CN116897197A - 包含生物可降解的水性聚氨酯压敏胶黏剂的不干胶标签 - Google Patents
包含生物可降解的水性聚氨酯压敏胶黏剂的不干胶标签 Download PDFInfo
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- CN116897197A CN116897197A CN202280016694.0A CN202280016694A CN116897197A CN 116897197 A CN116897197 A CN 116897197A CN 202280016694 A CN202280016694 A CN 202280016694A CN 116897197 A CN116897197 A CN 116897197A
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- polyurethane
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- 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
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- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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Abstract
记载的不干胶标签包含衬底材料,附着于衬底材料的压敏胶黏剂层,以及附着于所述胶黏剂层的剥离衬垫或者在衬底材料的另一侧面上的剥离涂层。衬底材料由纸或家用可堆肥的且生物可降解的聚合物膜制成,并且压敏胶黏剂层由水性聚氨酯分散体压敏胶黏剂制成。至少60重量%的聚氨酯由二异氰酸酯、聚酯二醇和至少一种选自二羟基羧酸和二氨基羧酸的二官能化羧酸组成,其中聚氨酯的熔点不高于20℃,或者其中聚氨酯的熔点高于20℃且熔化焓低于10J/g,并且其中聚氨酯胶黏剂的膜在家用堆肥条件下在360天内大于90重量%地分解为CO2和水。
Description
本发明涉及包含水性聚氨酯分散体压敏胶黏剂的不干胶标签(adhesive label)。聚氨酯胶黏剂优选是生物可降解的,以致在家用堆肥条件下、在360天内大于90重量%地分解成CO2和水。
目前,包装和标签行业对于更多的可持续解决方案的需求不断增长。使用期相对较短的产品(例如软包装标签)应当是可堆肥,特别是在家用堆肥条件下。为了完全可降解,所有层,包括胶黏剂和标签基材都应当是可堆肥的。特别是在标签中,常用的胶黏剂是已经被成熟开发的通常基于聚丙烯酸酯的压敏胶黏剂,其通常是不可生物降解或是不可堆肥的。
对于生物可降解的标签包装的需求很高,这些包装在使用后可以通过堆肥的方式进行处理。
主要的挑战在于提供这样的胶黏剂材料,在其使用期内具有必要的功能和稳定性,但当受到生物活性环境的刺激时,其会高速且高程度地降解或分解。对于降解过程的触发因素可以是胶黏剂聚合物主链内的特定位点的微生物降解、水解或氧化降解。所有降解产物应表现出最大的安全性和最小的毒性,并且在自然环境中不会积累,这意味着它们应是在理想上优选地能够进行完全且最终的微生物降解。用于将标签粘合到包装材料上的胶黏剂也对标签和包装的生物崩解性有影响。胶黏剂的首先的目的是在标签和包装之间提供稳定的粘合,其次是在其正常使用期之后还促进可降解性。要同时满足和优化胶黏剂在使用前和使用过程中的稳定性和足够的粘合强度以及使用后易于降解的这些从根本上说是相互矛盾的要求是极其困难的。
基于聚氨酯的非水性生物可降解胶黏剂记载于WO2015/091325、WO 2015/189323和EP 3257882中。出于环境和可持续发展的原因,需要以水性胶黏剂体系来替代非水性、基于有机溶剂的胶黏剂。为了提高应用的便利性,需要以水性胶黏剂体系来替代非水性、无溶剂热熔性胶黏剂。
WO 2012/013506记载了水性聚氨酯分散体胶黏剂用于制备生物崩解性复合箔的用途,其中至少两个基材通过使用水性聚氨酯分散体胶黏剂进行粘合,并且其中至少一个基材是生物崩解性聚合物箔。聚氨酯由至少60重量%的二异氰酸酯、聚酯二醇和至少一种选自二羟基羧酸和二氨基羧酸的二官能化羧酸制成。WO 2012/013506中记载的生物崩解性在一些方面仍然不能令人满意。虽然层压物的完全生物降解在包括堆肥温度高于50℃(这是在工业堆肥设施中的常规条件)在内的多种堆肥条件下可以很好地实现,但是在家用堆肥条件下例如在私人花园中,其中温度通常无法达到高于50℃时,生物降解为二氧化碳和水则要慢很多。
尽管已知聚酯型聚氨酯中的酯键可通过与水反应发生的水解而促进降解,但是相互矛盾的要求的问题也必须要解决。胶黏剂聚合物应当足够稳定,以抵抗在水性聚合物分散体(其固有地包含大量水)的制造和储存过程中与水反应引起的水解,但是胶黏剂聚合物应当在家庭堆肥条件下进行快速降解。并且聚合物胶黏剂应具有足够的粘性(例如,根据环形初粘力(loop tack)的测量)和足够的粘附力以用作用于标签目的的压敏胶黏剂。
因此,需要解决的问题是提供更多的用于生物可降解的或家用可堆肥的标签胶黏剂的材料,其中这些胶黏剂是水基的且具有高的稳定性,可以容易地生产,具有高质量的粘性和粘附性能,并且同时在分家用堆肥条件下(即低于50℃,例如25±5℃)还具有快速生物崩解性(biodisintegratability)。已经发现该问题可以通过下文所述的不干胶标签来解决。
本发明提供不干胶标签,其包括具有第一侧面和第二侧面的衬底材料,附着于衬底材料的第一侧面的压敏胶黏剂层,以及附着于所述胶黏剂层的剥离衬垫或者在衬底材料的第二侧面上的剥离涂层(无衬标签),
其中衬底材料由纸或家用可堆肥聚合物膜制成,以及压敏胶黏剂层由水性聚氨酯分散体压敏胶黏剂制成,
其中至少60重量%的聚氨酯由以下组成:
(a)至少一种二异氰酸酯,
(b)至少一种聚酯二醇,和
(c)至少一种选自二羟基羧酸和二氨基羧酸的二官能化羧酸;
其中聚氨酯的玻璃化转变温度低于20℃,
其特征在于聚氨酯的熔点不高于20℃,或者其中聚氨酯的熔点高于20℃且熔化焓低于10J/g。
优选地,聚氨酯胶黏剂的膜是生物可降解的,以致:在家用堆肥条件下(25±5℃)在360天内大于90重量%地分解为CO2和水。
优选地,聚氨酯胶黏剂的膜和衬底材料是家用可堆肥降解的。
如果在家用堆肥条件下(环境温度为25±5℃),材料是生物崩解性的,并且如果在家用堆肥条件下、在360天内,材料90重量%以上分解为CO2和水(基于澳大利亚AS5810-2010“Biodegradable plastics-Biodegradable plastics suitable for homecomposting(生物可降解的塑料——适用于家庭堆肥的生物可降解的塑料”)),则该材料是家用可堆肥的。
分解成CO2可以根据ISO 14855-1(2012)在受控堆肥测试中通过有氧降解来确定,但在环境温度(25±5℃)下以模拟家用堆肥条件,而不是58℃的规定温度下,这通常是在工业堆肥设施中模拟堆肥条件。
如果在环境温度(25±5℃)下的崩解测试环境中,在有氧堆肥至多180天后,在筛分>2毫米的情况下,发现该材料存在的量为至多10%的原始干重,则该材料在家用堆肥条件下是生物崩解性的。生物崩解性可以根据ISO 20200进行测试,但是在25±5℃下以模拟家用堆肥条件。
生物降解速率可以通过对产生的二氧化碳进行定量分析来确定。
生物可降解性是有机物质在氧气(有氧)存在下被微生物分解为二氧化碳、水、生物质和矿物盐或其他存在元素(矿化)的能力。堆肥是有机物的有氧降解以制成堆肥。家用堆肥是在自用下产生的有机废物(例如食品、花园和纸制品废物)的产物,这些废物已经经历过堆肥,并且将其产物施用到私有土地上,通常没有商业交易。
本发明还提供水性聚氨酯分散体压敏胶黏剂用于制备不干胶标签的用途,所述不干胶标签包括具有第一侧面和第二侧面的衬底材料,附着于衬底材料的第一侧面的压敏胶黏剂层,以及附着于所述胶黏剂层的剥离衬垫或者在衬底材料的第二侧面上的剥离涂层(无衬标签),其中衬底材料由纸或家用可堆肥聚合物膜制成,以及
压敏胶黏剂层由水性聚氨酯分散体压敏胶黏剂制成,
其中至少60重量%的聚氨酯由以下组成:
(a)至少一种二异氰酸酯,
(b)至少一种聚酯二醇,和
(c)至少一种选自二羟基羧酸和二氨基羧酸的二官能化羧酸;
其中聚氨酯的玻璃化转变温度低于20℃,
其特征在于聚氨酯的熔点不高于20℃,或者其中聚氨酯的熔点高于20℃且熔化焓低于10J/g。
优选地,聚氨酯胶黏剂的膜在家用堆肥条件下在360天内大于90重量%地分解为CO2和水。
尤其是发现优选的无定形聚酯聚氨酯——其具有大量的聚酯醇(>80重量%,基于聚氨酯的总重量)、低异氰酸酯含量(<20重量%的异氰酸酯化合物,基于聚氨酯的总重量计)、少量的尿素(<100mmol/kg脲基)——特别适合在家用堆肥条件下进行堆肥,并且干燥的薄膜具有粘性,并且由于低的聚氨酯含量能够特别好地用作压敏胶黏剂。
玻璃化转变温度通过差示扫描量热法(ASTM D 3418-08,第二加热曲线的“中点温度”,加热速率20K/min)测定。
用于本发明的胶黏剂包含(优选基本上由其组成)作为聚合物粘合剂的至少一种分散在水中的聚氨酯,以及任选的添加物质,例如填料、增稠剂、消泡剂等。聚合物粘合剂优选采取分散在水中的形式,或分散在由水和具有沸点优选低于150℃(1bar)的水溶性有机溶剂制成的混合物中的形式。特别优选水作为唯一溶剂。水或其他溶剂不包括在与胶黏剂的组成相关的重量数据的计算中。
聚氨酯优选一方面主要由脂族多异氰酸酯、特别是二异氰酸酯组成,另一方面由优选为非结晶聚酯二醇的反应物、以及双官能化羧酸组成。优选聚氨酯由至少60重量%、非常特别是至少80重量%的二异氰酸酯、聚酯二醇和双官能化羧酸组成。
聚氨酯优选是无定形的。优选聚氨酯包含基于聚氨酯计的大于10重量%、大于50重量%或至少80重量%的量的脂族聚酯二醇。
聚酯二醇优选由至少一种二元酸和至少一种支链二元醇制成,或者聚酯二醇在低于60℃时为液体。聚酯二醇优选地由至少10mol%、优选至少20mol%或至少30mol%的支链脂族二元醇制成,基于用于制备聚酯二醇的二元醇的总和计。优选的支链脂族二元醇是新戊二醇、3-甲基戊二醇、2-甲基丙二醇和羟基新戊酸新戊二醇酯(3-羟基-2,2-二甲基丙酸3-羟基-2,2-二甲基丙酯)。最优选的支链脂族二元醇是新戊二醇。
低于60℃下为液体的聚酯二醇的实例由二元酸和至少两种不同的脂族二元醇的混合物制成,其中至少一种二元醇在链中含有杂原子;例如乙二醇、二乙二醇、聚乙二醇或聚四氢呋喃。优选的液体聚酯二醇由至少一种选自己二酸、丁二酸和癸二酸的二元酸以及乙二醇和二乙二醇制成。
聚氨酯优选由以下组成:
a)至少一种二异氰酸酯,其优选是脂族或脂环族的,
b)至少一种二元醇,其中,
b1)基于二元醇(b)的总量计的10至100mol%为具有500至5000g/mol的摩尔质量的聚酯二醇,
b2)基于二元醇(b)的总量计的0至90mol%具有60至500g/mol的摩尔质量,
c)至少一种选自二羟基羧酸或二氨基羧酸的二官能化羧酸,
d)任选地不同于单体(a)至(c)的其他多官能化合物,其具有反应性基团,其中所述反应性基团为醇羟基、伯氨基或仲氨基、或异氰酸酯基,和
e)任选地不同于单体(a)至(d)的单官能化合物,其具有的反应性基团为醇羟基、伯氨基或仲氨基、或异氰酸酯基。还优选的聚氨酯的至少60重量%由下述组成:
a)至少一种脂族二异氰酸酯,
b)至少一种脂族聚酯二醇,
c)至少一种选自二羟基羧酸或二氨基羧酸的二官能化羧酸,和
d)至少一种不同于单体(a)至(c)的且具有至少两个选自伯氨基或仲氨基的反应性基团的其他多官能化合物。
优选地,至少80重量%的至少一种聚酯二醇(b)由至少一种脂族二羧酸和至少一种脂族二元醇组成。
应特别提及的单体(a)为二异氰酸酯X(NCO)2,其中X为具有4至15个碳原子的脂族烃基或具有6至15个碳原子的脂环族或芳族烃基,或具有7至15个碳原子的芳脂族烃基,其中优选脂族和/或脂环族二异氰酸酯。这些二异氰酸酯的实例是四亚甲基二异氰酸酯,六亚甲基二异氰酸酯,十二亚甲基二异氰酸酯,1,4-二异氰酸酯基环己烷,1-异氰酸酯基-3,5,5-三甲基-3-异氰酸酯基甲基环己烷(IPDI),2,2-双(4-异氰酸酯基环己基)丙烷、三甲基己烷二异氰酸酯,双(4-异氰酸酯基环己基)甲烷(HMDI)的异构体,例如反式/反式、顺式/顺式和顺式/反式异构体,以及由所述化合物组成的混合物。芳族二异氰酸酯的实例为1,4-二异氰酸酯基苯、2,4-二异氰酸酯基甲苯、2,6-二异氰酸酯基甲苯、4,4'-二异氰酸酯基二苯基甲烷、2,4'-二异氰酸酯基二苯基甲烷、对亚二甲苯基二异氰酸酯、四甲基亚二甲苯基二异氰酸酯(TMXDI)。这种类型的二异氰酸酯是可商购的。
所述异氰酸酯的混合物是,例如为二异氰酸酯基甲苯和二异氰酸酯基二苯基甲烷的各自的结构异构体的混合物,例如由80mol%2,4-二异氰酸酯基甲苯和20mol%2,6-二异氰酸酯基甲苯制成的混合物;或芳族异氰酸酯如2,4-二异氰酸酯基甲苯和/或2,6-二异氰酸酯基甲苯与脂族或脂环族异氰酸酯例如六亚甲基二异氰酸酯或IPDI的混合物,其中脂族异氰酸酯与芳族异氰酸酯的优选混合比率为4:1至1:4。
最优选六亚甲基二异氰酸酯。
除了上述化合物之外,可用于聚氨酯结构中的其他化合物是除了游离异氰酸酯基团之外还具有其他盖帽的异氰酸酯基(例如脲二酮基团)的那些化合物。
为了取得良好的成膜性和弹性,可以使用的二元醇(b)主要是相对高分子量的二元醇(b1),其摩尔质量为约500至5000g/mol,优选约1000至3000g/mol。这是数均摩尔质量Mn。Mn通过测定末端基团的数值(OH值)来计算的。
二元醇(b1)可以是聚酯多元醇,其中这些例如从Ullmanns Enzyklopadie dertechnischen Chemie[乌尔曼工业化学百科全书],第4版,第19卷,第62至65页已知。优选使用通过二官能化醇与二官能化羧酸的反应获得的聚酯多元醇。代替游离的多元羧酸,还可以使用相应的多元羧酸酐或相应的低级醇的多元羧酸酯,或它们的混合物来生产聚酯多元醇。多元羧酸可以是脂族、脂环族、芳脂族、芳族或杂环族的,并且可以任选地具有不饱和度和/或取代基,例如被卤素原子取代。可以提及的实例是:辛二酸、壬二酸、邻苯二甲酸、间苯二甲酸、邻苯二甲酸酐、四氢邻苯二甲酸酐、六氢邻苯二甲酸酐、四氯邻苯二甲酸酐、内亚甲基四氢邻苯二甲酸酐、戊二酸酐、马来酸、马来酸酐、富马酸和二聚脂肪酸。优选通式HOOC-(CH2)y-COOH的二元羧酸,其中y是1至20的数字,优选2至20的偶数,实例是丁二酸、己二酸、癸二酸和十二烷二羧酸。
可以使用的多官能化醇的实例是乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁烯二醇、1,4-丁炔二醇、1,5-戊二醇、新戊二醇、双(羟甲基)环己烷(例如1,4-双(羟甲基)环己烷)、2-甲基丙烷-1,3-二醇、甲基戊二醇(例如3-甲基戊二醇)、羟基新戊酸新戊二醇酯(3-羟基-2,2-二甲基丙酸3-羟基-2,2-二甲基丙酯)以及二乙二醇、三乙二醇、四乙二醇、聚乙二醇、二丙二醇、聚丙二醇、二丁二醇,和聚丁二醇。优选通式HO-(CH2)x-OH的醇(其中x是1至20的数字,优选2至20的偶数),与支链脂族二元醇,尤其是新戊二醇的混合物,其中支链脂族二元醇的量优选为二元醇的总量的至少10mol%、至少25mol%或至少30mol%。
任选地还可以使用聚碳酸酯二醇,例如可通过使光气与过量的上述提及的作为聚酯多元醇的结构组分的低分子量的醇发生反应而获得。
还可以使用基于内酯的聚酯二醇,其单独使用或与上述聚酯二醇结合使用,其中这些是内酯的均聚物或共聚物,优选具有末端羟基的加合物,并且这些加合物是通过内酯在合适的二官能化起始剂分子上的加成反应而产生的。可以使用的优选内酯是衍生自通式HO-(CH2)z-COOH的化合物的那些内酯,其中z是1至20的数字,并且亚甲基单元的H原子也可以被C1-C4-烷基替代。实例是ε-己内酯、β-丙内酯、γ-丁内酯和/或甲基-ε-己内酯,以及它们的混合物。合适的起始组分的实例是上述提及的作为聚酯多元醇的结构组分的低分子量的双官能化醇。特别优选ε-己内酯的相应聚合物。低级聚酯二醇或聚醚二醇也可以用作生产内酯聚合物的起始剂。代替内酯的聚合物,还可以使用对应的、与内酯对应的羟基羧酸的化学上等价的缩聚物。
除了聚酯二醇之外,还可以任选地同时使用聚醚二醇。聚醚二醇尤其是可以通过环氧乙烷、环氧丙烷、环氧丁烷、四氢呋喃、氧化苯乙烯或环氧氯丙烷自身的聚合获得,例如在BF3存在下;或通过所述化合物任选地以混合物或连续的方式在具有反应性氢原子的起始剂组分上的加成反应而获得,所述具有反应性氢原子的起始剂组分是例如醇或胺,其实例为水、乙二醇、1,2-丙烷二醇、1,3-丙烷二醇、2,2-双(4-羟基苯基)丙烷或苯胺。聚醚二醇的实例是摩尔质量为240至5000g/mol、尤其是500至4500g/mol的聚环氧丙烷和聚四氢呋喃。然而,优选不使用聚醚二醇作为聚氨酯的结构组分。
还任选地可以同时使用聚羟基烯烃,优选具有2个末端羟基的那些,例如α,ω-二羟基聚丁二烯、α,ω-二羟基聚甲基丙烯酸酯或α,ω-二羟基聚丙烯酸酯。其他合适的多元醇是聚缩醛、聚硅氧烷和醇酸树脂。
优选至少95mol%或100mol%的二元醇b1)是聚酯二醇。特别优选所使用的二元醇b1)仅包含聚酯二醇。聚酯二醇优选仅由脂族和/或脂环族组分组成。
优选地,聚氨酯由至少50重量%、更优选至少85重量%或至少95重量%或100重量%的聚酯二醇制成,基于全部的多羟基化合物计。
如果使用的二醇(b)除了二元醇(b1)之外还包含摩尔质量为约60至500g/mol、优选62至200g/mol的低摩尔质量二元醇(b2),则可以增加聚氨酯的硬度和弹性模量。所使用的单体(b2)尤其是用于产生聚酯多元醇的短链链烷二醇的结构组分,其中优选具有2至12个碳原子且具有偶数个碳原子的直链(unbranched)二元醇,以及1,5-戊二醇和新戊二醇。
可以使用的二元醇b2)的实例是乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁烯二醇、1,4-丁炔二醇、1,5-戊二醇、新戊二醇、双-(羟甲基)环己烷(例如1,4-双(羟甲基)环己烷)、2-甲基丙烷-1,3-二醇、甲基戊二醇,以及二乙二醇、三乙二醇、四乙二醇、聚乙二醇、二丙二醇、聚丙二醇、二丁二醇和聚丁二醇。优选通式HO-(CH2)x-OH的醇,其中x是1至20的数字,优选2至20的偶数。此处实例是乙二醇、1,4-丁二醇、1,6-己二醇、1,8-辛二醇和1,12-十二烷二醇。还优选新戊二醇。
优选地,基于二元醇(b)的总量计,二元醇(b1)的比例为10至100摩尔%或60至100摩尔%,并且单体(b2)的比例为0至90摩尔%,或0至40摩尔%,基于二醇(b)的总量计。
为了实现聚氨酯的水分散性并且改善生物可降解性,聚氨酯包含至少一种选自二羟基羧酸和二氨基羧酸的二官能化羧酸。任选地还可以另外使用亲水性结构组分,其促进分散性并且带有至少一个异氰酸酯基或至少一个对异氰酸酯基呈反应性的基团,另外还带有至少一个亲水性基团,或一个可转换成亲水性基团的基团。在下文中,“亲水性基团或潜在的亲水性基团”缩写为“(潜在)亲水性基团”。与用于构建聚合物主链的单体的官能团相比,(潜在)亲水性基团与异氰酸酯的反应要慢得多。
基于组分(a)至(e)的总量计,具有(潜在)亲水性基团的组分的比例通常以如下方式判断:(潜在)亲水性基团的摩尔量为30至1000mmol/kg,优选50至500mmol/kg,特别优选80至300mmol/kg,基于全部单体(a)至(e)的总量计。(潜在)亲水性基团可以是非离子型亲水性基团或优选(潜在)离子型亲水性基团。可以使用的具体的非离子型亲水性基团是呈优选由5至100个环氧乙烷重复单元、优选10至80个环氧乙烷重复单元构成的聚乙二醇醚的形式。聚环氧乙烷单元的含量通常为0至10重量%,优选0至6重量%,基于所有单体(a)至(e)的总量计。具有非离子型亲水性基团的单体的实例是使用至少20重量%环氧乙烷的聚环氧乙烷二醇、聚环氧乙烷一元醇、以及聚乙二醇和二异氰酸酯的反应产物,其中它们带有醚化的末端聚乙二醇基团。这种类型的二异氰酸酯及其生产方法在专利说明书US-A 3 905 929和US-A 3 920 598中给出。
所用的二官能化羧酸通常包括脂族、脂环族、芳脂族或芳族羧酸,其中这些化合物带有至少两个羟基或两个伯氨基或仲氨基。优选二羟基烷基羧酸,尤其是具有3至10个碳原子的那些,也如US-A 3 412 054中所述。特别优选通式(c1)的化合物,
其中R1和R2是C1-C4亚烷基,并且R3是C1-C4烷基,并且尤其是二羟甲基丙酸(DMPA)。
可以使用的并且具有对异氰酸酯呈反应性的氨基的单体(c)是二氨基羧酸,或DE-A 2034479中提到的加合物,该加合物衍生自脂族二伯胺(aliphatic diprimarydiamines)在α,β-不饱和羧酸上的加成反应。该类型的化合物例如符合式(c2)
H2N-R4-NH-R5-X (c2)
其中R4和R5彼此独立地是C1-C6亚烷基,优选亚乙基,并且X是COOH。特别优选的式(c2)化合物是N-(2-氨基乙基)-2-氨基乙烷甲酸和相应的碱金属盐,其中特别优选Na作为抗衡离子。
除了二官能化羧酸之外,还可以任选地使用具有亲水性基团的其他单体,实例是合适的二羟基磺酸和二羟基膦酸,例如2,3-二羟基丙烷膦酸或二氨基磺酸。然而,优选不使用任何二官能化磺酸或膦酸。
离子型亲水性基团尤其是阴离子基团,例如磺酸根、羧酸根和磷酸根,以其碱金属盐或铵盐的形式,以及阳离子基团,例如铵根,特别是质子化的叔氨基,或季铵基团。潜在离子型亲水性基团尤其是可通过简单的中和、水解或季铵化反应转化为上述离子型亲水性基团的那些基团,因此例如是羧酸基团或叔氨基。(潜在)离子型单体被详细记载在例如Ullmanns Enzyklopadie dertechnischen Chemie[乌尔曼工业化学百科全书],第4版,第19卷,第311-313页中,并且例如在DE-A 1 495 745中。
实际上特别重要的(潜在)阳离子型单体(c)尤其是具有叔氨基的单体,实例是:三(羟烷基)胺、N,N'-双-(羟烷基)烷基胺、N-羟烷基二烷基胺、三(氨基烷基)胺、N,N'-双-(氨基烷基)烷基胺和N-氨基烷基二烷基胺,其中所述叔胺的烷基和亚烷基单元彼此独立地由1至6个碳原子组成。可以使用的其他化合物是具有叔氮原子的并且优选具有两个末端羟基的聚醚,例如可以以其本身常规的方式通过其中具有与胺氮键合的两个氢原子的胺(甲胺、苯胺或N,N’-二甲基肼)的烷氧基化而获得的那些。这种类型的聚醚的摩尔质量通常为500至6000g/mol。使用酸——优选强无机酸(例如磷酸、硫酸、氢卤酸)或强有机酸,或通过与合适的季铵化试剂(例如C1-C6-烷基卤化物或苄基卤化物,如溴化物或氯化物)反应,将所述叔胺转换成铵盐。
就使用具有潜在离子基团的单体而言,将这些单体转换成离子形式,可以在异氰酸酯加聚反应之前、期间或优选在其之后进行,因为离子型单体通常仅微溶于反应混合物中。特别优选地,羧酸根以其与碱金属离子或铵离子作为抗衡离子的盐的形式存在。
不同于单体(a)至(c)并且任选地也是聚氨酯的成分的单体(d)通常用于交联或用于扩链。它们通常是具有大于两个官能度的非酚类醇、具有2个或更多个伯氨基和/或仲氨基的胺、或者不仅具有一个或多个醇羟基而且还具有一个或多个伯氨基和/或仲氨基的化合物。具有大于2的官能度并且可用于调节至一定的支化度或交联度的醇的实例是三羟甲基丙烷、丙三醇或糖。还可以使用一元醇,其中它们不仅带有羟基而且还带有另外的对异氰酸酯呈反应性的基团,实例是具有一个或多个伯氨基和/或仲氨基的一元醇,例如单乙醇胺。
具有2个或更多个伯氨基和/或仲氨基的多胺,尤其是意欲在水存在下进行扩链反应或交联反应时被使用,因为胺与异氰酸酯的反应速度通常大于醇或水与异氰酸酯的反应速度。当需要交联聚氨酯或高分子量聚氨酯的水分散体时,这通常是必需的。在这种情况下,制备过程是产生具有异氰酸酯基的预聚物,将其快速分散在水中,然后通过添加具有多个对异氰酸酯呈反应性的氨基的化合物来使它们进行扩链或交联。适用于该目的的胺通常是摩尔质量为32至500g/mol、优选60至300g/mol的多官能化胺,其中它们包含至少两个选自伯氨基和仲氨基的氨基。此处实例是二胺例如二氨基乙烷、二氨基丙烷、二氨基丁烷、二氨基己烷、哌嗪、2,5-二甲基哌嗪、1-氨基-3-(氨基甲基)-3,5,5-三甲基环己烷(异佛尔酮二胺,IPDA)、4,4'-二氨基二环己基甲烷、1,4-二氨基环己烷、氨基乙基乙醇胺、肼、水合肼,或三胺例如二亚乙基三胺或1,8-二氨基-4-氨基甲基辛烷。
胺也可以以盖帽的形式使用,例如其形式为相应的酮亚胺(参见例如CA-A 1 129128)、酮连氮(ketazines)(参见例如US-A 4 269748)或胺盐(参见US-A 4 292 226)。噁唑烷,例如US-A 4 192 937中使用的那些,也是盖帽多胺,其可用于生产本发明的聚氨酯,用于预聚物的扩链目的。当使用这种类型的盖帽多胺时,它们通常在不存在水的情况下与预聚物混合,然后将该混合物与分散体水或与一部分的分散体水混合,从而通过水解释放相应的多胺。
优选使用二胺和三胺的混合物,特别优选使用异佛尔酮二胺(IPDA)和二亚乙基三胺(DETA)的混合物。
聚氨酯优选包含作为单体(d)的1至30mol%、尤其是4至25mol%的具有至少2个对异氰酸酯呈反应性的氨基的多胺,基于对异氰酸酯呈反应性的单体的官能团总量计。还可以使用官能度大于2的异氰酸酯作为用于相同目的的单体(d)。市售化合物的实例是异氰脲酸酯或六亚甲基二异氰酸酯的缩二脲。
任选同时使用的单体(e)是单异氰酸酯、一元醇、以及单伯胺和单仲胺。它们的比例通常为至多10摩尔%,基于单体的总摩尔量计。所述单官能化合物通常带有其他官能团(例如烯基或羰基),并且用于将官能团引入到聚氨酯中,其中这些官能团使得聚氨酯分散和各自地进行交联或其他的聚合物类似反应。可用于该目的的单体是例如异丙烯基-α,α-二甲基苄基异氰酸酯(TMI)以及丙烯酸或甲基丙烯酸的酯,例如丙烯酸羟乙酯或甲基丙烯酸羟乙酯。
优选地,聚氨酯的至少50重量%、更优选至少80重量%或至少90重量%由二异氰酸酯(a)、二元醇(b)和二官能化羧酸(c)组成,基于所有单体的总和计。
单体(d)和(e)的总量优选为至多或小于10重量%,例如0.1至10重量%或0.5至5重量%。
如果使用的单体(a)本质上仅是脂族二异氰酸酯、脂环族二异氰酸酯或芳脂族二异氰酸酯,则尤其是获得具有特别良好的性能特征的胶黏剂。优选地,所述单体的组合是以二羟基-或二氨基一元羧酸的碱金属盐(此处Na盐是最合适的)作为组分(c)来补充。
最优选的是这样的组分(a)至(e),其产生的聚氨酯具有低于20℃的玻璃化转变温度并且要么是熔点不高于20℃,要么是其中聚氨酯的熔点高于20℃且熔化焓低于10J/g。
通过对相互反应的单体的比例的选择,以及对每个分子的反应性官能团的算术平均数的选择,以调节聚氨酯的分子量的方法在聚氨酯化学领域是众所周知的。通常的方法选择组分(a)至(e),以及它们各自的摩尔量,使得比率A:B可以是0.5:1至2:1、0.8:1至1.5:1,或0.9:1至1.2:1,其中:
A是异氰酸酯基的摩尔量,并且
B是羟基的摩尔量和在加成反应中可以与异氰酸酯反应的官能团的摩尔量的总和。
异氰酸酯基与对异氰酸酯呈反应性的基团的比率A:B为优选至少1:1或大于1:1,例如至多2:1,或至多1.5:1或至多1.2:1,最优选尽可能接近1:1,使得聚氨酯没有尚待反应的NCO反应性基团(例如尚待反应的羟基)。
所使用的单体(a)至(e)通常具有平均1.5至2.5个、优选1.9至2.1个、特别优选2.0个异氰酸酯基,和相应地,在加成反应中可以与异氰酸酯反应的官能团。
出于可持续性原因,优选使用生物基材料来生产聚氨酯胶黏剂。术语“生物基”表示该材料具有生物来源并且来自生物材料/可再生资源。可再生来源的材料或生物材料是一种有机材料,其中碳来自最近通过大气光合作用固定的CO2(在人类规模上)。生物材料(100%天然来源的碳)具有大于10-12、通常约为1.2x1012的同位素比14C/12C,而化石材料具有的比率为零。事实上,同位素14C在大气中形成,然后通过光合作用掺入,时间尺度最多为数十年。14C的半衰期是5,730年。因此,来自光合作用的材料,即一般的植物,必然具有同位素14C的最大含量。生物材料或生物碳的含量的测定可以根据标准ASTM D 6866-12、方法B(ASTM D 6866-06)和ASTM D7026(ASTM D 7026-04)进行。
用于生产聚氨酯的合适的生物基材料例如是衍生自天然材料例如淀粉、蔗糖、葡萄糖、木质纤维素、天然橡胶或植物油的醇(特别是二元醇和多元醇)和有机酸(特别是二元酸)。衍生自天然材料的合适的醇和有机酸为例如乙醇、单乙二醇、聚乙二醇、异山梨醇、1,3-丙二醇、1,4-丁二醇、丙三醇、己二酸或丁二酸。优选地,至少部分聚氨酯由生物基材料制成。
用于生产聚氨酯的结构组分的加聚反应优选在最高达180℃、优选最高达150℃的反应温度下、在大气压或自生压力下进行。聚氨酯和聚氨酯水分散体的制备是本领域技术人员已知的。聚氨酯优选采用水性分散体的形式并以此形式使用。优选将聚合物分散体的pH调节至pH大于5,特别是调节至pH为5.5至10.5。
用于本发明的胶黏剂包含羧酸根并且优选包含其他反应性基团,其中这些基团可以彼此之间或与外交联剂进行交联反应。优选存在的所述反应性基团的量为0.0001至0.5mol/100g胶黏剂,特别是0.0005至0.5mol/100g胶黏剂。羧基也通过水解反应形成,因此也可能在聚氨酯中、在没有任何初始含量的羧基的情况下发生交联。
在本发明的一方面,本发明的聚氨酯分散体胶黏剂作为单组分组合物使用,即没有额外的交联手段,特别是没有异氰酸酯交联剂。然而,本发明的聚氨酯分散体胶黏剂也可用作双组分胶黏剂,其包含聚氨酯分散体在一种组分中和至少一种外交联剂例如水可乳化的异氰酸酯在另一种单独的组分中,并且在施加胶黏剂之前不久添加交联组分。双组分组合物是由两种单独包装的组合物组成的产品,这两种单独包装的组合物在使用前不久混合。
合适的交联剂的实例是具有至少两个异氰酸酯基的多异氰酸酯,例如由二异氰酸酯生成的异氰脲酸酯、具有至少一个碳二亚胺基团的化合物、化学上盖帽的异氰酸酯、包封的异氰酸酯、包封的脲二酮(uretdiones)、缩二脲或脲基甲酸酯(allophanates)。还合适的是氮丙啶(aziridines)、噁唑啉和环氧化物。外交联剂的用量为优选0.5至10重量%,基于分散体的固体含量计。外交联剂是这样的化合物,在交联反应之前,不与聚氨酯键合,而是分散或溶解在聚氨酯分散体中。然而,也可以使用已键合至聚氨酯的交联剂(内交联剂)。
优选的聚氨酯胶黏剂:
由大量的聚酯醇制成(>80重量%,基于聚氨酯的总重量计);
具有<20重量%异氰酸酯化合物的低异氰酸酯含量,基于聚氨酯的总重量计;并且
具有<100mmol/kg的少量脲基。
本发明的不干胶标签是自粘合的。衬底材料优选选自纸或热塑性膜。衬底材料优选是家用可堆肥的和/或生物可降解的。生物可降解的衬底材料包括聚乳酸、纤维素、改性淀粉、聚羟基烷酸酯(polyhydroxyalkanoates)和生物可降解的聚酯,例如基于至少一种C2-C12链烷二醇和至少一种选自己二酸、对苯二甲酸和丁二酸的二元羧酸的聚酯。优选的生物可降解的衬底材料是由木质素、淀粉、纤维素材料、聚乳酸(PLA)、聚乳酸立体(异构体)复合物(PLLA-PDLA)、聚乙醇酸(polyglycolic acid)(PGA)、脂族聚酯、脂族-芳族共聚酯分别制成的箔,以及聚羟基烷酸酯、玻璃纸、聚碳酸亚丙酯(PPC)制成的箔,以及上述材料的混合物制成的箔。脂族聚酯的实例是聚丁二酸丁二醇酯(PBS)、聚丁二酸丁二醇酯-共-己二酸丁二醇酯(PBSA)、聚丁二酸丁二醇酯-共-癸二酸丁二醇酯(PBSSe)、聚己内酯(PCL)和聚十五烷酸内酯(polypentadecanolide)。脂族-芳族共聚酯的实例是聚己二酸丁二醇酯-共-对苯二甲酸丁二醇酯(PBAT)、聚癸二酸丁二醇酯-共-对苯二甲酸丁二醇酯(PBSeT)、聚壬二酸丁二醇酯-共-对苯二甲酸丁二醇酯(PBAzeT)、聚十三烷二酸丁二醇酯-共-对苯二甲酸丁二醇酯(PBBrasT)。特别合适的材料的实例是箔,例如/>F或/>FS。聚羟基烷酸酯的实例是聚-3-羟基-丁酸酯(PHB)、聚-3-羟基丁酸酯-共-3-羟基戊酸酯(P(3HB)-co-P(3HV))、聚-3-羟基丁酸酯-共-4-羟基丁酸酯(P(3HB)-co-P(4HB))、聚-3-羟基丁酸酯-共-3-羟基己酸酯(P(3HB)-co-P(3HH))。
特别优选地,生物可降解的衬底材料是纸或至少95重量%、更具体地至少98重量%、非常优选100重量%由以下材料组成:聚乳酸、木质素、淀粉、纤维素材料、聚乙醇酸、聚羟基烷酸酯、聚碳酸亚丙酯、脂族聚酯(例如聚丁二酸丁二醇酯)、脂族-芳族共聚酯(例如丁二醇-己二酸-对苯二甲酸共聚物,或丁二醇-己二酸-对苯二甲酸共聚物和聚乳酸的共混物),以及上述材料的混合物,各自基于生物可降解的衬底材料的总重量计。
涂覆有压敏胶黏剂的衬底材料的一侧可以用剥离衬垫(例如硅化纸)覆盖,直至稍后使用。剥离衬垫的材料可以是聚乙烯、聚丙烯、多层层压聚丙烯/聚乙烯膜、聚酯或单面或双面涂有聚硅氧烷的纸(硅化纸)。无衬标签可以在没有剥离衬垫的情况下制成,并且包含在衬底材料的第二侧面(未涂覆有胶黏剂层的侧面)上包括剥离涂层(例如聚硅氧烷涂层)。意欲于将剥离衬垫保留在不干胶标签上,直到将标签施用在基材上。剥离衬垫的表面能或剥离涂层的表面能优选小于30mN/m。
优选的不干胶标签(没有剥离衬垫)是家用可堆肥的,其中如果材料在家用堆肥条件(25±5℃)下是生物崩解性的,以及如果材料在家用堆肥条件下、在360天内大于90重量%地分解成CO2和水,则该材料是家用可堆肥;并且其中如果在25±5℃环境温度下的有氧堆肥至多180天后,在筛分>2毫米的情况下,发现存在至多10%的原始干重的材料,则该材料在家用堆肥条件下是生物崩解性的。
有利地在其上施用自粘标签的基材可以是例如金属、木材、玻璃、纸或塑料。自粘标签特别适合粘结到包装表面、纸板箱、塑料包装、书籍、窗户、蒸汽阻挡层、机动车辆车身、轮胎或车身部件。
此处水性聚氨酯胶黏剂分散体可以在没有另外的添加剂的情况下使用或者在与常规助剂的进一步配制之后使用。常规助剂的实例是润湿剂、增稠剂、保护胶体、光稳定剂、杀生物剂、消泡剂、增粘剂、增塑剂等。本发明的胶黏剂制剂不一定需要添加增塑树脂(增粘剂)或其他增塑剂。胶黏剂组合物中聚氨酯胶黏剂聚合物的量优选为15至75重量%,更优选40至60重量%。胶黏剂制剂中添加剂的量优选为0.05至5重量份或0.1至3重量份,按每100重量份胶黏剂聚合物(基于固体)。
在本发明中,本发明的水性聚氨酯胶黏剂分散体用于生产标签的水性胶黏剂制剂中,即用于将标签粘合到基材上的水性压敏胶黏剂制剂中。因此,本发明还提供一种通过使用包含至少一种如本文所述的本发明的聚氨酯聚合物分散体的水性胶黏剂制剂来生产优选在家用堆肥条件(25±5℃)下具有生物崩解性的不干胶标签的方法。
该方法包括提供如上所述的具有基于聚氨酯的特征的水性聚氨酯分散体压敏胶黏剂,以及要么是将该分散体涂覆到剥离衬垫上;干燥;并且将剥离衬垫附着于胶黏剂层上;要么是将胶黏剂分散体涂覆在衬底材料的第一侧面上,该衬底材料在其第二侧面上包含剥离涂层,其中衬底优选是生物可降解的。
在本发明的用于生产不干胶标签的方法中,优选使用2至150g/m2、特别优选10至40g/m2的层厚度施用本发明的水性聚氨酯分散体或相应的进一步配制的制剂,例如通过刮涂、铺展等。可以使用常规的涂覆方法,例如辊涂、反向辊涂、凹版辊涂、反向凹版辊涂、刷涂、棒涂、喷涂、喷枪涂布、弯月面涂布、幕涂或浸涂。将分散体水进行风干的短时间后(优选1至60秒后),然后可将第一涂覆基材(例如剥离衬垫)层压至第二基材(例如衬底材料),并且涂覆温度可以是例如20至200℃,优选20至100℃。分散体涂料在施工前不一定需要加热。卷材速度(web speed)可以非常高:最高达3000m/min。
本发明的不干胶标签优选具有至少3N/25mm的环形初粘力,如实施例所述测量。
根据本发明的不干胶标签优选具有至少3N/25mm的90°剥离粘附力(peeladhesion),如实施例所述的在24小时接触时间之后测量。
本发明的优点在于,由水基胶黏剂制成的本发明的不干胶标签提供了良好的粘性(环形初粘力)、良好的剥离粘附性以及良好的生物可降解性和家庭可堆肥性。
实施例
玻璃化转变温度通过差示扫描量热法(ASTM D 3418-08,第二加热曲线的“中点温度”,加热速率20K/min)测定。
熔点和熔化焓是根据DIN 53765(1994)(熔点=峰值温度),通过在以20K/min加热,加热聚氨酯膜至120℃之后,又以20K/min冷却至23℃,于此处退火20小时而测定。
LD值:聚合物分散体和聚合物粒径通过聚合物分散体的LD值(光透射率)来表征,通过浊度测量间接地测定。为此目的,在室温下、相对于蒸馏水、以2.5cm的层厚度来测定固体含量为0.01重量%的分散体的浊度。
实施例1
在95℃下、在62g无水丙酮中,将由己二酸、1,6-己二醇和新戊二醇制成的483g聚酯二醇(1,6-己二醇:新戊二醇的摩尔比=1.8:1;OH值=56mg KOH/g),由己二酸、乙二醇和二乙二醇制成的121.7g聚酯二醇(OH值=56mg KOH/g),2.68g三羟甲基丙烷和13.4g二羟甲基丙酸(DMPA)与75.7g六亚甲基二异氰酸酯反应2小时。然后添加130g无水丙酮并将温度降低至67℃。继续反应直至NCO含量为0.28%。然后用646g丙酮稀释混合物并冷却至57℃。然后在5分钟内逐滴加入被稀释在13.6g丙酮中的3.4g异佛尔酮二胺(IPDA),并将混合物搅拌30分钟。将该混合物用23.8g、5%浓度的氨水溶液中和,并使用900g去离子水以分散该混合物。通过真空蒸馏除去丙酮。调整固体含量至46%。
分析值:LD:82;pH:7.4。
实施例2
在95℃下、在62g无水丙酮中,将由己二酸、1,6-己二醇和新戊二醇制成的604g聚酯二醇(OH值=56mg KOH/g),10gN120(经聚乙二醇侧链改性的二醇,OH值为112mgKOH/g,来自Perstorp),1.34g三羟甲基丙烷和13.4g二羟甲基丙酸(DMPA)与74.8g六亚甲基二异氰酸酯反应1小时。然后添加130g无水丙酮并将温度降低至67℃。继续反应直至NCO含量为0.22%。然后用646g丙酮稀释混合物并冷却至57℃。然后在5分钟内逐滴加入被稀释在13.6g丙酮中的3.4g异佛尔酮二胺(IPDA),并将混合物搅拌30分钟。将该混合物用23.8g、5%浓度的氨水溶液中和,并使用800g去离子水以分散该混合物。通过真空蒸馏除去丙酮,并且调整固体含量至45%。
分析值:LD:79;pH:7.6。
实施例3
在90℃下,将由己二酸、1,6-己二醇和新戊二醇制成的405g聚酯二醇(OH值=56mgKOH/g)与8.9g苯四甲酸二酐反应直至酸酐基团被消耗。然后将该混合物用120g无水丙酮稀释,冷却至60℃,并且加入被稀释在10g无水丙酮中的30.3g六亚甲基二异氰酸酯,使反应在67℃下继续反应直至NCO含量为0.2%。然后用500g丙酮稀释混合物并冷却至33℃。然后逐滴加入3.14g异佛尔酮二胺(IPDA),并将混合物搅拌5分钟。将该混合物用22.1g、6%浓度的氨水溶液中和,并使用550g去离子水以分散该混合物。通过真空蒸馏除去丙酮,并且调整固体含量至50%。
分析值:LD:23;pH:8.2。
实施例4
在94℃下、在62g无水丙酮中,将由己二酸、乙二醇和二乙二醇制成的608.7g聚酯二醇(OH值=56mg KOH/g)、13.4g二羟甲基丙酸(DMPA)与70.6g六亚甲基二异氰酸酯反应4小时。然后在3小时内加入130g无水丙酮,并且降低温度至67℃。继续反应直至NCO含量为0.19%。然后用646g丙酮稀释混合物并冷却至57℃。然后在5分钟内逐滴加入被稀释在13.6g丙酮中的3.4g异佛尔酮二胺(IPDA),并将混合物搅拌30min。将该混合物用23.8g、5%浓度的氨水溶液中和,并使用844g去离子水以分散该混合物。通过真空蒸馏除去丙酮,并且调整固体含量至45%。
分析值:LD:48;pH:7.5。
无定形、没有熔点;Tg:-40℃。
实施例5
在98℃下、在62g无水丙酮中,将由己二酸、1,6-己二醇和新戊二醇制成的604g聚酯二醇(OH值=56mg KOH/g),20g N120(经聚乙二醇侧链改性的二醇,OH值为112mg KOH/g,来自Perstorp),2.68g三羟甲基丙烷和13.4g二羟甲基丙酸(DMPA)与79g六亚甲基二异氰酸酯反应1小时30分钟。然后在4小时30分钟内加入130g无水丙酮并将温度降低至67℃。继续反应直至NCO含量为0.2%。然后用646g丙酮稀释混合物并冷却至57℃。然后在5分钟内逐滴加入被稀释在13.6g丙酮中的3.4g异佛尔酮二胺(IPDA),并将混合物搅拌30分钟。将该混合物用23.8g、5%浓度的氨水溶液中和,并使用825g去离子水以分散该混合物。通过真空蒸馏除去丙酮,并且调整固体含量至45%。
分析值:LD:84;pH:7.6。
实施例6
在96℃下、在62g无水丙酮中,将由己二酸、1,6-己二醇和新戊二醇制成的453g聚酯二醇(OH值=56mg KOH/g),基于二聚脂肪酸的145g聚酯二醇(3228,来自Croda;OH值=56mg KOH/g),2.68g三羟甲基丙烷和13.4g二羟甲基丙酸(DMPA)与75.6g六亚甲基二异氰酸酯反应1小时。然后在5小时内添加130g无水丙酮并将温度降低至65℃。继续反应直至NCO含量为0.19%。然后用646g丙酮稀释混合物并冷却至57℃。然后在5分钟内逐滴加入被稀释在13.6g丙酮中的3.4g异佛尔酮二胺(IPDA),并将混合物搅拌30分钟。将该混合物用23.8g、5%浓度的氨水溶液中和,并使用900g去离子水以分散该混合物。通过真空蒸馏除去丙酮,并且调整固体含量至52%。
分析值:LD:35;pH:7.5。
实施例7
在90℃下、在70g无水丙酮中,将由己二酸、1,6-己二醇和新戊二醇制成的604g聚酯二醇(OH值=56mg KOH/g),0.94g三羟甲基丙烷和9.39g二羟甲基丙酸(DMPA)与70.9g六亚甲基二异氰酸酯反应3小时30分钟。然后在7小时内添加180g无水丙酮并将温度降低至65℃。继续反应直至NCO含量为0.4%。然后用450g丙酮稀释混合物并冷却至57℃。将该混合物用26.3g、10%浓度的氢氧化钠水溶液中和,并使用664g去离子水以分散该混合物。通过真空蒸馏除去丙酮,并且调整固体含量至50%。
分析值:LD:74;pH:8.0。
无定形,没有熔点;Tg:-52℃。
实施例8
在94℃下、在62g无水丙酮中,将由己二酸、1,4-丁二醇和2-甲基-1,3-丙二醇制成的649.8g聚酯二醇(OH值=52mg KOH/g),和13.4g二羟甲基丙酸(DMPA)与70.6g六亚甲基二异氰酸酯反应2小时30分钟。然后在7小时内添加130g无水丙酮并将温度逐步降低至67℃。继续反应直至NCO含量为0.2%。然后用646g丙酮稀释混合物并冷却至57℃。然后在5分钟内逐滴加入被稀释在13.6g丙酮中的3.4g异佛尔酮二胺(IPDA),并将混合物搅拌30分钟。将该混合物用23.8g、5%浓度的氨水溶液中和,并使用795g去离子水以分散该混合物。通过真空蒸馏除去丙酮,并且调整固体含量至49%。
分析值:LD:52;pH:8.0。
实施例9
在94℃下、在71.3g无水丙酮中,将由己二酸、1,6-己二醇和新戊二醇制成的556g聚酯二醇(OH值=56mg KOH/g),由己二酸、1,4-丁二醇、乙二醇和二乙二醇和丙三醇制成的150.9g聚酯二醇(OH值=55mg KOH/g),和15.4g二羟甲基丙酸(DMPA)与81.2g六亚甲基二异氰酸酯反应2小时30分钟。然后在4小时内分步添加150g无水丙酮并将温度逐步降低至67℃。继续反应直至NCO含量为0.25%。然后用743g丙酮稀释混合物并冷却至57℃。然后在5分钟内逐滴加入被稀释在15.7g丙酮中的3.92g异佛尔酮二胺(IPDA),并将混合物搅拌30分钟。将该混合物用28.4g、5%浓度的氨水溶液中和,并使用972g去离子水以分散该混合物。通过真空蒸馏除去丙酮,并且调整固体含量至45%。
分析值:LD:84.5;pH:7.6。
向该分散体中如下加入交联剂:将70重量份LR 9056(BASF;基于异氰脲酸酯化的六亚甲基二异氰酸酯的多异氰酸酯)与30重量份的甘油三乙酸酯(一种可生物降解的增塑剂)混合以降低粘度。然后将0.64g该混合物加入到98.58g聚氨酯分散体中以获得比例为每100份固体聚氨酯1份的/>LR 9056。
实施例10
在70-75℃下、在169g无水丙酮中,将由己二酸、1,6-己二醇和新戊二醇制成的551g聚酯二醇(1,6-己二醇:新戊二醇的摩尔比=1.8:1;OH值=56mg KOH/g),和20.1g二羟甲基丙酸(DMPA)与96.19g六亚甲基二异氰酸酯反应至NCO含量为1.4%。然后用735g丙酮稀释混合物并冷却至35-38℃。将该混合物用125.4g、5%浓度的氢氧化钠水溶液中和,并使用1201g去离子水以分散该混合物。在10分钟内逐滴加入9.08g二亚乙基三胺(DETA)于110g去离子水的溶液。将该混合物用127g水稀释,通过真空蒸馏除去丙酮,并且调整固体含量至30%。
分析值:LD:97;pH:8.9;Tg:-42℃。
无定形,没有可检测到的熔点。
实施例11(比较)
聚氨酯分散体胶黏剂按照WO 2012/013506 A1的实施例1进行制备。
熔点:52℃,熔化焓:60J/g,Tg:-51℃.
实施例12(比较)
基于聚醚醇的聚氨酯分散体胶黏剂按照WO 2006/087348 A1(EP 1853640)的实施例1进行制备。
实施例13
在75-78℃下、在120g无水丙酮中,将由己二酸、1,6-己二醇和新戊二醇制成的725g聚酯二醇(OH值=56mg KOH/g),10.6g二羟甲基丙酸(DMPA)与81.2g六亚甲基二异氰酸酯反应直至NCO值为0.43%。然后用600g丙酮稀释混合物并冷却至57℃。将该混合物用31.6g、7.6%浓度的氢氧化钠水溶液中和,混入被稀释在16.4g丙酮中的8.2g基于六亚甲基异氰酸酯的水可分散性异氰酸酯(LR 9056,BASF),并使用791g去离子水以分散该混合物。通过真空蒸馏除去丙酮,并且固体含量达到53.6%。
分析值:LD:40.8;pH:7.6;
Tg:-53℃,没有检测到熔点。
实施例14
在75-78℃下、在60g无水丙酮中,将由己二酸、1,6-己二醇和新戊二醇制成的485g聚酯二醇(OH值=56mg KOH/g),由己二酸、乙二醇和二乙二醇制成的248.4g聚酯二醇(OH值=46mg KOH/g),0.9g丙三醇和11.27g二羟甲基丙酸(DMPA)与82.5g六亚甲基二异氰酸酯反应5小时。然后两次慢慢地加入30g无水丙酮并将温度降低至70℃。继续反应直至NCO含量为0.43%。然后用600g丙酮稀释混合物并冷却至57℃。将该混合物用31.6g、10%浓度的氢氧化钠水溶液中和,并使用802g去离子水以分散该混合物。通过真空蒸馏除去丙酮,并且调整固体含量至49%。
分析值:LD:82;pH:8。
Tg:-49℃,没有检测到熔点。
实施例15
重复上述实施例(实施例13),不同之处在于:在85℃下,将聚酯二醇混合物与29g六亚甲基二异氰酸酯于熔体中反应直至NCO-基团全部消耗。将熔体温度冷却至60℃,加入预装料的所有其他组分,并且反应在与剩余的六亚甲基二异氰酸酯的条件下继续,如上所述。在NCO值达到0.43%后,用600g丙酮稀释混合物并冷却至57℃。将该混合物用31.6g、10%浓度的氢氧化钠水溶液中和,并使用802g去离子水以分散该混合物。通过真空蒸馏除去丙酮,并且调整固体含量至47%。
分析值:LD:82.4;pH:7.7。
Tg:-49.4℃,没有检测到熔点。
实施例16
在75-78℃下、在60g无水丙酮中,将由己二酸、1,6-己二醇和新戊二醇制成的601g聚酯二醇(OH值=56mg KOH/g),27g分子量为600的聚乙二醇(E 600,BASF),0.9g丙三醇和11.27g二羟甲基丙酸(DMPA)与82.5g六亚甲基二异氰酸酯反应5小时。然后慢慢地加入60g无水丙酮并将温度降低至70℃。继续反应直至NCO含量为0.48%。然后用600g丙酮稀释混合物并冷却至57℃。将该混合物用31.6g、10%浓度的氢氧化钠水溶液中和,并使用697g去离子水以分散该混合物。通过真空蒸馏除去丙酮,在蒸馏过程中加入另外的613g去离子水,并且固体含量达到35%。
分析值:LD:86.2;pH:7.5。
Tg:-52℃,没有检测到熔点。
堆肥测试
根据美国澳大利亚标准AS 5810-2010和ISO 14855-1(2012),“Determination ofthe ultimate aerobic biodegradability of plastic materials under controlledcomposting conditions-Method by analysis of evolved carbon dioxide(在受控的堆肥条件下塑料材料的最终有氧可生物降解性的测定——通过分析释放的二氧化碳的方法)”,在为了模拟家用堆肥条件的环境温度(28±2℃)下而不是所述58℃温度下,测试家用可堆肥性。
结果归纳于表1中。
表1:家用可堆肥性的测试结果
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基于这些结果,与实施例10类似的家用可堆肥性,预期在例如具有类似组成的实施例,和/或本文所述的在预筛选的基于酶的快速测试中显示相同的可降解性的实施例中可具有。
用于生物可降解性的基于酶的快速测试
为了评估潜在的生物可降解性,根据Tokiwa的方法(Nature 270.76,1977)应用基于酶的快速测试来模拟家用可堆肥性。酶能够水解聚合物中的酯键,产生的羧酸会导致pH值下降,这在pH指示剂和光度计的帮助下可见。
如果将聚氨酯分散体胶黏剂的由酶导致的降解的测试结果与在家用堆肥条件下的这些聚氨酯分散体胶黏剂产生的家用堆肥测试结果(参见实施例10)进行比较,可以发现,酶降解能力与在家用堆肥条件下的降解能力之间存在良好的相关性。比较对照探针——例如根本不会降解的聚氨酯分散体胶黏剂(实施例12;基于聚醚醇的聚氨酯)——没有显示出任何酶降解的迹象,而仅在工业条件下可堆肥的聚氨酯分散体胶黏剂(实施例11)在该测试中只会显示出酶的缓慢降解。
使用的试剂和物质:
缓冲液:
20mM磷酸盐缓冲液,pH 7.0
储备溶液:将13.6g磷酸二氢钾KH2PO4(Sigma;P9791)溶解于800ml去离子水中,通过加入NaOH调节pH至pH 7。使用去离子水填充至1000ml,完成溶液配制。
酶:
米根霉脂肪酶(Rhizopus oryzae Lipase)(Sigma;62305)
荧光假单胞菌酯酶(Pseudomonas fluorescens Esterase)(Sigma;75742)
洋葱假单胞菌脂肪酶(Pseudomonas cepacia Lipase)(Sigma;62309)
假单胞菌属胆固醇酯酶(Pseudomonas sp.Cholesterol Esterase)(CreativeEnzymes;DIA-134))。
假单胞菌属脂蛋白脂肪酶(Pseudomonas sp.Lipoprotein Lipase)(CreativeEnzymes;DIA-210)。
所有的酶均溶解在20mM磷酸盐缓冲液(pH 7.0)中,并且用50%(v/v)丙三醇稳定,以便在-20℃下储存。制备每种酶浓度为100U/ml的储备溶液。
pH指示剂:
pH指示剂是溴百里酚蓝(Sigma;B8630)。将200mg百里酚蓝溶解在100ml磷酸钾缓冲液(5mM,pH 7.0)中制备储备溶液。
对照:
将聚己内酯粉末(PCL;Sigma;440744)用作对照底物。
测试容器:
使用96微孔板(Sigma;TM0267556)作为测试容器。
光度计:
试验测定通过光度计(Microwell-Reader;Tecan Infinite M1000Pro)进行分析。
测试过程:
对于一种底物,制备以下物质:
3×测试物质,200μl:
-0.5%(w/v)测试物质
-20mM磷酸盐缓冲液(pH 7.0)
-0.2mg/ml溴百里酚蓝
-每一种酶为5U/ml
1×测试盲,200μl:
-0.5%(w/v)测试物质
-20mM磷酸盐缓冲液(pH 7.0)
-0.2mg/ml溴百里酚蓝
3×对照,200μl:
-0.5%(w/v)聚己内酯
-20mM磷酸盐缓冲液(pH 7.0)
-0.2mg/ml溴百里酚蓝
-每一种酶为5U/ml
1×对照盲,200μl:
-0.5%(w/v)聚己内酯
-20mM磷酸盐缓冲液(pH 7.0)
-0.2mg/ml溴百里酚蓝
1×酶盲,200μl:
-20mM磷酸盐缓冲液(pH 7.0)
-0.2mg/ml溴百里酚蓝
-每一种酶为5U/ml
1×缓冲液盲,200μl:
-20mM磷酸盐缓冲液(pH 7.0)
-0.2mg/ml溴百里酚蓝
将待测试的底物在DMSO中制备成5%(w/v)溶液。将缓冲液、pH指示剂和酶混合成最终浓度并预热至37℃。每个孔中预先加入20μl量的测试物质(或对照物质)的储备溶液,加入180μl反应混合物以启动反应,并且放入读数器中。将微孔板加热至37℃,同时振荡。测量持续数小时。每5分钟记录433nm和615nm处的吸收。这两个波长是溴百里酚蓝在不同质子化状态(由pH值)决定下的最大吸收。
测试结果可以通过照片或时间依赖性的曲线图来记录。将433nm和615nm处的吸收的吸收值商数用作信号读数。在20mM磷酸盐缓冲液(pH 7.0)和0.2mg/ml溴百里酚蓝的混合物中,433nm/615nm的吸收值商数为0.5。商数越高,pH值越低。与对照物质比较的pH值变化越大,测试物质的酶促降解程度越高。
将本发明实施例4至8和10在酶降解测试中进行测试,并且与实施例11(WO2012/013506实施例1)和实施例12(WO 2006/087348A1实施例1)进行比较。酶降解测试的结果如图1至8所示。
图1:
图1示出实施例10的聚氨酯的433nm/615nm吸光度比随时间的变化。433nm/615nm吸光度比显示出急剧增加,在50分钟内达到稳定阶段。这与上述实施例10的堆肥测试结果具有良好的相关性。
图2:
图2示出实施例7的聚氨酯的433nm/615nm吸光度比随时间的变化。433nm/615nm吸光度比显示出急剧增加,在不到100分钟内达到稳定阶段。
图3:
图3示出实施例4的聚氨酯的433nm/615nm吸光度比随时间的变化。433nm/615nm吸光度比在开始时显示出急剧增加,并且在不到300分钟内达到稳定阶段。
图4:
图4示出实施例11(比较实施例,WO 2012/013506 A1的实施例1)的聚氨酯的433nm/615nm吸光度比随时间的变化。433nm/615nm吸光度比显示出平缓增加,在300分钟内没有达到稳定阶段。这与上述堆肥测试结果具有良好的相关性。该实施例是工业可堆肥的(可在工业堆肥设施的高温下堆肥),但在家用堆肥条件的较低温度下的可堆肥性显著降低。
图5:
图5示出实施例12(比较实施例,WO 2006/087348 A1的实施例1)的聚氨酯的433nm/615nm吸光度比随时间的变化。433nm/615nm吸光度比没有增加,因此在测试条件下没有酶促降解。
图6:
图6示出实施例5的聚氨酯在433nm/615nm吸光度比随时间的变化。433nm/615nm吸光度比在开始时显示出急剧地增加,并且在不到100分钟内达到稳定阶段。
图7:
图7示出实施例6的聚氨酯的433nm/615nm吸光度比随时间的变化。433nm/615nm吸光度比在开始时显示出急剧增加,并且在不到100分钟内达到稳定阶段。
图8:
图8示出实施例8的聚氨酯的433nm/615nm吸光度比随时间的变化。433nm/615nm吸光度比在开始时显示出急剧增加,并且在不到300分钟内达到稳定阶段。
酶降解试验的结果如图1至图8所示。家用可堆肥材料(实施例4、5、6、7、8和10;图1、2、3、6、7和8)的433nm/615nm吸光度比(快速酶促降解)在首先的50分钟内急剧增加,在300分钟内达到稳定阶段(完全酶促降解,基于所使用的酶)。非家用可堆肥材料(实施例11和12;分别为图4和5)的433nm/615nm吸光度比在首先的50分钟内没有增加或仅有少量的增加(没有或缓慢地酶促降解),并且没有在300分钟内没有达到稳定阶段(在所使用的酶的条件下,没有完全酶促降解)。
胶黏片材的制备(带有硅化离型纸的纸质标签)
将选定的实施例的水性聚氨酯分散体与润湿剂(I-SC,BASF)混合以获得每100g(固体)聚氨酯含有1g(固体)润湿剂的混合物。然后使用棒涂机将混合物施用于硅化离型纸上,并且在90℃的烘箱中干燥3分钟。干施用重量为17g/m2。用70g/m2标签面纸覆盖胶黏剂层以获得胶黏层压片。测试前,将片材在23℃和50%相对湿度(rH)下放置至少16小时。/>
粘附力测试
环形初粘力测量和90°剥离粘附力测试分别按照FINAT测试方法No.9和FINAT测试方法No.2中所述进行。然而,测试基材不是使用浮法玻璃(float glass),而是通过使用双面胶带将纸条粘附到刚性基材上来制备。使用与制备胶黏片材相同的标签面纸。如果没有另外说明,则使用标准FINAT测试滚筒以10mm/s将样品滚压到基材上。剥离测试在20分钟(或所示1分钟)和24小时的接触时间后进行。如果没有另外说明,则放置、接触和测试均在23℃和50%相对湿度下进行。
环形初粘力和剥离测试中的大于3N/25mm的值表明聚合物适用于压敏胶黏剂。
测试结果如表2所示。这些值是三次重复的平均值。
表2:环形初粘力测量和90°剥离粘附力测试结果
1)接触时间1min
CP=干净的面板——面板上没有可见的污渍。
PS=面板污渍——测试区域变色,但没有粘性残留物。
CF=内聚破坏——胶黏剂膜在测试过程中破裂,在面板和正面材料上留下胶黏剂残留物。
AT=胶黏剂转移——胶黏剂与正面材料干净地分离,在测试面板上留下胶黏剂膜。
PT=纸撕裂——粘合力超过纸面材料的强度。所用的结果应该是纸张撕裂之前达到的最大值。
分解测试和粘附力测试表明,测试的实施例可用于压敏胶黏剂标签应用,以获得例如用于软包装的家用可堆肥标签。
Claims (17)
1.不干胶标签,其包括具有第一侧面和第二侧面的衬底材料,附着于衬底材料的第一侧面的压敏胶黏剂层,以及附着于所述胶黏剂层的剥离衬垫或者在衬底材料的第二侧面上的剥离涂层,
其中衬底材料由纸或家用可堆肥聚合物膜制成,以及压敏胶黏剂层由水性聚氨酯分散体压敏胶黏剂制成,
其中至少60重量%的聚氨酯由以下组成:
(a)至少一种二异氰酸酯,
(b)至少一种聚酯二醇,和
(c)至少一种选自二羟基羧酸和二氨基羧酸的二官能化羧酸;
其中聚氨酯的玻璃化转变温度低于20℃,
其特征在于聚氨酯的熔点不高于20℃,或者其中聚氨酯的熔点高于20℃且熔化焓低于10J/g。
2.根据权利要求1所述的不干胶标签,其中聚氨酯胶黏剂的膜在家用堆肥条件下在360天内大于90重量%地分解为CO2和水。
3.根据前述权利要求中任一项所述的不干胶标签,其中剥离衬垫的表面能或剥离涂层的表面能小于30mN/m;并且剥离衬垫优选为硅化纸。
4.根据前述权利要求中任一项所述的不干胶标签,其中如实施例所述测定的环形初粘力为至少3N/25mm。
5.根据前述权利要求中任一项所述的不干胶标签,其中如实施例所述在24小时接触时间后测定的90°剥离粘附力为至少3N/25mm。
6.根据前述权利要求中任一项所述的不干胶标签,其中聚酯二醇由至少一种二元酸和至少一种支链二元醇制成,或者其中聚酯二醇在20℃下为液体。
7.根据前述权利要求中任一项所述的不干胶标签,其中在制备聚氨酯时,异氰酸酯基团与对于异氰酸酯呈反应性的基团的比率至少为1。
8.根据前述权利要求中任一项所述的不干胶标签,其中至少60重量%的聚氨酯由以下组成:
(a)至少一种脂族二异氰酸酯,
(b)至少一种脂族聚酯二醇,
(c)至少一种选自二羟基羧酸和二氨基羧酸的二官能化羧酸,和
(d)至少一种不同于单体(a)至(c)的且具有两个选自伯氨基和仲氨基的反应性基团的多官能化化合物。
9.根据前述权利要求中任一项所述的不干胶标签,其中至少80重量%的聚氨酯由至少一种脂族聚酯二醇(b)组成。
10.根据前述权利要求中任一项所述的不干胶标签,其中至少80重量%的至少一种脂族聚酯二醇(b)由至少一种脂族二元羧酸和至少一种脂族二元醇组成。
11.根据前述权利要求中任一项所述的不干胶标签,其中聚酯二醇由至少mol%、优选至少20mol%的支链脂族二元醇,优选新戊二醇制成,基于制备聚酯二醇所用的二元醇的总量计。
12.根据前述权利要求中任一项所述的不干胶标签,其中聚氨酯由以下组成:
a)至少一种二异氰酸酯,
b)至少一种二元醇,其中,
b1)基于二元醇(b)的总量计的10至100mol%为具有500至5000g/mol的摩尔质量的聚酯二醇,
b2)基于二元醇(b)的总量计的0至90mol%,具有60至500g/mol的摩尔质量,
c)至少一种选自二羟基羧酸或二氨基羧酸的二官能化羧酸,
d)任选地不同于单体(a)至(c)的且具有反应性基团的其他多官能化化合物,其中所述反应性基团为醇羟基、伯氨基或仲氨基、或异氰酸酯基,和
e)任选地不同于单体(a)至(d)的且具有的反应性基团为醇羟基、伯氨基或仲氨基、或异氰酸酯基的单官能化化合物,其中聚氨酯优选至少部分地由生物基材料制成。
13.根据前述权利要求中任一项所述的不干胶标签,其中聚氨酯由基于聚氨酯的总重量计的至少80重量%的聚酯醇、基于聚氨酯的总重量计的小于20重量%的异氰酸酯化合物制成,且包含小于100mmol/kg的脲基。
14.根据前述权利要求中任一项所述的不干胶标签,其中聚氨酯分散体胶黏剂包含至少一种外交联剂;优选地选自由二异氰酸酯生成且具有至少两个异氰酸酯基的异氰脲酸酯、具有至少一个碳二亚胺基团的化合物、化学上盖帽的异氰酸酯、包封的异氰酸酯、包封的脲二酮、缩二脲、脲基甲酸酯、氮丙啶、噁唑啉、环氧化合物、以及所提及的物质的混合物。
15.根据前述权利要求中任一项所述的不干胶标签,其中衬底材料是家用可堆肥的,并且选自纸、聚乳酸、木质素、淀粉、纤维素材料、聚乙醇酸、聚羟基烷酸酯、聚碳酸亚丙酯、脂族聚酯、脂族-芳族共聚酯和上述材料的混合物。
16.水性聚氨酯分散体压敏胶黏剂用于制备不干胶标签的用途,所述不干胶标签包括具有第一侧面和第二侧面的衬底材料,附着于衬底材料的第一侧面的压敏胶黏剂层,以及附着于所述胶黏剂层的剥离衬垫或者在衬底材料的第二侧面上的剥离涂层,其中衬底材料由纸或家用可堆肥聚合物膜制成,以及
压敏胶黏剂层由水性聚氨酯分散体压敏胶黏剂制成,
其中至少60重量%的聚氨酯由以下组成:
(a)至少一种二异氰酸酯,
(b)至少一种聚酯二醇,和
(c)至少一种选自二羟基羧酸和二氨基羧酸的二官能化羧酸;
其中聚氨酯的玻璃化转变温度低于20℃,
其特征在于聚氨酯的熔点不高于20℃,或者其中聚氨酯的熔点高于20℃且熔化焓低于10J/g。
17.根据前述权利要求的用途,其中聚氨酯胶黏剂的膜在家用堆肥条件下在360天内大于90重量%地分解为CO2和水。
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DE1495745C3 (de) | 1963-09-19 | 1978-06-01 | Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung wäßriger, emulgatorfreier Polyurethan-Latices |
US3412054A (en) | 1966-10-31 | 1968-11-19 | Union Carbide Corp | Water-dilutable polyurethanes |
DE2034479A1 (de) | 1970-07-11 | 1972-01-13 | Bayer | Polyurethan Kunststoffe und Verfahren zu ihrer Herstellung |
DE2314513C3 (de) | 1973-03-23 | 1980-08-28 | Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung von wäßrigen Polyurethandispersionen |
DE2314512C3 (de) | 1973-03-23 | 1980-10-09 | Bayer Ag, 5090 Leverkusen | Thermoplastische, nichtionische, in Wasser despergierbare im wesentlichen lineare Polyurethanelastomere |
DE2725589A1 (de) | 1977-06-07 | 1978-12-21 | Bayer Ag | Verfahren zur herstellung von waessrigen polyurethan-dispersionen und -loesungen |
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DE2843790A1 (de) | 1978-10-06 | 1980-04-17 | Bayer Ag | Verfahren zur herstellung von waessrigen dispersionen oder loesungen von polyurethan-polyharnstoffen, die nach diesem verfahren erhaeltlichen dispersionen oder loesungen, sowie ihre verwendung |
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