CN117777396A - 热封性水系树脂组合物、层压板 - Google Patents
热封性水系树脂组合物、层压板 Download PDFInfo
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- CN117777396A CN117777396A CN202311183169.0A CN202311183169A CN117777396A CN 117777396 A CN117777396 A CN 117777396A CN 202311183169 A CN202311183169 A CN 202311183169A CN 117777396 A CN117777396 A CN 117777396A
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Classifications
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- 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
- C08L75/08—Polyurethanes from polyethers
-
- 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
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
-
- 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
- C08G18/08—Processes
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
- C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
- C08G18/0847—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers
- C08G18/0852—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers the solvents being organic
-
- 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
- C08G18/08—Processes
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
- C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
- C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
- C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
-
- C—CHEMISTRY; METALLURGY
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Abstract
本发明的课题在于提供一种热封性水系树脂组合物,其提供具有优异的热封强度及耐粘连性的层压板。本发明涉及一种热封性水系树脂组合物、基材的至少一面上具有所述组合物的涂层的层压板,所述热封性水系树脂组合物包含氨基甲酸酯树脂(A),所述氨基甲酸酯树脂(A)为包含聚醚多元醇(a1)、聚异氰酸酯(a2)及链伸长剂(a3)的反应成分的生成物,或者所述热封性水系树脂组合物包含所述氨基甲酸酯树脂(A)及蜡(B)。
Description
技术领域
本发明涉及一种热封性水系树脂组合物、层压板。
背景技术
近年来,就降低环境负荷的观点而言,逐渐要求使用水系树脂组合物。在医疗用具包装体或食品包装中所利用的热封性膜(在基材上涂布热封性树脂组合物(热封剂)而得的膜)中,从以前起也推进水性化,例如,开发了包含聚烯烃树脂或聚氨基甲酸酯树脂的热封性水系树脂组合物(专利文献1、专利文献2)。
但是,在此种树脂组合物中,不仅热封强度有改善的余地,而且于抑制在利用辊卷取时粘接层与其上重叠的膜的粘连的方面,也有改善的余地。
[现有技术文献]
[专利文献]
[专利文献1]日本专利特开2006-045313号公报
[专利文献2]日本专利特开2014-004799号公报
发明内容
[发明所要解决的问题]
本发明的课题在于提供一种热封性水系树脂组合物,其提供热封强度高、耐粘连性也优异的层压板。
[解决问题的技术手段]
本发明人们进行了努力研究,由此发现解决了所述课题,从而完成了本发明。即,本发明涉及以下的热封性水系树脂组合物、层压板。
1.一种热封性水系树脂组合物,包含氨基甲酸酯树脂(A),所述氨基甲酸酯树脂(A)为包含聚醚多元醇(a1)、聚异氰酸酯(a2)及链伸长剂(a3)的反应成分的生成物。
2.根据前项1所述的热封性水系树脂组合物,其中,所述反应成分还包含(甲基)丙烯酸羟基烷基酯((meth)acrylic acid hydroxyalkyl ester)(a4)。
3.根据前项1或2所述的热封性水系树脂组合物,还包含蜡(B)。
4.一种层压板,基材的至少一面上具有根据前项1或2所述的热封性水系树脂组合物的涂层。
[发明的效果]
根据本发明的热封性水系树脂组合物,可提供热封强度高、耐粘连性也优异的层压板。
具体实施方式
本发明的热封性水系树脂组合物包含氨基甲酸酯树脂(A)(以下,称为(A)成分),所述氨基甲酸酯树脂(A)为包含聚醚多元醇(a1)(以下,称为(a1)成分)、聚异氰酸酯(a2)(以下,称为(a2)成分)及链伸长剂(a3)(以下,称为(a3)成分)的反应成分的生成物。
(a1)成分为聚醚多元醇,为用于使热封性水系树脂组合物的涂层显示出高的热封强度及优异的耐粘连性的成分。作为(a1)成分,例如可列举:聚乙二醇、聚丙二醇、聚丁二醇、聚四亚甲基二醇、聚六亚甲基二醇(polyhexamethylene glycol)、聚七亚甲基二醇(polyheptamethylene glycol)、聚十二亚甲基二醇(polydecamethylene glycol)、聚氧乙烯-聚氧丙烯二醇、聚氧四亚甲基-聚氧乙烯二醇、聚氧四亚甲基-聚氧丙烯二醇等。此外,聚醚多元醇的结构不论是无规型还是嵌段型,均可使用。这些可为单独一种,也可将两种以上加以组合。
作为聚醚多元醇的市售品,可列举:『艾迪科(Adeka)聚醚P-400』、『艾迪科(Adeka)聚醚G-400』、『艾迪科(Adeka)聚醚T-400』、『艾迪科(Adeka)聚醚AM-302』、『艾迪科(Adeka)聚醚P1000』、『艾迪科(Adeka)聚醚P2000』(以上为艾迪科(ADEKA)(股)制造);『聚乙二醇#1,540』(那卡莱泰库斯(Nacalai Tesque)(股)制造);『二丙二醇』、『聚丙二醇400』(以上为纯正化学(股)制造);『PEG#200』、『PEG#300』、『PEG#400』、『PEG#600』、『PEG#1000』、『PEG#1500』、『PEG#2000』、『PEG#4000』、『尤尼奥尔(UNIOL)D-200』、『尤尼奥尔(UNIOL)D-700』、『尤尼奥尔(UNIOL)D-1000』、『尤尼奥尔(UNIOL)D-1200』、『尤尼奥尔(UNIOL)D-2000』、『尤尼奥尔(UNIOL)D-4000』、『尤尼奥尔(UNIOL)PB-500』、『尤尼奥尔(UNIOL)PB-700』、『尤尼奥尔(UNIOL)PB-1000』、『尤尼奥尔(UNIOL)PB-2000』、『珀利赛林(Polycerin)DC-1100』、『珀利赛林(Polycerin)DC-1800E』、『珀利赛林(Polycerin)DC-3000E』、『珀利赛林(Polycerin)DCB-1000』、『珀利赛林(Polycerin)DCB-2000』、『珀利赛林(Polycerin)DCB-4000』(以上为日油(股)制造)等。
作为(a2)成分,例如可列举:亚甲基二异氰酸酯、异丙烯二异氰酸酯、丁烷-1,4-二异氰酸酯、六亚甲基二异氰酸酯、2,2,4-三甲基六亚甲基二异氰酸酯、2,4,4-三甲基六亚甲基二异氰酸酯、将二聚酸所具有的羧基取代为异氰酸酯基而成的二聚物二异氰酸酯等脂肪族二异氰酸酯;
环己烷-1,4-二异氰酸酯、异佛尔酮二异氰酸酯、二环己基甲烷-4,4'-二异氰酸酯、1,3-二(异氰酸酯甲基)环己烷、甲基环己烷二异氰酸酯等脂环族二异氰酸酯;
4,4'-二苯基甲烷二异氰酸酯、4,4'-二苯基二甲基甲烷二异氰酸酯、4,4'-二苯基四甲基甲烷二异氰酸酯、1,4-亚苯基二异氰酸酯、甲苯二异氰酸酯、二甲苯基二异氰酸酯(xylene diisocyanate)、间四甲基二甲苯基二异氰酸酯(m-tetramethylxylylenediisocyanate)、1,5-萘二异氰酸酯、4,4'-二苄基二异氰酸酯、1,3-亚苯基二异氰酸酯等芳香族二异氰酸酯;
赖氨酸二异氰酸酯(lysine diisocyanate)等氨基酸二异氰酸酯等。这些可为单独一种,也可将两种以上加以组合。另外,作为(a2)成分,也可使用这些的异氰脲酸体、加合物体或缩二脲体。
(a1)成分及(a2)成分的使用比率通常优选为设为以(a2)成分的异氰酸酯基的摩尔数(NCO(a2))与(a1)成分的羟基的摩尔数(OH(a1))的比率(NCO(a2)/OH(a1))计为1.1/1~8/1左右。
(a3)成分为链伸长剂。
作为(a3)成分,例如可列举:乙二胺、丙二胺、六亚甲基二胺、异佛尔酮二胺、二聚物二胺、二环己基甲烷-4,4'-二胺、2-羟基乙基乙二胺、2-羟基乙基丙二胺、二-2-羟基乙基乙二胺、二-2-羟基乙基丙二胺、2-羟基丙基乙二胺、二-2-羟基丙基乙二胺等二胺;
二乙三胺、二丙三胺、二丁三胺等三胺;
三乙四胺、三丙四胺等四胺;
N-甲基二乙醇胺、N-乙基二乙醇胺、N-丙基二乙醇胺、N-异丙基二乙醇胺、N-丁基二乙醇胺、N-异丁基二乙醇胺、N-油烯基二乙醇胺(N-oleyldiethanolamine)、N-硬脂基二乙醇胺、N-甲基二异丙醇胺、N-乙基二异丙醇胺、N-丙基二异丙醇胺、N-丁基二异丙醇胺等N-烷基二烷醇胺;
肼(hydrazine)或其肼衍生物(己二酸酰肼等);
甘油酸、二氧马来酸、二氧富马酸、二羟甲基乙酸、二羟甲基丙酸、二羟甲基丁酸、二羟甲基戊酸、二羟甲基己酸等二烷醇烷酸;
4,4-二(羟基苯基)丁酸、4,4-二(羟基苯基)戊酸、2,6-二氧苯甲酸等芳香族系羟基羧酸等。这些可为单独一种,也可将两种以上加以组合。其中,就使生成的(A)成分容易溶解或分散于水中的方面而言,优选为二烷醇烷酸。
此外,所述二烷醇胺也可使用其四级化盐(quaternary salt)。所述四级化盐是指所述二烷醇胺与四级化剂进行反应而得的物质,作为四级化剂,例如可列举:盐酸、硫酸、磷酸等无机酸;二甲基硫酸、乙酸、丙酸等有机酸;甲基氯化物、苄基氯化物、表氯醇等有机卤化合物等。
另外,所述二烷醇烷酸及芳香族系羟基羧酸的羧基可由中和剂中和。
作为所述中和剂,例如可列举:氢氧化钠、氢氧化钾等碱金属氢氧化物;氨;三甲胺、三乙胺、三乙醇胺、三异丙醇胺、N,N-二甲基乙醇胺、N,N-二乙基乙醇胺等有机胺等。这些可为单独一种,也可将两种以上加以组合。
作为(a3)成分的使用量,相对于100重量%的构成(A)成分的反应成分,通常为1重量%~30重量%,优选为3重量%~20重量%。
在本发明的(A)成分中,作为反应成分,也可还包含(甲基)丙烯酸羟基烷基酯(a4)(以下,称为(a4)成分)。
作为(a4)成分,例如可列举:(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸2-羟基正丙酯、(甲基)丙烯酸3-羟基正丙酯、(甲基)丙烯酸3-羟基正丁酯、(甲基)丙烯酸4-羟基正丁酯、(甲基)丙烯酸6-羟基正己酯等。这些可为单独一种,也可将两种以上加以组合。其中,优选为具有碳数为2~3的羟基烷基(hydroxyalkyl)的成分,更优选为(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸2-羟基正丙酯。
作为(a4)成分的使用量,相对于100重量%的构成(A)成分的反应成分,通常为10重量%以下,优选为0.1重量%~5重量%。
在本发明的(A)成分中,作为反应成分,也可还包含不具有羟基的(甲基)丙烯酸单烷基酯(a5)(以下,称为(a5)成分)。
作为(a5)成分,例如可列举:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸异丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸仲丁酯(s-butyl(meth)acrylate)、(甲基)丙烯酸叔丁酯(t-butyl(meth)acrylate)、(甲基)丙烯酸正戊酯、(甲基)丙烯酸环戊酯(cyclopentyl(meth)acrylate)、(甲基)丙烯酸正己酯、(甲基)丙烯酸环己酯(cyclohexyl(meth)acrylate)、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸正癸酯、(甲基)丙烯酸异冰片酯、(甲基)丙烯酸异癸酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸肉豆蔻酯、(甲基)丙烯酸异肉豆蔻酯、(甲基)丙烯酸棕榈酸酯、(甲基)丙烯酸硬脂酯、(甲基)丙烯酸异硬脂酯等。这些可为单独一种,也可将两种以上加以组合。其中,优选为具有碳数12~18的烷基的成分,更优选为(甲基)丙烯酸月桂酯(lauryl(meth)acrylate)、(甲基)丙烯酸肉豆蔻酯(myristyl(meth)acrylate)、(甲基)丙烯酸棕榈酸酯(palmityl(meth)acrylate)、(甲基)丙烯酸硬脂酯(stearyl(meth)acrylate)。
作为(a5)成分的使用量,相对于100重量%的构成(A)成分的反应成分,通常为50重量%以下,优选为10重量%~40重量%。
在所述反应成分中,也可还包含链伸长停止剂(a6)(以下,称为(a6)成分)。作为(a6)成分,例如可列举:甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇等一元醇;乙胺、正丙胺、二乙胺、二正丙胺、二正丁胺等单胺;单乙醇胺、二乙醇胺等烷醇单胺等。这些可为单独一种,也可将两种以上加以组合。
作为(a6)成分的使用量,相对于100重量%的构成(A)成分的反应成分,通常为5重量%以下,优选为3重量%以下。
(A)成分例如可通过如下方式来获得:使(a1)成分与(a2)成分反应来制造氨基甲酸酯预聚物,继而,使氨基甲酸酯预聚物及(a3)成分、视需要的(a4)成分~(a6)成分反应。
作为获得氨基甲酸酯预聚物的工序的反应条件,温度通常为40℃~150℃左右,优选为60℃~100℃左右。另外,时间通常为1小时~20小时左右,优选为1小时~10小时左右。
继而,作为使(a3)成分、视需要的(a4)成分~(a6)成分与氨基甲酸酯预聚物反应时的条件,温度通常为20℃~100℃左右,优选为30℃~80℃左右。另外,时间通常为1小时~10小时左右,优选为1小时~5小时左右。此外,各成分的混合方法、混合顺序并无特别限定。
这些(A)成分的制造可在无溶剂下进行,也可在亲水性溶媒的存在下进行。
作为亲水性溶媒,例如可列举:丙酮、甲基乙基酮、甲基异丁基酮、异佛尔酮、环己酮、甲基环己酮等酮;乙二醇单甲醚、乙二醇单乙醚、乙二醇单丁醚、二乙二醇单甲醚、二乙二醇单乙醚、二乙二醇单丁醚、丙二醇单甲醚、丙二醇单乙醚、丙二醇单正丁醚、丙二醇单叔丁醚等烷二醇单醚;3-甲氧基丁醇、3-甲氧基-3-甲基丁醇等烷氧基醇;甲基溶纤剂、乙基溶纤剂、正丁基溶纤剂、叔丁基溶纤剂等溶纤剂;甲基溶纤剂乙酸酯、乙基溶纤剂乙酸酯等溶纤剂乙酸酯;甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、仲丁醇、叔丁醇等烷基醇;N,N-二甲基甲酰胺、N,N-二甲基乙酰胺等酰胺;N-甲基吡咯烷酮等胺;离子交换水、超纯水、纯水、精制水、自来水、软水、硬水、工业用水等水;二甲基亚砜等。这些可为单独一种,也可将两种以上加以组合。另外,在反应结束后,也可将所述溶媒在减压下等蒸馏去除。
作为溶媒的使用量,优选为以反应浓度成为10重量%以上的方式进行调整。
另外,在所述反应中,也可加入后述的(B)成分。
(A)成分中也可还包含颜料、保水剂、消泡剂、防腐剂、流平剂、着色剂、防粘连剂、抗氧化剂、塑化剂、硬化剂、紫外线吸收剂、增稠剂、乳化剂、分散剂、填料等添加剂。这些添加剂可为单独一种,也可将两种以上加以组合。
所获得的(A)成分的重量平均分子量为5000~2000000。此外,重量平均分子量为利用凝胶渗透色谱(gel permeation chromatography,GPC)法并以聚苯乙烯为标准物质进行测定所得的值。
另外,温度25℃下的不挥发成分浓度35重量%的(A)成分的溶液的粘度通常为5mPa·s~20000mPa·s,优选为10mPa·s~10000mPa·s。此处的“粘度”是指利用B型粘度计进行测定所得的值。
本发明的热封性水系树脂组合物也可还包含蜡(B)(以下,称为(B)成分)。通过调配(B)成分,热封性水系树脂组合物的涂层容易显示出优异的耐粘连性。另外,作为(B)成分的形态,可列举固体状、液状、乳液状等。
作为(B)成分,例如可列举:动物系蜡、植物系蜡、石油系蜡、矿物系蜡等天然蜡;合成烃系蜡、改性蜡、氢化蜡等合成蜡等。
作为动物系蜡,例如可列举:蜜蜡、白蜡、鲸蜡等。
作为植物系蜡,例如可列举:巴西棕榈蜡(carnauba wax)、米蜡(rice wax)、小烛树蜡(candelilla wax)、木蜡等。
作为石油系蜡,例如可列举:石蜡(paraffin wax)、微晶蜡(microcrystallinewax)、矿脂(petrolatum)等。
作为矿物系蜡,例如可列举:褐煤蜡(montan wax)、纯地蜡(ceresin wax)、地蜡(ozokerite)等。
作为合成烃系蜡,例如可列举:聚乙烯蜡、氧化聚乙烯蜡、氧化聚丙烯蜡、费-托(Fischer-Tropsch)蜡等。
作为改性蜡,例如可列举:褐煤蜡衍生物、石蜡衍生物、微晶蜡衍生物等。
作为氢化蜡,例如可列举硬化蓖麻油、硬化蓖麻油衍生物等。
另外,作为(B)成分,例如也可列举烷基烯酮二聚物系蜡、聚四氟乙烯蜡等。
所述(B)成分可为单独一种,也可将两种以上加以组合。其中,优选为植物系蜡、石油系蜡。
另外,(B)成分中也可还包含颜料、保水剂、消泡剂、防腐剂、流平剂、着色剂、防粘连剂、抗氧化剂、紫外线吸收剂、增稠剂、乳化剂、分散剂、填料等添加剂。这些添加剂可为单独一种,也可将两种以上加以组合。
作为(A)成分与(B)成分的使用重量比率,例如可列举:以不挥发成分重量(以下相同)计而为(A)/(B)=100/0、99/1、98/2、97/3、96/4、95/5、94/6、93/7、92/8、91/9、90/10、87.5/12.5、85/15、82.5/17.5、80/20、77.5/22.5、75/25、72.5/27.5、70/30、67.5/32.5、65/35、62.5/37.5、60/40、57.5/42.5、55/45、52.5/47.5、50/50等。其中,就涂层容易显示出高的热封强度的方面而言,所述重量比率优选为(A)/(B)=100/0~50/50,更优选为(A)/(B)=100/0~70/30。此外,所谓不挥发成分,是指去除亲水性溶媒等挥发成分后残留的成分。
本发明的热封性水系树脂组合物是将(A)成分及(B)成分、视需要的水混合来获得。作为混合条件,例如温度为10℃~90℃(优选为20℃~80℃)。另外,各成分的混合顺序或混合方法、混合时间并无特别限定。
另外,本发明的热封性水系树脂组合物中也可还包含颜料、保水剂、消泡剂、防腐剂、流平剂、着色剂、防粘连剂、抗氧化剂、紫外线吸收剂、增稠剂、乳化剂、分散剂、填料等添加剂。这些添加剂可为单独一种,也可将两种以上加以组合。
作为所获得的热封性水系树脂组合物的物性,不挥发成分浓度通常为10重量%~60重量%,优选为20重量%~50重量%。
另外,温度25℃下的不挥发成分浓度30重量%的热封性水系树脂组合物的溶液的粘度通常为10mPa·s~2000mPa·s,优选为20mPa·s~1000mPa·s。此外,此处的“粘度”是利用B型粘度计进行测定所得的值。
本发明的层压板为基材的至少一面上具有所述热封性水系树脂组合物的涂层的层压板。
所述层压板例如可通过在基材的至少一面上涂敷热封性水系树脂组合物并使其干燥的方法等而获得。
作为基材,例如可列举:原纸、支撑膜、金属板等。
作为原纸,例如可列举:阔叶树纸浆(阔叶树漂白牛皮纸浆(leaf bleached kraftpulp,LBKP))、针叶树纸浆(针叶树漂白牛皮纸浆(needle bleached kraft pulp,NBKP))等化学纸浆;碎木纸浆(磨石磨纸浆(ground pulp,GP))、精炼机磨石磨纸浆(refiner groundpulp,RGP)、热磨机械纸浆(thermo-mechanical pulp,TMP)等机械纸浆;使用脱墨废纸浆(deinked pulp,DIP)、实施了丝光化处理的纸浆、废纸纸浆等,利用各种抄纸机抄纸而得的纸浆等,更具体而言,可列举:漂白牛皮纸、未漂白牛皮纸、优质纸、中质纸、微涂敷纸、涂敷纸、加工原纸、板纸、白板纸、挂面纸(liner)、半透明纸、透明纸、羊皮纸等。另外,也可使用在所述纸浆中包含硫酸铝、硫酸或氢氧化钠等pH值调整剂;施胶剂、纸力增强剂(例如可列举淀粉或聚丙烯酰胺等)、湿润纸力剂等制纸用化学品;滑石、粘土、高岭土、二氧化钛、碳酸钙等填料等的纸浆。
作为支撑膜,例如可列举:聚酰亚胺、聚酰亚胺-二氧化硅杂化物等聚酰亚胺树脂;聚乙烯、聚丙烯、环烯烃聚合物等聚烯烃树脂;聚对苯二甲酸乙二酯、聚萘二甲酸乙二酯、聚丁二酸丁二酯、聚丁二酸-己二酸丁二酯、聚己二酸-对苯二甲酸丁二酯、聚羟基脂肪酸酯、聚乳酸等聚酯树脂;聚甲基丙烯酸甲酯等丙烯酸树脂;聚四氟乙烯(Polytetrafluoroethylene,PTFE)、全氟烷氧基烷烃(Perfluoroalkoxy alkane,PFA)、聚偏二氟乙烯(polyvinylidene fluoride,PVDF)等氟系树脂;由对苯二甲酸乙二酯、苯酚、邻苯二甲酸、羟基萘甲酸等与对羟基苯甲酸获得的芳香族系聚酯树脂(所谓的液晶聚合物;可乐丽(KURARAY)(股)制造,“百库斯达(Vecstar)”等);乙酰纤维素、玻璃纸(cellophane)等纤维素树脂;聚苯乙烯树脂、聚碳酸酯树脂、丙烯腈-丁二烯-苯乙烯树脂等。这些可为单独一种,也可将两种以上加以组合。
作为金属板,可列举:铝板、镀铝钢板、镀Al-Si合金钢板等铝系金属板;镀锌钢板、镀Zn-Fe合金钢板、镀Zn-Co合金钢板、镀Zn-Co-Cr合金钢板、镀Zn-Cr-Ni合金钢板、镀Zn-Cr-Fe合金钢板、镀Zn-Al合金钢板、镀Zn-Mg合金钢板、镀Zn-Al-Mg合金钢板、镀Zn-Ni合金钢板等锌系金属板;铜板、钢板、钛板、不锈钢钢板、白铁板、镀镍钢板、镀铬钢板、磷酸处理钢板等。这些可为单独一种,也可将两种以上加以组合。
另外,作为原纸、支撑膜或金属板,也可使用在其一面或两面上进一步设置有锚固层、填料层、耐水层、耐油层、阻挡层、防静电层等的材料。
作为热封性水系树脂组合物的涂敷方法,例如可列举:棒涂布机、刀式涂布机、施胶压榨涂布机、辊涂布机、逆转辊涂布机、帘式涂布机、凹版涂布机、柔版涂布机、气刀涂布机、压延机、门辊涂布机、刮刀涂布机、两辊施胶压榨或刮棒式计量等。另外,热封性水系树脂组合物的涂敷量(换算成不挥发成分)也并无特别限定,通常为0.1g/m2~10g/m2左右,优选为1g/m2~7g/m2左右。
涂敷后的基材通过热、送风、自然干燥来进行干燥。作为热源,例如可列举:热风干燥机、红外线加热器、旋转干燥器等。另外,作为干燥条件,例如温度为80℃~220℃(优选为100℃~200℃),时间为1秒~180分钟(优选为30秒~60分钟)。
[实施例]
以下,列举实施例进一步具体地说明本发明,但本发明并不限定于这些例子。此外,只要无特别记载,则实施例中,份及%全部为质量基准。
<实施例1:氨基甲酸酯树脂(A-1)的制备>
向包括搅拌机、温度计、冷却管及氮气导入管的反应容器中投入二羟甲基丁酸59.4份、聚四亚甲基二醇(商品名:“PTMG1000”、数量平均分子量1000、三菱化学(股)制造)489.9份、异佛尔酮二异氰酸酯275.5份、丙烯酸2-羟基乙酯2.0份,在氮气流下且在85℃下进行5小时反应,获得氨基甲酸酯预聚物826.8份。继而,在搅拌下,向包含水1300.0份、异丙醇225.0份、三乙胺40.5份、己二酸二酰肼37.5份的水溶液中添加所述氨基甲酸酯预聚物并使其分散,在50℃下反应3小时。接下来,添加V-50(富士胶片和光纯药(股)制造)0.1份,在80℃下反应1小时。进而加入规定量的水,从而获得不挥发成分浓度35%、粘度300mPa·s、pH值8.0的氨基甲酸酯树脂(A-1)。
<实施例2:氨基甲酸酯树脂(A-2)的制备>
向与实施例1相同的反应容器中投入二羟甲基丁酸59.4份、聚四亚甲基二醇(商品名:“PTMG1000”、数量平均分子量1000、三菱化学(股)制造)489.9份、异佛尔酮二异氰酸酯285.5份,在氮气流下且在85℃下进行5小时反应,获得氨基甲酸酯预聚物834.8份。继而,在搅拌下,向包含水1365.0份、异丙醇225.0份、三乙胺40.5份、己二酸二酰肼65.0份的水溶液中添加所述氨基甲酸酯预聚物并使其分散。在50℃下反应3小时,进而加入规定量的水,从而获得不挥发成分浓度35%、粘度1500mPa·s、pH值8.0的氨基甲酸酯树脂(A-2)。
<实施例3:氨基甲酸酯树脂(A-3)的制备>
向与实施例1相同的反应容器中投入二羟甲基丙酸59.4份、聚四亚甲基二醇(商品名:“PTMG1000”、数量平均分子量1000、三菱化学(股)制造)489.9份、异佛尔酮二异氰酸酯275.5份、甲基乙基酮208.7份,在氮气流下且在85℃下进行5小时反应,获得氨基甲酸酯预聚物1043.5份。继而,在搅拌下,向包含水1230.0份、异丙醇100.0份、三乙胺44.7份、己二酸二酰肼37.5份的水溶液中添加所述氨基甲酸酯预聚物并使其分散,在50℃下反应3小时,获得不挥发成分浓度35%、粘度350mPa·s、pH值8.0的氨基甲酸酯树脂(A-3)。
<实施例4:氨基甲酸酯树脂(A-4)的制备>
向与实施例1相同的反应容器中投入二羟甲基丁酸59.4份、珀利赛林(Polycerin)DCB-2000(聚氧四亚甲基-聚氧丙烯二醇、数量平均分子量2000、日油(股)制造)489.9份、异佛尔酮二异氰酸酯200.8份,在氮气流下且在85℃下进行5小时反应,获得氨基甲酸酯预聚物750.1份。继而,在搅拌下,向包含水1170.0份、异丙醇225.0份、三乙胺40.5份、己二酸二酰肼43.3份的水溶液中添加所述氨基甲酸酯预聚物并使其分散。在50℃下反应3小时,进而加入规定量的水,从而获得不挥发成分浓度35%、粘度500mPa·s、pH值8.0的氨基甲酸酯树脂(A-4)。
<实施例5:氨基甲酸酯树脂(A-5)的制备>
向与实施例1相同的反应容器中投入二羟甲基丁酸59.4份、聚四亚甲基二醇(商品名:“PTMG1500”、数量平均分子量1000、三菱化学(股)制造)489.9份、二苯基甲烷二异氰酸酯250.0份,在氮气流下且在85℃下进行5小时反应,获得氨基甲酸酯预聚物750.3份。继而,在搅拌下,向包含水1208.0份、异丙醇225.0份、三乙胺40.5份、己二酸二酰肼43.3份的水溶液中添加所述氨基甲酸酯预聚物并使其分散。在50℃下反应3小时,进而加入规定量的水,从而获得不挥发成分浓度35%、粘度500mPa·s、pH值8.0的氨基甲酸酯树脂(A-5)。
<实施例6:氨基甲酸酯树脂(A-6)的制备>
向与实施例1相同的反应容器中投入二羟甲基丁酸38.1份、珀利赛林(Polycerin)DCB-2000(聚氧四亚甲基-聚氧丙烯二醇、数量平均分子量2000、日油(股)制造)314.5份、异佛尔酮二异氰酸酯128.9份、丙烯酸2-羟基乙酯12.7份、甲基丙烯酸硬脂酯256.1份,在氮气流下且在85℃下进行5小时反应,获得氨基甲酸酯预聚物750.3份。继而,在搅拌下,向包含水1208.0份、异丙醇225.0份、三乙胺26.6份、己二酸二酰肼27.8份的水溶液中添加所述氨基甲酸酯预聚物并使其分散,在50℃下反应3小时。接下来,添加V-601(富士胶片和光纯药(股)制造)5.0份,在80℃下反应3小时。进而加入规定量的水,从而获得不挥发成分浓度35%、粘度300mPa·s、pH值8.0的氨基甲酸酯树脂(A-6)。
比较例1~比较例2
作为比较例1,将聚碳酸酯系氨基甲酸酯系树脂(商品名:“斯帕福莱库斯(SUPERFLEX)460S”、第一工业制药(股)制造)供于以下评价,作为比较例2,将聚酯系氨基甲酸酯系树脂(商品名:“斯帕福莱库斯(SUPERFLEX)500M”、第一工业制药(股)制造)供于以下评价。
<涂敷液的制备>
向各氨基甲酸酯系树脂中加入离子交换水,分别制备不挥发成分浓度30%的涂敷液。
<层压板的制作>
在牛皮纸(商品名:“海科(HEIKO)”、下岛(SHIMOJIMA)(股)制造、基重70g/m2)上使用迈耶棒(Mayer bar),将各涂敷液以干燥后的固体成分量为7g/m2的方式涂敷后,在100℃下干燥30秒,分别获得层压板。
<热封强度>
将各层压板裁断成纵75mm×横110mm,将涂敷面向内侧纵向对折。在折痕侧,以距端部20mm的密封宽度,使用热封测试仪(heat seal tester)TP-701S(测试仪产业(股)制造),在温度130℃、压力2kgf/cm2下热压接1秒。将其5等分,制作5个15mm×55mm的试验片。在各试验片中,以密封部为中心打开180°,使用滕喜龙(tensilon)万能试验机(装置名:“RTG1210”,A&D(股)制造),以夹具间隔30mm、剥离速度300mm/min在上下方向上拉伸,测定最大载荷的值。将5个试验片的平均值设为热封强度(单位:N/15mm)的值。将结果示于表1中。
[表1]
表1所示的记号表示以下内容。
·A-1:实施例1的聚醚系氨基甲酸酯树脂
·A-2:实施例2的聚醚系氨基甲酸酯树脂
·A-3:实施例3的聚醚系氨基甲酸酯树脂
·A-4:实施例4的聚醚系氨基甲酸酯树脂
·A-5:实施例5的聚醚系氨基甲酸酯树脂
·A-6:实施例6的聚醚系氨基甲酸酯树脂
·C-1:聚碳酸酯系氨基甲酸酯系树脂、商品名:“斯帕福莱库斯(SUPERFLEX)460S”、第一工业制药(股)制造
·C-2:聚酯系氨基甲酸酯系树脂、商品名:“斯帕福莱库斯(SUPERFLEX)500M”、第一工业制药(股)制造
实施例7
将氨基甲酸酯树脂(A-1)88.5份(不挥发成分:31.0份)及石蜡(商品名:“赛兹派因(Sizepine)W-116H”、不挥发成分浓度:30%、荒川化学工业(股)制造)11.5份(不挥发成分:3.45份)及离子交换水12.9份混合,从而获得热封性水系树脂组合物。
实施例8~实施例13
以表2所示的组成及不挥发成分重量,与实施例7同样地进行,分别获得热封性水系树脂组合物。
(层压板的制作)
使用实施例7~实施例13的热封性水系树脂组合物,利用之前段落中记载的方法同样地进行,分别获得层压板。
(热封强度)
使用利用实施例7~实施例13的热封性水系树脂组合物获得的层压板,利用之前段落中记载的方法同样地进行,测定热封强度。将结果示于表2中。(以下相同)
<耐粘连性>
将使用实施例7~实施例13的热封性水系树脂组合物获得的层压板裁断成纵20mm×横40mm,以涂敷面与非涂敷面相接的方式重叠2片,使用永久变形试验机(测试仪产业(股)制造),在温度40℃、湿度90%的环境下以压制压力10kgf/cm2加压30分钟,用双手握住加压后的重叠的2片层压板的接触面并进行剥离,按照以下基准进行评价。
(评价基准)
○:材料未破裂,涂敷面与非涂敷面完全撕离。
×:涂敷面侧的硬化物的层粘附于非涂敷面侧而撕离。
[表2]
表2所示的记号表示以下内容。
·B-1:石蜡、商品名:“赛兹派因(Sizepine)W-116H”、不挥发成分浓度:30%、荒川化学工业(股)制造
·B-2:巴西棕榈蜡、商品名:“艾沐斯达(EMUSTAR)-0413”、不挥发成分浓度:35%、日本精蜡(股)制造
·B-3:米蜡、商品名:“珈库瓦斯普劳特(XAQUASPROUT)-0010”、不挥发成分浓度:40%、日本精蜡(股)制造
·B-4:微晶蜡、商品名:“艾沐斯达(EMUSTAR)-0001”、不挥发成分浓度:40%,日本精蜡(股)制造。
Claims (4)
1.一种热封性水系树脂组合物,包含氨基甲酸酯树脂(A),所述氨基甲酸酯树脂(A)为包含聚醚多元醇(a1)、聚异氰酸酯(a2)及链伸长剂(a3)的反应成分的生成物。
2.根据权利要求1所述的热封性水系树脂组合物,其中,所述反应成分还包含(甲基)丙烯酸羟基烷基酯(a4)。
3.根据权利要求1或2所述的热封性水系树脂组合物,还包含蜡(B)。
4.一种层压板,基材的至少一面上具有根据权利要求1或2所述的热封性水系树脂组合物的涂层。
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