的范围的观点出发，以起泡的前后计，优选为成为1.3～7倍的体积，更优选为成为1.2～2倍的体积，进一步更优选为成为1.3～1.7倍的体积。
作为将得到的起泡液涂布于脱模纸等基材的方法，可举出例如，使用辊涂机、刀涂机、逗号涂机、涂抹器等方法。
作为上述涂布物的干燥方法，可举出例如，在60～130℃的温度进行30秒钟～10分钟干燥的方法。
作为利用以上的方法得到的发泡氨基甲酸酯片的厚度，例如为5～200μm。
上述发泡氨基甲酸酯片的密度必须为200～1000kg/m3。若上述密度为该范围，则为兼具优异的手感与拉伸强度的片。从可作为发泡氨基甲酸酯片用于各种用途的观点出发，作为上述密度，优选为300～900kg/m3的范围，更优选为400～800kg/m3的范围。需要说明的是，上述发泡氨基甲酸酯片的密度表示通过将发泡氨基甲酸酯片的质量除以体积而算出的数值。
接下来，对于本发明的合成皮革进行说明。
本发明的合成皮革，其是至少具有基材(i)、及聚氨酯层(ii)的合成皮革，上述聚氨酯层(ii)由上述发泡氨基甲酸酯片形成。
作为上述合成皮革的制造方法，可举出例如：
(X)使上述氨基甲酸酯树脂组合物起泡，得到起泡液，将该起泡液涂布于脱模纸上，并进行干燥，与上述基材(i)贴合的方法；
(Y)使上述氨基甲酸酯树脂组合物起泡，得到起泡液，将该起泡液涂布于在脱模纸上制作的表皮层上，并进行干燥，与上述基材(i)贴合的方法；及
(Z)使上述氨基甲酸酯树脂组合物起泡，得到起泡液，将该起泡液涂布于上述基材(i)上，并进行干燥，且根据需要，在其上贴合在脱模纸上制作的表皮层(iii)的方法等。
作为上述基材(i)，例如可使用：利用聚酯纤维、聚乙烯纤维、尼龙纤维、丙烯酸系纤维、聚氨基甲酸酯纤维、乙酸酯纤维、嫘萦纤维、聚乳酸纤维、棉、麻、桑蚕丝、羊毛、玻璃纤维、碳纤维、这些的混纺纤维等所得的无纺布、织布、针织物等纤维基材；对上述无纺布浸渗聚氨酯树脂等树脂的基材；进一步在上述无纺布上设置多孔质层的基材；热塑性氨基甲酸酯(TPU)等树脂基材等。
上述聚氨酯层(ii)由上述发泡片形成，从可得到兼具更优异的手感和剥离强度的合成皮革的观点出发，作为其密度，优选为300～900kg/m3的范围，更优选为400～800kg/m3的范围。需要说明的是，上述聚氨酯层(ii)的密度表示，由10cm见方的合成皮革的重量减去10cm见方的基材(i)的重量的数值，除以聚氨酯层(ii)的厚度而得的数值。需要说明的是，上述聚氨酯层(ii)的密度，可通过起泡状况对上述氨基甲酸酯树脂组合物进行调整。
作为上述表皮层(iii)，可利用公知的材料以公知的方法形成，例如可使用：溶剂系氨基甲酸酯树脂、水系氨基甲酸酯树脂、硅酮树脂、聚丙烯树脂、聚酯树脂等。重视柔软的手感、及耐热性、耐水解性时，优选使用聚碳酸酯系氨基甲酸酯树脂。另外，为了在环保对策下的DMF减少化，更优选使用水系聚碳酸酯系氨基甲酸酯树脂。
在上述表皮层(iii)上，根据需要，为了耐擦伤性提升等也可设置表面处理层(iv)。作为上述表面处理层(iv)，可利用公知的材料以公知的方法形成。
如上所述，本发明的合成皮革通过使用上述的手感及拉伸强度优异的发泡氨基甲酸酯片，进一步为剥离强度也优异、且能在其表面上均匀地制作外观设计性优异的压印加工的合成皮革。
作为在上述聚氨酯层(ii)上实施压印加工的方法，可举出例如：在合成皮革的聚氨酯层(ii)上，载置施加有凹凸花纹等外观设计性的脱模纸，以预热了的辊等进行热压制的方法；及使用施加有凹凸花纹等外观设计性的辊涂机，进行热压制的方法。在上述热压制时，例如，可在50～200℃加热辊。
实施例
以下使用实施例更详细地说明本发明。
[合成例1]氨基甲酸酯树脂(A-1)的制备
在甲乙酮3281质量份及辛酸亚锡0.1质量份的存在下，在70℃使聚碳酸酯多元醇(“NIPPOLLAN 980R”日本聚氨酯株式会社制、数均分子量：2000)1000质量份、2,2-二羟甲基丙酸17质量份、乙二醇47质量份、及二苯基甲烷二异氰酸酯(以下简称为“MDI”)344质量份进行反应至溶液粘度达到20000mPa·s，然后加入甲醇3质量份，使反应停止，得到氨基甲酸酯树脂的甲乙酮溶液。在该氨基甲酸酯树脂溶液中混合聚氧乙烯二苯乙烯化苯醚(亲水亲油平衡值(以下简称为“HLB”)：14)70质量份、及三乙胺13质量份，然后加入离子交换水800质量份，进行相转移乳化，由此得到上述氨基甲酸酯树脂(A-1)分散于水中的乳化液。
接下来，通过从上述乳化液中馏去甲乙酮，得到包含氨基甲酸酯树脂(A-1)50质量％的氨基甲酸酯树脂组合物。
[合成例2]氨基甲酸酯树脂(A-2)的制备
在甲乙酮3281质量份及辛酸亚锡0.1质量份的存在下，在70℃使聚醚多元醇(“PTMG 2000”三菱化学株式会社制、数均分子量：2000)1000质量份、2,2-二羟甲基丙酸17质量份、乙二醇47质量份、及MDI 344质量份进行反应至溶液粘度达到20000mPa·s，然后加入甲醇3质量份，使反应停止，得到氨基甲酸酯树脂的甲乙酮溶液。在该氨基甲酸酯树脂溶液中混合聚氧乙烯二苯乙烯化苯醚(HLB：14)70质量份、及三乙胺13质量份，然后加入离子交换水800质量份，进行相转移乳化，由此得到上述氨基甲酸酯树脂(A-2)分散于水中的乳化液。
接下来，通过从上述乳化液中馏去甲乙酮，得到包含氨基甲酸酯树脂(A-2)50质量％的氨基甲酸酯树脂组合物。
[合成例3]氨基甲酸酯树脂(A-3)的制备
在甲乙酮3281质量份及辛酸亚锡0.1质量份的存在下，在70℃使聚酯多元醇(“PLACCEL220”Daicel株式会社制、数均分子量：2000)1000质量份、2,2-二羟甲基丙酸17质量份、乙二醇47质量份、及MDI 344质量份进行反应至溶液粘度达到20000mPa·s，然后加入甲醇3质量份，使反应停止，得到氨基甲酸酯树脂的甲乙酮溶液。在该氨基甲酸酯树脂溶液中混合聚氧乙烯二苯乙烯化苯醚(HLB：14)70质量份、及三乙胺13质量份，然后加入离子交换水800质量份，进行相转移乳化，由此得到上述氨基甲酸酯树脂(A-3)分散于水中的乳化液。
接下来，通过从上述乳化液中馏去甲乙酮，得到包含氨基甲酸酯树脂(A-3)50质量％的氨基甲酸酯树脂组合物。
[合成例4]氨基甲酸酯树脂(A-4)的制备
在甲乙酮1279质量份及辛酸亚锡0.1质量份的存在下，在70℃使聚碳酸酯多元醇(“NIPPOLLAN980R”日本聚氨酯株式会社制、数均分子量：2000)1000质量份、2,2-二羟甲基丙酸17质量份、及二环己基甲烷二异氰酸酯(以下简称为“H12MDI”)262质量份进行反应至异氰酸酯浓度达到1.2质量％，得到氨基甲酸酯预聚物的甲乙酮溶液。在该氨基甲酸酯树脂溶液中混合聚氧乙烯二苯乙烯化苯醚(亲水亲油平衡值(以下简称为“HLB”)：14)64质量份、及三乙胺28质量份，然后加入离子交换水2650质量份，进行相转移乳化，由此得到上述氨基甲酸酯预聚物分散于水中的乳化液。在得到的乳化液中混合乙二胺21质量份与离子交换水189份，进行扩链反应，由此得到氨基甲酸酯树脂组合物。
接下来，通过从氨基甲酸酯树脂组合物中馏去甲乙酮与水分，得到包含氨基甲酸酯树脂(A-4)50质量％的氨基甲酸酯树脂组合物。
[合成例5]氨基甲酸酯树脂(A-5)的制备
在甲乙酮1279质量份及辛酸亚锡0.1质量份的存在下，在70℃使聚醚多元醇(“PTMG2000”三菱化学株式会社制、数均分子量：2000)1000质量份、2,2-二羟甲基丙酸17质量份、及H12MDI 262质量份进行反应至异氰酸酯浓度达到1.2质量％，得到氨基甲酸酯树脂预聚物(A‘-2)的甲乙酮溶液。在该氨基甲酸酯树脂溶液中混合聚氧乙烯二苯乙烯化苯醚(亲水亲油平衡值(以下简称为“HLB”)：14)64质量份、及三乙胺28质量份，然后加入离子交换水2650质量份，进行相转移乳化，由此得到上述氨基甲酸酯预聚物分散于水中的乳化液。在得到的乳化液中混合乙二胺21质量份与离子交换水189份，进行扩链反应，由此得到氨基甲酸酯树脂组合物。
接下来，通过从氨基甲酸酯树脂组合物中馏去甲乙酮与水分，得到包含氨基甲酸酯树脂(A-5)50质量％的氨基甲酸酯树脂组合物。
[合成例6]氨基甲酸酯树脂(A-6)的制备
在甲乙酮1279质量份及辛酸亚锡0.1质量份的存在下，在70℃使聚酯多元醇(“PLACCEL 220”Daicel株式会社制、数均分子量：2000)1000质量份、2,2-二羟甲基丙酸17质量份、及H12MDI 262质量份进行反应至异氰酸酯浓度达到1.2质量％，得到氨基甲酸酯树脂预聚物的甲乙酮溶液。在该氨基甲酸酯树脂溶液中混合聚氧乙烯二苯乙烯化苯醚(亲水亲油平衡值(以下简称为“HLB”)：14)64质量份、及三乙胺28质量份，然后加入离子交换水2650质量份，进行相转移乳化，由此得到上述氨基甲酸酯预聚物分散于水中的乳化液。在得到的乳化液中混合乙二胺21质量份与离子交换水189份，进行扩链反应，由此得到氨基甲酸酯树脂组合物。
接下来，通过从氨基甲酸酯树脂组合物中馏去甲乙酮与水分，得到包含氨基甲酸酯树脂(A-6)50质量％的氨基甲酸酯树脂组合物。
[实施例1]
在合成例1所得的氨基甲酸酯树脂组合物100质量份中，加入增粘剂(Borchers公司制“Borchi Gel ALA”)2质量份、硬脂酸铵0.5质量份、及交联剂(日本触媒株式会社制“EPOCROSWS-700”)4质量份，使用机械混合机，以2000rpm搅拌1分钟，进行起泡，得到成为1.5倍的体积的起泡液。
将其涂布于脱模纸，在80℃干燥3分钟，进一步在120℃干燥2分钟，由此制造发泡氨基甲酸酯片。
[实施例2～8]
将使用的水性氨基甲酸酯树脂组合物的种类、及硬脂酸铵的使用量，如表1～3所示那样地进行变更，除此以外与实施例1同样地进行得到发泡氨基甲酸酯片。
[比较例1]
在合成例1中所得的氨基甲酸酯树脂组合物100质量份中，加入增粘剂(Borchers公司制“Borchi Gel ALA”)2质量份、十二基苯磺酸钠1.5质量份、及交联剂(日本触媒株式会社制“EPOCROS WS-700”)4质量份，使用机械混合机，以2000rpm搅拌1分钟，进行起泡，得到成为1.5倍的体积的起泡液。
将其涂布于脱模纸，在80℃干燥3分钟，进一步在120℃干燥2分钟，由此制造片。
[比较例2]
在合成例1中所得的氨基甲酸酯树脂组合物100质量份中，加入增粘剂(Borchers公司制“Borchi Gel ALA”)2质量份、及交联剂(日本触媒株式会社制“EPOCROSWS-700”)4质量份，使用机械混合机，以2000rpm搅拌1分钟，进行起泡，得到成为1.5倍的体积的起泡液。
将其涂布于脱模纸，在80℃干燥3分钟，进一步在120℃干燥2分钟后，由于气泡在干燥工序中消失，因此形成几乎无孔的片。
[比较例3]
在合成例1所得的氨基甲酸酯树脂组合物100质量份中，加入增粘剂(Borchers公司制“Borchi Gel ALA”)2质量份、十二基苯磺酸钠1.5质量份、硬脂酸铵1质量份、及交联剂(日本触媒株式会社制“EPOCROS WS-700”)4质量份，使用机械混合机，以2000rpm搅拌1分钟，进行起泡，得到成为7倍的体积的起泡液。
将其涂布于脱模纸，在80℃干燥3分钟，进一步在120℃干燥2分钟，由此制造片。
[数均分子量的测定方法]
合成例所使用的多元醇等的数均分子量利用凝胶渗透色谱柱层析(GPC)法，以下述的条件进行测定。
测定装置：高速GPC装置(Tosoh株式会社制“HLC-8220GPC”)
色谱柱：将Tosoh株式会社制的下述的色谱柱串联使用。
“TSKgel G5000”(7.8mmI.D.×30cm)×1根
“TSKgel G4000”(7.8mmI.D.×30cm)×1根
“TSKgel G3000”(7.8mmI.D.×30cm)×1根
“TSKgel G2000”(7.8mmI.D.×30cm)×1根
检测器：RI(示差折射仪)
柱温：40℃
洗脱液：四氢呋喃(THF)
流速：1.0mL/分钟
进样量：100μL(试样浓度0.4质量％的四氢呋喃溶液)
标准试样：使用下述的标准聚苯乙烯，作成校准曲线。
(标准聚苯乙烯)
Tosoh株式会社制“TSKgel标准聚苯乙烯A-500”
Tosoh株式会社制“TSKgel标准聚苯乙烯A-1000”
Tosoh株式会社制“TSKgel标准聚苯乙烯A-2500”
Tosoh株式会社制“TSKgel标准聚苯乙烯A-5000”
Tosoh株式会社制“TSKgel标准聚苯乙烯F-1”
Tosoh株式会社制“TSKgel标准聚苯乙烯F-2”
Tosoh株式会社制“TSKgel标准聚苯乙烯F-4”
Tosoh株式会社制“TSKgel标准聚苯乙烯F-10”
Tosoh株式会社制“TSKgel标准聚苯乙烯F-20”
Tosoh株式会社制“TSKgel标准聚苯乙烯F-40”
Tosoh株式会社制“TSKgel标准聚苯乙烯F-80”
Tosoh株式会社制“TSKgel标准聚苯乙烯F-128”
Tosoh株式会社制“TSKgel标准聚苯乙烯F-288”
Tosoh株式会社制“TSKgel标准聚苯乙烯F-550”
[氨基甲酸酯树脂(A)的流动起始温度的测定方法]
将合成例所得的水性氨基甲酸酯树脂组合物涂布于脱模纸(涂布厚度150μm)，并以热风干燥机，在70℃干燥4分钟，接着在120℃干燥2分钟，由此得到干燥物。将该干燥物，使用岛津制作所株式会社制流动试验机“CFT-500A”(使用口径1mm、长度1mm的模具、载荷98N、升温速度3℃/分钟)，测定流动起始温度。
[手感的评价方法]
以手触摸得到的发泡氨基甲酸酯片，并按以下方式评价。
“A”：富有柔软性。
“B”：稍有柔软性。
“C”：柔软性差。
“D”：硬。
[拉伸强度的测定方法]
将所得到的氨基甲酸酯片裁切为宽10mm、长度60mm，将其作为试验片。将该试验片的两端以夹具夹持，使用拉伸试验机“Autograph AG-I”(岛津制作所株式会社制)，在温度23℃、湿度60％的环境下，以十字头速度300mm/分钟拉伸，测定100％伸长时的拉伸强度，并按以下方式评价。
“T”：10N/cm2以上
“F”：小于10N/cm2
[表1]
Figure BDA0002433303820000151
[表2]
Figure BDA0002433303820000152
[表3]
Figure BDA0002433303820000153
可知：作为本发明的发泡氨基甲酸酯片的实施例1～8具有优异的手感及拉伸强度。
另一方面，比较例1为使用具有芳香环的十二基苯磺酸钠代替表面活性剂(C)的实施方式，气泡保持性不良，片的手感硬而不良。
比较例2为未使用表面活性剂(C)的实施方式，气泡保持性不良，片的手感硬而不良。
比较例3为使发泡倍率过剩，密度低于本发明所限定的范围的实施方式，拉伸强度不良。
[实施例9]
在合成例1所得的氨基甲酸酯树脂组合物100质量份中，加入增粘剂(Borchers公司制“Borchi Gel ALA”)2质量份、硬脂酸铵1.5质量份、及交联剂(日本触媒株式会社制“EPOCROS WS-700”)4质量份，使用机械混合机，以2000rpm搅拌1分钟，进行起泡，得到成为1.5倍的体积的起泡液。
将其涂布于聚酯纤维无纺布，在80℃干燥3分钟，进一步在120℃干燥2分钟，由此形成聚氨酯层。接下来，在得到的聚氨酯层上，载置施加有凹凸图案的脱模纸，并实施预热为180℃的辊加压，由此得到压印加工了的合成皮革。
[实施例10～12]
将使用的氨基甲酸酯树脂组合物的种类、及硬脂酸铵的使用量，如表4所示那样进行变更，除此以外与实施例9同样进行，得到合成皮革。
[手感的评价方法]
以手触摸得到的合成皮革，并按以下方式评价。
“A”：富有柔软性。
“B”：稍有柔软性。
“C”：柔软性差。
“D”：硬。
[剥离强度的测定方法]
将实施例及比较例所得到的合成皮革，使用岛津Autograph“AG-1”(岛津制作所株式会社制)，以满刻度5kg、测试头20mm/分钟的条件，测定剥离强度，并按以下方式评价。
“A”：0.15MPa以上
“B”：0.1MPa以上且小于0.15MPa
“C”：小于0.1MPa
[压印加工性的评价方法]
以目视观察实施例及比较例所得到的合成皮革，并按以下方式评价。
“T”：可均匀地制作通过压印加工形成的表面上的皱褶。
“F”：通过压印加工形成的表面上的皱褶不均匀。
[表4]
Figure BDA0002433303820000171
可知：作为本发明的合成皮革的实施例9～12具有优异的手感、剥离强度、及压印加工性。

Claims (5)

1.一种发泡氨基甲酸酯片，其特征在于，由含有氨基甲酸酯树脂(A)、水(B)、及表面活性剂(C)的氨基甲酸酯树脂组合物形成，密度为200～1000kg/m3，
所述表面活性剂(C)不具有芳香环且具有碳原子数为10以上的疏水部，
所述氨基甲酸酯树脂(A)以选自4,4’-二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、二环己基甲烷二异氰酸酯和异佛尔酮二异氰酸酯中的一种以上的多异氰酸酯、多元醇、具有羧基的二醇化合物、以及扩链剂作为原料，
所述氨基甲酸酯树脂(A)的流动起始温度为80～220℃的范围，
所述流动起始温度是以使用口径1mm、长度1mm的模具、载荷98N、升温速度3℃/分钟的方式，使用流动试验机对将所述氨基甲酸酯树脂(A)以厚度150μm的方式涂布于脱模纸、并以热风干燥机干燥而得的干燥物进行测定而得的。
2.如权利要求1所述的发泡氨基甲酸酯片，其中，所述表面活性剂(C)为硬脂酸盐。
3.如权利要求1或2所述的发泡氨基甲酸酯片，其中，所述氨基甲酸酯树脂(A)具有阴离子性基团。
4.一种合成皮革，其特征在于，其是至少具有基材(i)、及聚氨酯层(ii)的合成皮革，所述聚氨酯层(ii)为由权利要求1～3中任一项所述的发泡氨基甲酸酯片形成的层。
5.如权利要求4所述的合成皮革，其中，所述聚氨酯层(ii)为实施了压印加工的层。
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JP6521349B1 (ja) 2019-05-29
US20210164157A1 (en) 2021-06-03
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KR20200055006A (ko) 2020-05-20
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