CN113316509B - 形成自动洗碗袋的方法、真空形成***以及袋 - Google Patents
形成自动洗碗袋的方法、真空形成***以及袋 Download PDFInfo
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- CN113316509B CN113316509B CN202080009990.9A CN202080009990A CN113316509B CN 113316509 B CN113316509 B CN 113316509B CN 202080009990 A CN202080009990 A CN 202080009990A CN 113316509 B CN113316509 B CN 113316509B
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- Prior art keywords
- automatic dishwashing
- pouch
- cavities
- sheet
- cavity
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- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003890 succinate salts Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
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- DTXLBRAVKYTGFE-UHFFFAOYSA-J tetrasodium;2-(1,2-dicarboxylatoethylamino)-3-hydroxybutanedioate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)C(O)C(C([O-])=O)NC(C([O-])=O)CC([O-])=O DTXLBRAVKYTGFE-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
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- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
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- B29C51/421—Heating or cooling of preforms, specially adapted for thermoforming
- B29C51/422—Heating or cooling of preforms, specially adapted for thermoforming to produce a temperature differential
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- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
- C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
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- C—CHEMISTRY; METALLURGY
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- B29K2995/0037—Other properties
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- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
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- B65B—MACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
- B65B47/00—Apparatus or devices for forming pockets or receptacles in or from sheets, blanks, or webs, comprising essentially a die into which the material is pressed or a folding die through which the material is moved
- B65B47/02—Apparatus or devices for forming pockets or receptacles in or from sheets, blanks, or webs, comprising essentially a die into which the material is pressed or a folding die through which the material is moved with means for heating the material prior to forming
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- B65B—MACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
- B65B47/00—Apparatus or devices for forming pockets or receptacles in or from sheets, blanks, or webs, comprising essentially a die into which the material is pressed or a folding die through which the material is moved
- B65B47/08—Apparatus or devices for forming pockets or receptacles in or from sheets, blanks, or webs, comprising essentially a die into which the material is pressed or a folding die through which the material is moved by application of fluid pressure
- B65B47/10—Apparatus or devices for forming pockets or receptacles in or from sheets, blanks, or webs, comprising essentially a die into which the material is pressed or a folding die through which the material is moved by application of fluid pressure by vacuum
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- C—CHEMISTRY; METALLURGY
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Landscapes
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- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Detergent Compositions (AREA)
Abstract
一种形成自动洗碗袋的方法包括以下步骤:提供材料的片材(10);识别所述材料的一个或更多个范围;用具有非均匀加热分布的加热装置加热所述材料,所述非均匀加热分布被布置为将所识别的范围加热至比所述材料的其他范围高的温度;以及在模具中形成所述材料以形成所述自动洗碗袋,所述自动洗碗袋包括多个空腔(12)。
Description
本发明涉及自动洗碗袋、形成自动洗碗袋的方法以及配置为形成自动洗碗袋的***。
水溶性自动洗碗袋一般是熟知的产品。这些袋通常由一个或更多个空腔形成,每个空腔都填充有诸如洗涤剂这样的洗碗组合物。
这样的自动洗碗袋可通过将诸如聚乙烯醇(PVOH)这样的合适的水溶性和可变形片材热成形来形成。热成形包括将这种片材加热至柔韧成形温度,并与一个或更多个模具结合,将片材成形为一个或更多个空腔。多个空腔具有分离不相容组分和提高最终产品美观性的优点。
然而,每添加一个隔离壁(形成空腔所必需的)导致空腔可被拉深所能达到的深度减小。此外,对于添加的每个空腔,空腔壁的厚度减小。结果,袋的总体积小于所需,壁的厚度可低于稳定性和产品完整性所需的余量。自动洗碗袋也有有限的占地面积,使得它们能够适应商购的自动洗碗机。
因此,在不减少洗涤剂组合物可用体积、不减小壁厚、和/或不将占地面积增大至不可接受水平的情况下,自动洗碗袋可拥有的空腔的数量存在实际限制。使用目前的技术,对于具有三个空腔的袋,可接受空腔深度(进而产品体积)和壁厚度存在有效商业限制。任何被制作为具有四个或更多空腔的袋都将无法具有足够的深度和/或壁厚度。
因此,需要一种形成解决这些问题的自动洗碗袋的改进方法。
根据权利要求1提供了一种形成根据本发明的自动洗碗袋的方法。
该方法得到了具有大量空腔而没有牺牲空腔深度或壁厚,因为它更容易拉伸被加热至更大程度的区域。
材料可在模具中形成,使得自动洗碗袋包括两个或更多个空腔,优选地三个或更多个或最优选地四个或更多个。这使更大数量的洗碗组合物能够被袋保留。
所识别的范围可以超过Von Mises尺度上的应变值极限1,优选地,1.5、2.0、2.4或甚至2.8。这使承受最大应变的范围能够被另外加热,以获得更坚固和更稳定的袋。
识别范围的步骤可包括对材料的行为和/或袋的最终形式进行计算机建模。这使能够预先针对任何形状的任何自动洗碗袋确定必要的加热分布。
该材料的所识别范围可对应于空腔的壁和/或基底。这些通常是在成形过程期间经受最显著变形的范围。
空腔的壁可被加热至比空腔的基底高的温度。特别地,壁经受最大的变形量,因此看到本发明的最大益处。
所形成的自动洗碗袋的最小厚度可不小于30μm,优选地不小于25μm。这样的最小厚度确保了自动洗碗袋的稳定性和完整性。在实施方式中,空腔的厚度根据它们是包含凝胶还是粉末而变化。包含粉末的空腔的最小厚度可为10至30μm,优选地15至25μm。包含凝胶的空腔的最小厚度可为15至35μm,优选地20至30μm。
空腔可限定至少11ml、优选地至少12ml、更优选地至少13ml、最优选地至少15ml的累积体积。这使通过袋能够提供合适剂量的洗碗组合物。
该材料可以是水溶性聚合物,例如,聚乙烯醇膜。其他可能的水溶性材料是聚(乳酸)膜、水溶性丙烯酸酯共聚物、甲基纤维素、羧甲基纤维素钠、糊精、乙基纤维素、羟乙基纤维素、羟丙基甲基纤维素、麦芽糊精、聚甲基丙烯酸酯、最优选地聚乙烯醇、聚乙烯醇共聚物和羟丙基甲基纤维素。这些材料对于成形步骤和最终使用二者都是合适的。
自动洗碗袋的占地面积可小于或等于60mm×50mm,优选为52至58mm×42至48mm,诸如55mm×45mm。具有这些占地面积的袋适用于自动洗碗机。
术语“热成形”在此被视为包括经由真空将片材吸入模具中的“真空成形”。成形步骤可包括真空成形。真空成形是特别适于将自动洗碗袋成形的方法。另选地或另外地,作为成形步骤的部分,可用一个或更多个空气射流迫使片材进入模具中。
该方法还可包括将一种或更多种洗碗组合物注射到空腔中的一个或更多个中的步骤。引入洗碗组合物是自动洗碗袋制造中的后续步骤。
该***还可包括用于将自动洗碗组合物引入空腔的一个或更多个中的一个或更多个配给装置。下面,描述用于包含在自动洗碗组合物中的合适成分。
根据权利要求14提供了在模具中使用非均匀加热分布和加热材料以在多个空腔中形成自动洗碗袋。这样的使用得到了具有以上讨论的优点的自动洗碗袋。
根据权利要求15或16提供了配置为形成根据本发明的自动洗碗袋的真空成型***。该***得到了具有以上讨论的优点的自动洗碗袋。
提供了通过所描述过程制备的包括至少两个空腔的自动洗碗袋。该自动洗碗袋具有如以上讨论的优点。这样的自动洗碗袋不能用先前已知的方法制作。优选地,该袋具有至少三个空腔或甚至至少四个空腔。
现在,将通过仅参照附图描述本发明,在附图中:
图1示出了根据现有技术制作的自动洗碗袋;以及
图2示出了根据本发明制造的自动洗碗袋。
通常,经由成型工艺制造自动洗碗袋100。提供材料片材并将该材料加热至给定温度。然后,将加热后的材料成型为最终自动洗碗袋制品的所期望形状。该材料通常是聚乙烯醇(PVOH),但可另选地是任何适于热成形的水溶性材料。在图1中示出了具有四个空腔12的自动洗碗袋100。在材料片材10中限定这四个空腔12,并且各空腔具有空腔深度和空腔壁厚度。由于自动洗碗袋具有四个空腔12,因此片材10中的可用材料一定比空腔12较少时拉伸得更多。结果,各空腔的深度有限,并且各空腔12的壁厚也可减小。
本发明人已发现,可通过用具有非均匀加热分布的加热装置加热材料片材10来改进该方法。也就是说,与跨工作区域(并且常来自单个加热元件)产生恒定热的典型加热装置相比,非均匀加热分布意味着工作区域的不同范围被提供不同的温度。根据本发明,工作区域的与材料片材10的在成形过程期间必须变形达最大量的范围对齐的特定范围(由加热装置限定)被加热至与材料片材10中的将不经历同样变形的其他区域相比更高的温度和/或被加热更长时间。对最多变形的范围进行该附加加热的结果是,各空腔12的深度可增加,并且同样地,各空腔12的壁厚度得以保持。发现的其他优点是在空腔12的拐角处的半径增大。例如,图2上指示的拐角22可形成为具有与图1中的相同拐角相比增大的半径。特别地,半径可至少为3mm。
不想受理论束缚,因为不是所有的膜区域都是均匀拉伸的从而能够在不牺牲厚度的情况下拉深得更深,所以需要能够从拉伸较少的区域“借用”材料。非均匀加热分布导致了膜必要移动。特别地,在成形期间可在某些范围实现较低的材料流,因此可选择性实现较大的壁厚。
尽管最大变形的范围的识别可回顾性地进行并涉及反复试验,但优选的是,可使用计算机建模***预先识别这些范围。在这种意义上,操作者能够模拟自动洗碗袋的形状和布置,并且计算机建模软件能够预测将变形达最大程度的范围,因此设计对于所期望空腔布置而言最优的非均匀加热分布。
已观察到,如下表1中所示,通过根据该改进方法形成自动洗碗袋100,可制作具有四个空腔的设计:各空腔具有至少11ml、优选地至少12ml、更优选地至少13ml的体积和不小于25微米、优选地不小于30微米的最小壁厚度。
表1-自动洗碗袋比较
从该数据中可看出,与常规的(均匀)加热方法相比,非均匀加热分布制作了具有适当壁厚度和增大容积的袋。因此,这首次使自动洗碗袋能够形成有四个空腔,具有适当的容积和壁厚度。
在实施方式中,适于制作这种自动洗碗袋100的***包括用于接纳待成形的材料片材的工作区域。还提供用于将该片材成形为具有多个空腔12的自动洗碗袋100的模具。最后,提供加热元件并将其布置为向工作区域提供非均匀的加热分布。
在特定实施例中,该***采用组装线的形式。加热装置被布置为与热成形工位相邻,并被配置为接纳待成形的材料片材。加热装置包括两个接触加热装置,可使接触加热装置从相对侧同时与材料片材接触。接触加热装置限定了工作区域。各接触加热装置包括加热回路,该加热回路由在热绝缘支撑件上的陶瓷加热层形成。加热回路按它们在该面上方发出局部不同的加热功率--即跨二维平面的非均匀热分布这样的方式形成在支撑件的面上。
然后,将加热后的该材料层传递到热成形工位。经由真空泵,在布置在材料层下面的模具的空腔中产生真空。结果,加热后的材料层被吸靠在模具的内壁上。例如,经由受压缩的空气供应,可同时在材料层之上施加过压,以便辅助成形过程。在该过程之后,产品在这个模具中冷却,同时保持吸力效应和(如有需要)过压。这使能够在模具内约束下进行冷却。在冷却之后,可从模具中取出自动洗碗袋100。
在替代实施方式中,该***包括诸如圆柱形辊这样的旋转元件,该旋转元件被配置为接纳待成形的材料片材,并被布置为与热成形工位相邻。旋转元件包括加热元件,该加热元件被布置为在片材正被传送到热变形工位时向材料片材提供非均匀加热分布。以这种方式,旋转元件同时起作用,提供工作区域并分配材料片材。然后,将加热后的片材传递到热成形工位。经由真空泵,在布置在材料层下面的模具的空腔中产生真空。结果,加热后的材料层被吸靠在模具的内壁上。例如,经由受压缩的空气供应,可同时在材料层之上施加过压,以便辅助成形过程。在该过程之后,产品在这个模具中冷却,同时保持吸力效应和(如有需要)过压。这使能够在模具内约束下进行冷却。在冷却之后,可从模具中取出自动洗碗袋100。
该实施方式的优点是,减少了组装线所需空间,因为在片材和热成形工位之间不需要加热材料片材的单独工作区域。由于这样的***还消除了在返回到起始位置之前分配材料片材时工作区域的供材料片材行进所需的空间,因此节省的空间量是显著的。***中的移动机器零件的总量和复杂度也降低了。
陶瓷加热回路可应用于陶瓷支撑件。加热回路可由于在加热元件上的分布而产生不均匀的热分布。通过在支撑件上适当布局加热回路的加热线路,可在任何时间实现任何期望的温度分布。
在成形步骤之后,可将一种或更多种自动洗碗组合物引入自动洗碗袋100的空腔12中,以制作最终消费制品。
自动洗碗组合物
优选地,该自动洗碗组合物或每种自动洗碗组合物包括从由助洗剂、漂白剂、漂白活化剂、漂白催化剂、表面活性剂、酶、防腐剂、聚合物和控泡剂组成的组中选择的一种或更多种活性成分。
助洗剂
该自动洗碗组合物或每种自动洗碗组合物可包括一种或更多种助洗剂(或共助洗剂)。助洗剂/共助洗剂可如期望地要么是含磷助洗剂,要么是无磷助洗剂。在许多司法管辖区,磷酸盐助洗剂是被禁止的。因此,优选地,自动洗碗组合物是无磷酸盐的。
如果包含无磷助洗剂,则优选地包含氨基羧酸盐或柠檬酸盐。最优选地,助洗剂选自由甲基甘氨酸二乙酸(MGDA)、N,N-二羧甲基谷氨酸(GLDA)、柠檬酸盐及其诸如MGDA和柠檬酸盐的组合物这样的其两种或更多种的组合物。要理解,术语MGDA、GLDA和柠檬酸盐涵盖游离酸以及它们的盐、酯和衍生物。优选地,柠檬酸盐为柠檬酸三钠。
其他无磷助洗剂包括丁二酸盐类化合物。术语“丁二酸盐类化合物”和“丁二酸类化合物”在本文中可互换使用。
特别合适的助洗剂包括;例如,天冬氨酸-N-单乙酸(ASMA)、天冬氨酸-N,N-二乙酸(ASDA)、天冬氨酸-N-单丙酸(ASMP)、亚氨基二琥珀酸(IDA)、N-(2-磺甲基)天冬氨酸(SMAS)、N-(2-磺乙基)天冬氨酸(SEAS)、N-(2-磺甲基)谷氨酸(SMGL)、N-(2-磺乙基)谷氨酸(SEGL)、N-甲基亚胺基二乙酸(MIDA)、a-丙氨酸-Ν,Ν-二乙酸(a-ALDA)、β-丙氨酸-N,N-二乙酸(β-ALDA)、丝氨酸-N,N-二乙酸(SEDA)、异丝氨酸-N,N-二乙酸(ISDA)、苯丙氨酸-N,N-二乙酸(PHDA)、邻氨基苯甲酸-N,N-二乙酸(ANDA)、磺酸-N,N-二乙酸(SLDA)、牛磺酸-N,N-二乙酸(TUDA)和磺甲基-N,N-二乙酸(SM DA)及其碱金属盐或铵盐。
优选的示例包括亚氨基二琥珀酸。亚氨基二琥珀酸(IDS)和(羟基)亚氨基二琥珀酸(HIDS)及其碱金属盐或铵盐是尤其优选的是琥珀酸基助洗剂盐。无磷共助洗剂也可包括或另选地包括具有一个(多个)羧基的非聚合有机分子。作为含羧基的有机分子的助洗剂化合物包括柠檬酸、富马酸、酒石酸、马来酸、乳酸及其盐。特别地,可使用这些有机化合物的碱或碱土金属盐,尤其是钠盐。尤其优选的无磷助洗剂是柠檬酸钠。这种包括两个羧基的聚羧酸盐包括例如丙二酸、(乙烯二氧基)二乙酸、马来酸、二甘醇酸、酒石酸、酒石酸和富马酸的水溶性盐。这种含有三个羧基的聚羧酸盐包括例如水溶性柠檬酸盐。对应地,合适的羟基羧酸是例如柠檬酸。
优选的辅助助洗剂包括聚羧酸及其部分或完全中和的盐的均聚物和共聚物、单体聚羧酸和羟基羧酸及其盐、磷酸盐和膦酸盐以及这些物质的混合物。以上提到的化合物的优选盐是铵和/或碱金属盐,即,锂、钠和钾盐,特别优选的盐是钠盐。有机的辅助助洗剂是优选的。聚合物聚羧酸是丙烯酸的均聚物。在WO 95/01416中公开了特此明确地引用了其内容的其他合适的辅助助洗剂。最优选地,辅助助洗剂是柠檬酸三钠。
有利的是,1-羟基乙烷1,1-二膦酸(HEDP)和相关的膦酸盐可被用作阈值抑制剂和防垢剂,以防止水垢的形成。
漂白剂、漂白活化剂和漂白催化剂
漂白剂在存在时优选地选自由释放氧的漂白剂、释放氯的漂白剂及其两种或多种的混合物组成的组。更优选地,漂白剂是或包含释放氧的漂白剂。
漂白剂可包括活性漂白剂种类本身或该种类的前体。优选地,漂白剂选自由无机过氧化物、有机过氧化物(诸如,过氧乙酸)、氢过氧化物及其两种或多种的混合物组成的组。术语“无机过氧化物”和“有机过酸”涵盖盐及其衍生物。无机过氧化物包括过碳酸盐、过硼酸盐、过硫酸盐、过氧化氢及其衍生物和盐。这些无机过氧化物的钠盐和钾盐是合适的,尤其是钠盐。过碳酸钠和过硼酸钠是最优选的,尤其是过碳酸钠。
该自动洗碗组合物或每种自动洗碗组合物还可包含一种或更多种漂白剂活化剂和/或漂白剂催化剂。可包括任何合适的漂白剂活化剂,例如,TAED、NOBS和/或DOBS,如果这对于漂白剂的活化是期望的。可使用任何合适的漂白催化剂,但锰类化合物是特别优选的,例如,醋酸锰、草酸锰、TACN锰和/或双核锰络合物,诸如其内容通过引用并入本文中的EP1741774 A1中描述的那些。也可使用钴类化合物,例如,[Co(NH3)5(OAc)]。可在不使用漂白剂或催化剂的情况下使用诸如过苯甲酸和过氧羧酸(例如,邻苯二甲酰亚胺基过氧己酸(PAP))这样的有机过酸,因为这些漂白剂在诸如约30℃这样的相对低温下具有活性。
表面活性剂
表面活性剂也可被包括在自动洗碗产品中,并且可使用任何非离子、阴离子、阳离子、两性或两性离子表面活性剂或其合适的混合物。在本文中通过引用方式并入的KirkOthmer的“Surfactants and Detersive System”(Encyclopedia of ChemicalTechnology,第3版,第22卷,第360-379页)中描述了许多这些合适的表面活性剂。通常,根据本发明,漂白稳定的表面活性剂是优选的。
在自动洗碗产品的情况下,优选的是使阴离子表面活性剂的量最小化。优选地,该产品包含不超过按重量计2%的阴离子表面活性剂,不超过按重量计1%的阴离子表面活性剂,或不含阴离子表面活性剂。优选地,该产品包含不超过按重量计5%的离子表面活性剂,不超过按重量计1%的离子表面活性剂,或不含任何类型的离子表面活性剂。非离子型表面活性剂尤其预选地替代自动洗碗产品。
优选的一类非离子表面活性剂是烷氧基化非离子表面活性剂,它是由含有6至20个碳原子的一羟基烷醇或烷基苯酚反应制备的。优选地,表面活性剂每摩尔醇或烷基酚具有至少12摩尔,特别优选地至少16摩尔,更优选地至少20摩尔(诸如,至少25摩尔)的烯化氧。特别优选的非离子型表面活性剂是非离子型的,它来自具有16-20个碳原子的直链脂肪醇和每摩尔醇至少12摩尔,特别优选地至少16摩尔,更优选地至少20摩尔的烯化氧。
非离子表面活性剂另外可在分子中包括环氧丙烷单元。优选地,这些PO单元占非离子表面活性剂总分子重量的多达按重量计25%,优选地多达按重量计20%,更优选地多达按重量计15%。
可使用乙氧基化的单羟基烷醇或烷基酚的表面活性剂,其另外可包括聚氧乙烯-聚氧丙烯嵌段共聚物单元。这种表面活性剂的醇或烷基酚部分占非离子表面活性剂总分子重量的超过按重量计10%,优选地超过按重量计15%,小于按重量计70%,或按重量计50%。
另一类合适的非离子表面活性剂包括聚氧乙烯和聚氧丙烯的反向嵌段共聚物和三羟甲基丙烷引发的聚氧乙烯和聚氧丙烯嵌段的共聚物。
优选的另一类非离子表面活性剂可由下式描述:
R1O[CH2CH(CH3)O]x[CH2CH2O]y[CH2CH(OH)R2]
式中,R1表示具有4-18个碳原子的直链或支链脂肪族烃基或其混合物,R2表示具有2-26个碳原子的直链或支链脂肪族烃或其混合物,x是介于0.5和1.5之间的值,y是至少15的值。
另一组优选的非离子表面活性剂是下式的封端聚氧烷基化非离子表面活性剂:
R1O[CH2CH(R3)O]x[CH2]kCH(OH)[CH2]jOR2
式中,R1和R2表示具有1-30个碳原子的直链或支链、饱和或不饱和、脂肪族或芳香烃基团,R3表示氢原子或甲基、乙基、正丙基、异丙基、正丁基、2-丁基或2-甲基-2-丁基,x是介于1和30之间的值,k和j是介于1和12之间的值,优选地介于1和5之间的值。当x的值大于2时,上式中的各R3可以是不同的。R1和R2优选地为具有6-22个碳原子的直链或支链、饱和或不饱和、脂肪族或芳香烃基团,其中,具有8至18个碳原子的基团是特别优选的。对于基团R3,H、甲基或乙基是特别优选的。特别优选的x值被包括在1和20之间,优选地在6和15之间。
如上所述,在x>2的情况下,式中的各R3可以是不同的。例如,当x=3时,基团R3可被选定用于构建环氧乙烷(R3=H)或环氧丙烷(R3=甲基)单元,可按每个单个顺序例如(PO)(EO)(EO)、(EO)(PO)(EO)、(EO)(EO)(PO)、(EO)(EO)(EO)、(PO)(EO)(PO)、(PO)(PO)(PO)和(PO)(PO)(PO)来使用这些单元。x的值3只是示例,可选择更大的值,由此将引起更高数量的(EO)或(PO)单元的变化。特别优选的上式的封端聚氧烷基化醇是其中k=1和j=1的简化式的起始分子的那些:
R1O[CH2CH(R3)O]xCH2CH(OH)CH2OR2
另一组优选的非离子表面活性剂是混合烷氧基脂肪醇非离子表面活性剂。
标准的非离子表面活性剂结构是基于具有碳C8-C20链的脂肪醇,其中,脂肪醇已经过乙氧基化或丙氧基化。乙氧基化程度用环氧乙烷单元(EO)的数量描述,丙氧基化程度用环氧丙烷单元(PO)的数量描述。这种表面活性剂还可包含由于脂肪醇丁氧基化而得到的环氧丁烯单元(BO)。优选地,这将是具有PO和EO单元的混合。表面活性剂链可端接有丁基(Bu)部分。
优选地,混合烷氧基脂肪醇非离子表面活性剂包含3至5摩尔的高级烷氧基和6至10摩尔的低级基。特别优选的是具有4或5摩尔的高级烷氧基和7或8摩尔的低级烷氧基的混合烷氧基脂肪醇非离子表面活性剂。根据本发明的一方面,具有4或5个PO摩尔和7或8个EO摩尔的混合烷氧基脂肪醇非离子表面活性剂是尤其优选的,并且对于具有4个PO摩尔和8个EO摩尔的表面活性剂,获得了良好的结果。尤其优选的是混合烷氧基化脂肪醇非离子表面活性剂为C12-15 8EO/4PO(市售为Genapol EP 2584ex Clariant,德国)。
不同非离子表面活性剂的混合物的使用适用于本发明的背景中,例如,烷氧基化醇和含烷氧基化醇的羟基基团的混合物。
在通过引用并入本文中的WO 95/01416中公开了其他合适的表面活性剂。
酶
根据本发明,可使用在洗涤剂组合物中常规使用的任何类型的酶。优选的是,该酶选自蛋白酶、脂肪酶、淀粉酶、纤维素酶和过氧化物酶,其中蛋白酶和淀粉酶是最优选的。最优选的是,蛋白酶和/或淀粉酶被包括在根据本发明的组合物中;这种酶例如在洗碗洗涤剂组合物中是尤其有效的。可按期望使用任何合适种类的这些酶。
防腐蚀剂
防腐蚀剂可提供抗玻璃和/或金属腐蚀的益处,该术语包括旨在防止或减少有色金属特别地银和铜的变色的试剂。
优选的一类抗腐蚀元素是聚亚烷基亚胺,诸如,聚乙烯亚胺;按重量计可被包括0.001%至5%的数量。
已知为了抗腐蚀益处在洗涤剂组合物中包括多价离子的源,特别是在自动洗碗组合物中。例如,多价离子尤其是锌、铋和/或锰离子因其抑制这种腐蚀的能力而被包括在内。WO 94/26860和WO 94/26859中提及了已知适合用作银/铜缓蚀剂的有机和无机氧化还原活性物质。合适的无机氧化还原活性物质例如是从由锌、锰、钛、锆、铪、钒、钴和铈盐和/或络合物组成的组中选择的金属盐和/或金属络合物,该金属是氧化态II、III、IV、V或VI中的一种。特别合适的金属盐和/或金属络合物选自由MnSO4、柠檬酸锰(II)、硬脂酸锰(II)、乙酰丙酮锰(II)、[1-羟乙基-1,1-二膦酸]锰(II)、V2O5、V2O4、VO2、TiOSO4、K2TiF6、K2ZrF6、CoSO4、Co(NO3)2和Ce(NO3)3。可使用任何合适的多价离子源,该离子源优选地选自硫酸盐、碳酸盐、醋酸盐、葡萄糖酸盐和金属蛋白质化合物。锌盐是特别优选的缓蚀剂。
优选的银/铜防腐剂是苯并***(BTA)或双苯并***及其取代衍生物。其他合适的试剂是有机和/或无机氧化还原活性物质和石蜡油。苯并***衍生物是指芳环上的有效取代位部分或完全被取代的化合物。合适的取代基是直链或支链C1-20烷基和羟基、硫代、苯基或诸如氟、氯、溴和碘这样的卤素。优选的取代苯并***是甲苯基***(TTA)。
因此,根据本发明的尤其优选的任选成分是多价离子的源,诸如就在前面段落中提到的那些,特别是包括锌、铋和/或锰离子和/或苯并***(包括取代的苯并***)的化合物。特别地,锌离子源和未取代的苯并***作为防腐蚀剂是优选的,根据本发明,这两种成分的混合物是尤其优选的。
聚合物
用于改善自动洗碗产品的清洁性能的聚合物也可被包括在该自动洗碗组合物中或每种自动洗碗组合物中。例如,可使用磺化聚合物。优选示例包括共聚物CH2=Cr1CR2R3-O-C4h3R4-SO3X,其中,R1、R2、R3、R4独立地为1至6个碳烷基或氢,并且X是具有任何合适的其他单体单元的氢或碱,该单体单元包括改性丙烯酸、富马酸、马来酸、衣康酸、乌头酸、中康酸、柠康酸和亚甲基丙二酸或它们的盐、马来酸酐、丙烯酰胺、亚烷基、乙烯基甲基醚、苯乙烯及其任何混合物。其他适合的引入磺化(共)聚合物中的磺化单体有2-丙烯酰胺-2-甲基-1-丙磺酸、2-甲基丙烯酰胺-2-甲基-1-丙磺酸、3-甲基丙烯酰胺-2-羟基-丙磺酸、烯丙磺酸、甲基磺酸、2-羟基-3-(2-丙烯氧基)丙磺酸、2-甲基-2-丙烯-1-磺酸、苯乙烯磺酸、乙烯磺酸、3-丙烯酸磺丙酯、3-甲基丙烯酸磺丙酯、磺甲基丙烯酰胺、磺甲基甲基丙烯酸酰胺及其水溶性盐。在通过引用并入本文中的US 5308532和WO 2005/090541中也描述了合适的磺化聚合物。
特别优选的是丙烯酸的均聚物和/或丙烯酸与马来酸的共聚物和/或丙烯酸与含硫单体的共聚物。
控泡剂
该自动洗碗组合物或每种自动洗碗组合物还可包括一种或更多种控泡剂。适用于此目的的控泡剂是该领域中常规使用的所有那些,诸如,例如,硅氧烷及其衍生物和石蜡油。
该自动洗碗组合物或每种自动洗碗组合物还可包括少量的常规量的防腐剂、芳香剂等。
该自动洗碗组合物或每种自动洗碗组合物可以是粉末、颗粒、液体、凝胶或膏体的形式。例如,当自动洗碗组合物被引入四个空腔中时,一种自动洗碗组合物可以是粉末或颗粒的形式,而其余三种自动洗碗组合物是液体、凝胶、膏体或其组合的形式。在一些实施方式中,所有四种自动洗碗组合物可以是凝胶形式。当自动洗碗组合物被引入不止一个空腔中时,每种自动洗碗组合物可以是相同的或不同的。
本发明由权利要求书来限定。
Claims (19)
1.一种形成自动洗碗袋的方法,所述方法包括以下步骤:
提供材料的片材;
识别所述材料的一个或更多个范围;
用具有非均匀加热分布的加热装置加热所述材料,所述非均匀加热分布被布置为将所识别的范围加热至比所述材料的其他范围高的温度;以及
在模具中对所述材料进行成形以形成所述自动洗碗袋,所述自动洗碗袋包括多个空腔;
其中,使用计算机建模***预先识别所述范围,
其中,操作者能够模拟自动洗碗袋的形状和布置,并且计算机建模软件能够预测将变形达最大程度的范围,因此设计对于所期望空腔布置而言最优的非均匀加热分布。
2.根据权利要求1所述的方法,其中,在所述模具中对所述材料进行成形,使得所述自动洗碗袋包括两个或更多个空腔。
3.根据权利要求1或2所述的方法,其中,所识别的范围超过2.0的应变值极限。
4.根据前述权利要求1或2所述的方法,其中,所述材料的所识别范围对应于所述空腔的壁和/或基底。
5.根据权利要求4所述的方法,其中,所述空腔的所述壁被加热至比所述空腔的所述基底高的温度。
6.根据前述权利要求1或2所述的方法,其中,所形成的所述自动洗碗袋的最小厚度不小于30μm。
7.根据前述权利要求1或2所述的方法,其中,所述空腔限定至少11ml的累积体积。
8.根据前述权利要求1或2所述的方法,其中,所述材料是聚乙烯醇。
9.根据前述权利要求1或2所述的方法,其中,所述材料的片材具有小于或等于60mm×50mm的占地面积。
10.根据前述权利要求1或2所述的方法,其中,所述成形的步骤包括真空成形。
11.根据前述权利要求1或2所述的方法,该方法还包括将自动洗碗组合物引入所述空腔中的一个或更多个中的步骤。
12.根据权利要求2所述的方法,其中,所述自动洗碗袋包括三个或更多个空腔。
13.根据权利要求12所述的方法,其中,所述自动洗碗袋包括四个或更多个空腔。
14.根据前述权利要求7所述的方法,其中,所述空腔限定至少12ml的累积体积。
15.根据前述权利要求14所述的方法,其中,所述空腔限定至少13ml的累积体积。
16.根据前述权利要求15所述的方法,其中,所述空腔限定至少15ml的累积体积。
17.一种配置为使用权利要求1至16中任一项所述的方法形成自动洗碗袋的真空成型***,所述真空成型***包括:
工作区域,其用于接纳待成形的材料的片材;
模具,其用于将所述材料的片材成形为具有多个空腔的自动洗碗袋;以及
加热元件,其被布置为向所述工作区域提供非均匀的加热分布。
18.一种配置为使用权利要求1至16中任一项所述的方法形成自动洗碗袋的真空成型***,所述真空成型***包括:
旋转元件,其被配置为接纳待成形的材料的片材,其中,所述旋转元件包括加热元件,所述加热元件被布置为向所述材料的片材提供非均匀的加热分布;以及
模具,其用于将所述材料的片材成形为具有多个空腔的自动洗碗袋。
19.根据权利要求17或18所述的真空成型***,该真空成型***还包括用于将一种或更多种洗碗组合物引入所述空腔中的一个或更多个中的一个或更多个配给装置。
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- 2020-01-17 AU AU2020210492A patent/AU2020210492A1/en active Pending
- 2020-01-17 EP EP20701289.9A patent/EP3914435A1/en active Pending
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EP3914435A1 (en) | 2021-12-01 |
CN113316509A (zh) | 2021-08-27 |
WO2020152044A1 (en) | 2020-07-30 |
AU2020210492A1 (en) | 2021-08-05 |
US20220081656A1 (en) | 2022-03-17 |
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