CN1323818C - 木质产品防腐剂的改进 - Google Patents

木质产品防腐剂的改进 Download PDF

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CN1323818C
CN1323818C CNB2003801068834A CN200380106883A CN1323818C CN 1323818 C CN1323818 C CN 1323818C CN B2003801068834 A CNB2003801068834 A CN B2003801068834A CN 200380106883 A CN200380106883 A CN 200380106883A CN 1323818 C CN1323818 C CN 1323818C
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P·J·海沃德
G·W·梅森
T·贾特斯
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Abstract

一种三唑酮和/或三唑醇作为保护胶合木质产品免受微生物侵蚀和损坏的防腐剂的使用方法。该方法的特点是在制造胶合木质产品的过程中施加三唑酮和/或三唑醇。

Description

木质产品防腐剂的改进
发明领域
本发明涉及木质胶合产品的抗菌防腐剂。
发明背景
作为生物材料，木材易受真菌和昆虫的侵害。这些生物体可能损坏木材的外观，并可能严重降低木材的结构强度。涂布杀真菌剂和/或杀虫剂可以保护木材和木质产品免受损害木材生物体的影响。这些处理可以大大延长木制品的使用寿命，特别是天然耐久性低的乔木制品，如radiata松木和其它软木材料。
对于某些木质产品，涂布防腐剂处理的常规方法是不合适的。例如，砷酸铜铬(“CCA”)之类的水基处理剂不能涂布到层积单板产品、粒基产品或纤维基产品上，否则会引起明显的降解和产品损耗。这些产品的其它制造后处理剂，如轻质有机溶剂防腐剂(“LOSP”)是昂贵的，且需要附加处理步骤来进行处理，造成额外的成本。
受某些木质产品制造商喜爱的一种方法是在制造过程中把防腐剂加入胶合剂中来施加防腐剂。这种方法可以用于由较薄或较小颗粒(如木纤维、木屑或木片和薄木片)构成的任何木质产品。夹板、层积单板(LVL)、中密度纤维板(MDF)、干胶板/绞合板/取向绞合板和碎木板都属于这一类。
这种施加方法的主要缺点在于制造方法中所用胶合剂的性质和用于处理的化合物的类型。
一般来说，用于木质产品的胶合剂体系是高pH值(9-12)和高活性的(如异氰酸酯基胶合剂)。因此，把一种化合物加入到这种环境中会导致该化合物分子迅速分解。另一个对加入化合物坚固性的挑战是胶合剂的固化条件。这些固化条件通常是高压体系中的高温(～170℃)。
这些条件要求加入的防腐剂的坚固性足以在产品的使用寿命内保持至少一部分活性有效。
本领域中已知，三唑类化合物一般对担子菌类有效，这是一类导致木材腐烂的已知真菌。最常用于保护实心木材腐烂的三唑类化合物是戊唑醇(tebuconazole)和丙环唑。现已表明，为防止腐烂在木材中所需的活性成分的用量为50～300克戊唑醇/米3木材和220～490克丙环唑/米3木材。也有报道，在某些情况下这两种三唑化合物具有协同作用。
另外，同样已知的是由于胶合剂体系的性质、在随后工艺过程中的分解或在木质产品中的不均匀分布，上述的三唑化合物当用于胶缝处理时必须大量加入到胶合剂混合物中，才能在实心木材用途中显示活性。
因此，仍然需要一种可以在制造过程中涂布木质产品的防腐剂。
本申请人令人惊奇地发现，三唑酮和/或三唑醇可以用作防止木质产品免遭微生物(特别是真菌)侵蚀和损坏的防腐剂。
令人惊奇的是，三唑酮和/或三唑醇在胶缝处理条件下是稳定的，因此可以用作制造胶合木质产品的防腐剂。在某些情况下，三唑酮在碱性条件下转化为在这种条件下稳定且也显示所需生物性质的三唑醇。
发明目的
本发明的第一个目的是提供一种把三唑酮和/或三唑醇用作木质产品抗微生物防腐剂的方法。
本发明的第二个目的是提供一种用于制造木质产品并具有更高抗微生物性的防腐剂组合物。
发明概述
本发明的一个方面是提供三唑酮和/或三唑醇作为保护胶合木质产品免遭微生物侵蚀和损坏的防腐剂的使用方法，其特征在于在胶合木质产品的制造过程中施加三唑酮和/或三唑醇。
本发明的另一方面是提供一种用于保护胶合木质产品免遭微生物侵蚀和损坏的组合物，它含有胶合剂、三唑酮和/或三唑醇。
发明的详细说明
(±)1-(4-氯苯氧基-3，3-二甲基-1-(1H-1，2，4-三唑-1-基)丁-2-酮(三唑酮)是农业上用作杀真菌剂，特别是用于控制担子菌类的已知三唑化合物。三唑酮具有一个醇类似物，(±)1-(4-氯苯氧基-3，3-二甲基-1-(1H-1，2，4-三唑-1-基)丁-2-醇(三唑醇)。它显示相似的活性，并用于同样的目的。这些已知的化合物在农业应用中已被新的三唑化合物如丙环唑和戊唑醇代替，因为这些新的三唑化合物在更低的用量下具有更高的活性。
表1：所选三唑类的农业用量
  活性   用量范围，g/ha(农业用量)1
  丙环唑   100-150
  戊唑醇   100-250
  三唑酮   125-500
  三唑醇   125-500
1数据来自杀虫剂手册，第12版，英国谷物保护委员会，Farnham，Surrey，UK.2000
当已知的三唑通过胶缝施加到木质产品如绞合板、碎木板、中密度纤维板、夹板和层积单板中时，在预料的所述活性剂含量下不能满足预料的性能值。
令人惊奇地，在这些条件下，三唑酮和三唑醇在极低的用量下具有显著而持久的效果。这意味着，相对于三唑酮/三唑醇的低加入量显示了更高的性能值。
当例如在PF型胶合剂中发现的碱性条件下用于胶缝时，三唑酮可还原为醇类似物三唑醇。令人惊奇的是，三唑醇显示与三唑酮相同的效果。
表2.戊唑醇、丙环唑和三唑酮的有效剂量率
 1用量，克活性成分/米3   对目标微生物的效果2(表示为标准腐烂试验中重量损耗％，用瘤盖干酪菌作为目标物种)1
  戊唑醇   丙环唑   三唑酮
  80   9.2   -   -
  100   -   20.5   3.7
  160   20.9   -   -
  200   -   7.6   0.5
  320   6.3   -   -
  400   -   21.4   0.9
  640   18.5   -   -
  800   -   1.8   1.4
  未处理                 17.5
  商业标准3LOSP                 5.8
1在使用酚醛胶的松木夹板缝中
2使用日本木材防腐剂协会标准试验程序
3轻有机溶剂防腐剂(氧化三丁基锡)
这种新的活性使得三唑分子三唑酮和三唑醇特别适用于保护胶合木质产品免遭微生物的侵蚀，特别是某些引起腐烂的真菌的侵蚀。
按照本发明的方法，三唑酮和/或三唑醇较好在胶合木质产品的制造过程中加入到胶合剂中(胶缝处理)。按照本发明，令人惊奇地可以施加低剂量的三唑酮和/三唑醇，同时对木质产品提供高效的保护。
本发明的方法优选提供对胶合木质产品的保护，使其免遭真菌的侵蚀和损坏。
损坏木材的真菌的例子：
毛壳菌属，如球毛壳或chaetomium alba-arenulum
灰腐质霉(humicola grisea)
彼得克属(petriella)如刚毛彼得壳(petriella setifera)
毛束霉属(trichurus)如trichurus spiralis
担子菌纲
粉孢革菌属如粉孢革菌
革盖菌属如采绒革盖菌
conkioporia如dondioporia expans
glenospora如glenospora graphii
粘褶菌属(gloephyllum)如冷杉粘褶菌或
gloephyllum adoratum或
gloephyllum protactum或
篱边粘褶菌或
密粘褶菌
香茹属如浅杯状香茹或
香茹或
洁丽香茹或
lentinus grinus或
lentinus squarrolosus
桩茹属(paxillus)如耳状桩茹
侧耳属如糙皮侧耳
卧孔菌属如poria monticola或
poria placenta或
纤维卧孔菌或
绵腐卧孔菌
serpula如serpula himantoides或
serpula lacrymans
韧革菌属如毛韧革菌
干酪菌属如瘤盖干酪菌。
胶合木质产品的制造方法通常是已知的。这种制造方法一般用于由较薄或较小颗粒(如木纤维、木屑和薄木片)制成的木材复合产品。用这种方法可以制造夹板、层积单板(LVL)、中密度纤维板(MDF)、干胶板/绞合板/取向绞合板和碎木板。
在这种方法中，通过加入胶合剂并在加压下将薄或小的木粒相互结合在一起，形成木材复合产品。在制造过程中向胶合剂中加入木材防腐剂是一种已知的实践，即所谓的胶缝处理。
按照本发明的方法，三唑酮和/或三唑醇在木质产品的制造过程中加入到胶合剂中。也可以先制备含有胶合剂、三唑酮和/或三唑醇以及一种或多种与胶合剂相容的任选溶剂的组合物，然后在制造过程中把这种组合物施加到木粒上。
可用于本发明方法的溶剂例如是N-甲基-吡咯烷酮、二醇醚、texanole、苄醇、苯氧基乙醇、环己酮。
由于会影响胶合剂的粘度或固化时间，所以应避免加入大量的二醇(glycols)。
可用于制造胶合木质产品的胶合剂的例子包括如下胶合剂或胶合剂体系：脲基体系或脲酚基体系，如UF＝脲甲醛树脂、PF＝酚蜜胺(甲醛)树脂、MUF＝蜜胺(甲醛)-脲树脂；聚乙烯醇(PVA)体系；pMDI＝聚亚甲基二苯基二异氰酸酯。优选的是UF、MUF、PF和PVA体系。
在本发明的另一个实施方式中，三唑酮和/或三唑醇与至少另一种杀真菌剂混合使用。上述的杀真菌剂较好选自戊唑醇和环唑醇(cyproconazole)。
令人惊奇地发现，三唑酮和/或三唑醇当以混合产物涂布时能提高在胶合木质产品中其它三唑杀真菌剂即戊唑醇和环唑醇的保护效果。三唑酮与戊唑醇(摩尔比优选为5∶1～1∶2)的混合物或三唑酮与环唑醇(摩尔比优选为5∶1～1∶3)的混合物为胶合木质产品免遭腐烂真菌的侵蚀提供了宽范围的保护。
在本发明的另一个实施方式中，三唑酮和/或三唑醇与一种或多种已知经胶缝涂布时有效的杀虫剂混合涂布。合适的杀虫剂包括合成的拟除虫菊酯如二氯苯醚菊酯、氯氰菊酯、α-氯氰菊酯、溴氰菊酯、氟氯氰菊酯、联苯菊酯，拟灭虫碱(neonicotinoide)如吡虫啉、clothianidin、啶虫脒、thiamethoxam、溴虫清和氟虫腈。杀虫剂与三唑酮/三唑醇的混合物或者三唑酮/三唑醇与戊唑醇或环唑醇的混合物在合适比例下提供了在加工处理大多数木质复合材料时一步涂布防腐剂和胶合体系的简便方法。
本发明还提供了一种保护胶合木质产品免遭微生物侵蚀和损坏的组合物。这种组合物含有三唑酮和/或三唑醇和胶合剂或胶合剂体系。优选的胶合剂或胶合剂体系如上所述。本发明的组合物还含有其它添加剂，如与胶合剂或胶合剂体系相容的添加剂。这种组合物或者可悬浮在水中，使水成为该组合物的一个组份。本发明的组合物可以用通常已知的方法制备，如把各组份混合在一起。该组合物可以按照本发明的方法进行使用，即在木质胶合产品的制造过程中将其加入到木粒中。

Claims (10)

1.一种三唑酮和/或三唑醇作为保护胶合木质产品免遭微生物侵蚀和损坏的防腐剂的使用方法，其特征在于在胶合木质产品的制造过程中施加三唑酮和/或三唑醇。
2.如权利要求1所述的方法，其特征在于所述的木质产品选自木纤维、木屑或木片和薄木片、夹板、层积单板(LVL)、中密度纤维板(MDF)、干胶板/绞合板/取向绞合板(OSB)和碎木板。
3.如权利要求1或2中至少一项所述的方法，其特征在于三唑酮和/或三唑醇在木质产品的制造过程中加入胶合剂中。
4.如权利要求1-3中至少一项所述的方法，其特征在于通过胶缝添加涂布胶合剂、三唑酮和/或三唑醇和一种或多种任选溶剂的混合物。
5.如权利要求1-4中至少一项所述的方法，其特征在于使用三唑酮和/或三唑醇及至少另一种选自杀真菌剂和杀虫剂的活性剂的混合物。
6.如权利要求1-5中至少一项所述的方法，其特征在于使用三唑酮和/或三唑醇及至少一种选自戊唑醇和环唑醇的化合物的混合物。
7.用于保护胶合木质产品免遭微生物侵蚀和损坏的组合物，它含有胶合剂、三唑酮和/或三唑醇。
8.如权利要求7所述的组合物，其特征在于它含有至少另一种选自杀真菌剂和杀虫剂的活性剂以及一种或多种与胶合剂相容或在水中悬浮或乳化的任选溶剂。
9.如权利要求7所述的组合物，其特征在于它含有水作为溶剂。
10.胶合木质产品，它含有三唑酮和/或三唑醇。
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