CN105198277A - 制造石颗粒和聚酯树脂的聚结体的板或块的方法 - Google Patents
制造石颗粒和聚酯树脂的聚结体的板或块的方法 Download PDFInfo
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- CN105198277A CN105198277A CN201510508098.6A CN201510508098A CN105198277A CN 105198277 A CN105198277 A CN 105198277A CN 201510508098 A CN201510508098 A CN 201510508098A CN 105198277 A CN105198277 A CN 105198277A
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- conglomerate
- vibrin
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- acid anhydride
- triglyceride level
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Classifications
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- C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
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- C—CHEMISTRY; METALLURGY
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
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- B29C67/243—Moulding mineral aggregates bonded with resin, e.g. resin concrete for making articles of definite length
- B29C67/244—Moulding mineral aggregates bonded with resin, e.g. resin concrete for making articles of definite length by vibrating the composition before or during moulding
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- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
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- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
- B29C70/44—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using isostatic pressure, e.g. pressure difference-moulding, vacuum bag-moulding, autoclave-moulding or expanding rubber-moulding
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
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- C04B26/10—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B26/18—Polyesters; Polycarbonates
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- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/18—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mixtures of the silica-lime type
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0067—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability making use of vibrations
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
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- C04B40/0089—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability making use of vacuum or reduced pressure
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/02—Selection of the hardening environment
- C04B40/0263—Hardening promoted by a rise in temperature
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/02—Selection of the hardening environment
- C04B40/0272—Hardening under vacuum or reduced pressure
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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
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- B29C2791/004—Shaping under special conditions
- B29C2791/006—Using vacuum
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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
- B29C2791/00—Shaping characteristics in general
- B29C2791/004—Shaping under special conditions
- B29C2791/008—Using vibrations during moulding
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- B—PERFORMING OPERATIONS; TRANSPORTING
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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
- B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
- B29K2033/04—Polymers of esters
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- C04B20/0076—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials characterised by the grain distribution
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Abstract
本发明涉及制造石颗粒和聚酯树脂的聚结体的板或块的方法，具体地涉及制造板状或块状砾岩制品的方法，其中制备初始混合物，该初始混合物由具有选择的粒度的任何石或石类颗粒材料以及形成可硬化树脂的粘合剂构成，将该混合物沉积在具有最终制品尺寸的临时载体上或模具中，进行真空压制步骤，并以预设频率施加振动，然后进行所述粘合剂树脂的硬化步骤，其特征在于使用不含反应性溶剂、并且能够通过至少一种环氧化的甘油三酯与至少一种羧酸酐之间的反应形成的聚酯树脂作为粘合剂，所述初始混合物是通过将所述颗粒与形成所述聚酯树脂的组分混合而制备。
Description
本申请是申请号为200780019907.0、申请日为2007年5月23日、发明名称为“制造石颗粒和聚酯树脂的聚结体的板或块的方法”的专利申请的分案申请。
技术领域
本发明涉及聚结体制品的制造，更具体涉及以包含粒状石材等和树脂基粘合剂的混合物为原料制造板和块的方法。
背景技术
前述类型的块状和板状制品的制造方法多年来已为人所知，并已知其通用名为Bretonstone技术，在该技术中，制备初始混合物，该初始混合物由具有所选粒度的粒状石材或者无机或有机石类材料、以及可硬化树脂基粘合剂构成。
将该混合物沉积在临时载体上或具有最终制品尺寸的模具中，并进行真空压制步骤，同时以预设频率施加的振动。
然后将所得粗制品转移到硬化步骤中，在该步骤的最后，其具有所需机械特性。
然后将可由块状物锯得的板送往精加工(上胶、平滑化、抛光等)。
关于Bretonstone技术的更多信息和技术细节，应该考查以MarcelloToncelli的名义提交的欧洲专利786325和相同申请人提交的国际专利申请PCT/EP2006/062120，两者均经此引用并入本文。
在根据Bretonstone技术制造基于石或石类颗粒的聚结产品时，可以使用结构型树脂。这些包括聚酯树脂、丙烯酸类树脂、环氧树脂等。
在Bretonstone技术中使用这些树脂，可以获得具有显著的特有规格的优质产品。
最普遍的产品是包含用反应性合成单体(例如苯乙烯)稀释的邻苯二甲酸基聚酯树脂的聚结体。
要注意的是，聚酯树脂是衍生自油的合成产品，其问题是公知的。
此外，苯乙烯单体作为反应性溶剂存在于聚酯树脂中并因此存在于该混合物中，造成了数个不同的环境问题，这些问题与其有害性质和由高挥发性引起的爆炸危险相关；实际上，必须使用复杂昂贵的设备收集和除去苯乙烯蒸气，以符合日益严格的排放法规。
迄今未解决的另一问题在于，当暴露在紫外线中时，(由含溶剂的聚酯树脂获得的)制品相当明显地变黄。显然，这种长期问题，尤其是对用作建筑物外覆物的制品而言，影响了制品的美观特性。
发明内容
因此，本发明的目的是根据Bretonstone技术制造制品，其中保持了使用前述粘合剂树脂可获得的机械和美观特性，同时克服了上述问题；特别消除了混合物中苯乙烯的存在。
使用前述类型的方法实现了该目的，该方法的特征在于，在最终制品中，粘合剂树脂是不含反应性溶剂、并通过至少一种环氧化的甘油三酯与至少一种羧酸酐之间的反应形成的聚酯树脂。
因此，这是首次用在Bretonstone技术领域中的一种聚酯树脂类型，其中至少50重量％获自可再生来源、特别是植物来源的原材料，例如环氧化的甘油三酯，和获自至少一种羧酸酐。
关于本发明中所用的聚酯树脂的详细信息，可以参看公开的德国专利申请DE10148672A1。
具体实施方式
关于该第一上述组分，几个进一步规定是适当的。
天然产品，尤其是植物来源的那些，含有大量被甘油酯化的脂肪酸以形成甘油三酯，其可以通过已知技术提取。
在性质上，脂肪酸几乎从不自由存在，而是与醇、甘油结合。甘油可以结合1至3个脂肪酸：因此存在脂肪酸的甘油单酯、甘油二酯和甘油三酯。
脂肪酸由键合到氢原子上的碳原子链构成，该链通常具有含有氧(O)或氢和氧(OH)的端键。
脂肪酸被分成短链脂肪酸(4至8个碳原子)、中链脂肪酸(8至14个碳原子)和长链碳原子(14至24个碳原子)，以及被分成饱和脂肪、单不饱和脂肪和多不饱和脂肪。
后一种细分非常重要，因为脂肪酸根据不饱和度具有不同的物理和化学性质。
如果甘油三酯主要由饱和脂肪酸(棕榈酸和硬脂酸)或单不饱和酸(油酸)构成，这些化合物在室温下是固体，并且被称作“脂肪”，且特别为动物来源(猪油、牛油)。
如果甘油三酯主要由不饱和脂肪酸构成，例如单不饱和(棕榈油酸、油酸、顺式-9二十碳烯酸)或多不饱和酸(亚油酸、亚麻酸)，这些化合物在室温下是液体并且被称作“油”，且特别为植物来源(橄榄籽油、亚麻籽油、大豆油、玉米油)。
饱和脂肪酸具有线型空间构造，这使得它们可以以有序方式排列：这种排列促进分子相互作用(氢桥)，因此，它们具有高熔点。
单不饱和和多不饱和脂肪酸由于造成静电失衡的双键，没有线型分子，而是弯曲的分子，因此，由于它们自身不能以有序方式排列，分子间的键较少，因此熔融温度较低。双键的数越大，熔融温度越低。
为了用在本发明中，如下列示意图所示，这些油经过所存在的双键的环氧化反应(本身公知的反应)：
[Trigliceridediacidigrassipolinsaturi＝多不饱和脂肪酸的甘油三酯；AcidoFormico＝甲酸；Trigliceridediacidigrassiepossidati＝环氧化脂肪酸的甘油三酯]
对于酸酐组分，这些酸酐的化学性质(脂族或芳族)影响操作参数，并因此也影响所得树脂的最终特性。例如，下面列出两种酸酐的化学式，即脂族酸酐或饱和二羧酸的酸酐、和获自不饱和二羧酸的芳族酸酐：
[AnidrideAlifatica＝脂族；AnidrideAromatica＝芳族酸酐]
为了本发明的目的，可以使用下列酸酐(作为非限制性实例指出)：苯均四酸酐、马来酸酐、琥珀酸酐、六氢邻苯二甲酸酐、邻苯二甲酸酐、降冰片烯二甲酸酐、己二酐、戊二酐、甲基邻苯二甲酸酐、1,2-环己烷二甲酸酐、3-甲基-1,2-环己烷二甲酸酐、4-甲基-1,2-环己烷二甲酸酐、3-甲基-1,2-环己烷二甲酸酐和4-甲基-1,2-环己烷二甲酸酐的混合物、甲基-四氢邻苯二甲酸酐、四氢邻苯二甲酸酐、甲基-5-降冰片烯-2,3-二甲酸酐、十二烷基-琥珀酸酐及其混合物。
环氧化脂肪酸与一种或多种酸酐的混合物在引发剂存在下和根据所用添加剂在80-180℃的温度下固化和硬化。
反应图如下所示：
[Iniziatore＝引发剂；Calore＝热；ResinaIndurita＝硬化树脂]
如反应图中所示，在形成树脂的方法中，需要存在催化剂引发剂，其根据性质和量通过降低反应时间和工艺温度来发挥作用。
下面可以列出可能的引发剂：碱金属的卤化物，铝、锌和锡的有机金属化合物，季铵的卤化物，脂族和芳族胺，硼和钛基络合物。
含硅质或钙质粒子的树脂的硬化产生了聚结产品，从化学和物理角度看，其特性都与使用溶解在反应性合成单体中的聚酯树脂获得的那些相当。
在本发明的优选实施方案中，由于环氧化的油几乎完全饱和，优选使用脂族酸酐，因为所得聚酯树脂特别可抵抗由紫外线引起的变黄。
在本发明的优点中，必须强调使用可大量获自天然来源的原材料——天然脂肪酸的甘油三酯，因此从经济角度看，本发明的方法也是有利的。
下列非限制性实例例示了本发明的方法：
根据Bretonstone技术制造按体积计具有下列组成的板：
■树脂:19％
■325目石英填料:23％
■0.1至1.2毫米石英颗粒:58％
树脂的按重量计的组成为:
将板在炉中在140℃处理40分钟。冷却后，确定了下列物理特性：
■弯曲强度：59N/mm2
■深磨损耐受性：225mm3
■UV处理500小时：不变黄
要指出的是，这些机械特性相当于由含有苯乙烯的传统合成聚酯树脂制成的类似制品。
此外，与由含有苯乙烯的传统合成聚酯树脂制成的类似制品不同，该制品在紫外线下暴露500小时不会变黄。
应该指出的是，Bretonstone技术也能够制造块状制品，然后像从采石场中开采的正常天然石块那样送往锯切和精加工操作。本发明，如所附权利要求中定义的，同样适用于这类块状物的制造。
Claims (6)
1.制造板状或块状砾岩制品的方法，其中制备初始混合物，该初始混合物由具有选择的粒度的任何石或石类颗粒材料以及形成可硬化树脂的粘合剂构成，将该混合物沉积在具有最终制品尺寸的临时载体上或模具中，进行真空压制步骤，并以预设频率施加振动，然后进行所述粘合剂树脂的硬化步骤，其特征在于使用不含反应性溶剂、并且能够通过至少一种环氧化的甘油三酯与至少一种羧酸酐之间的反应形成的聚酯树脂作为粘合剂，所述初始混合物是通过将所述颗粒与形成所述聚酯树脂的组分混合而制备的，形成所述聚酯树脂的组分包含至少一种环氧化的甘油三酯和至少一种羧酸酐，所述至少一种羧酸酐选自4-甲基-1,2-环己烷二甲酸酐、3-甲基-1,2-环己烷二甲酸酐、4-甲基-1,2-环己烷二甲酸酐和3-甲基-1,2-环己烷二甲酸酐的混合物、甲基-四氢邻苯二甲酸酐、四氢邻苯二甲酸酐、以及甲基-四氢邻苯二甲酸酐和四氢邻苯二甲酸酐的混合物，且特征在于所述形成聚酯树脂的反应和硬化步骤在80-180℃的温度范围进行。
2.根据权利要求1的制造板状或块状砾岩制品的方法，其特征在于所述环氧化的甘油三酯选自在室温下是液体的单不饱和或多不饱和的不饱和脂肪酸的甘油三酯。
3.根据权利要求1的制造板状或块状砾岩制品的方法，其特征在于将催化剂引发剂添加到环氧化的甘油三酯和酸酐的混合物中。
4.根据权利要求3的制造板状或块状砾岩制品的方法，其特征在于所述催化剂引发剂选自碱金属的卤化物，铝、锌和锡的有机金属化合物，季铵的卤化物，脂族和芳族胺，硼和钛基络合物。
5.根据权利要求1的制造板状或块状砾岩制品的方法，其特征在于所述形成聚酯树脂的反应和硬化在140℃的温度进行。
6.可通过各个前述权利要求的方法获得的板状或块状砾岩制品，其特征在于所述粘合剂是通过至少一种环氧化的甘油三酯与至少一种羧酸酐在催化剂引发剂存在下和在80-180℃的温度范围的反应获得的聚酯树脂。
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| BE632074A (zh) | 1962-05-11 | |||
| GB1368468A (en) | 1971-05-10 | 1974-09-25 | Celmac Ag | Polyester compositions for use as mortars |
| DE3273103D1 (en) | 1981-04-03 | 1986-10-16 | Shell Int Research | Polymer concrete compositions and their use in preparing articles |
| DE3332080A1 (de) | 1983-09-06 | 1985-03-21 | Dow Chemical (Europe) S.A., Horgen | Verfahren, zusammensetzung und vorrichtung zum fuellen von schweissgurt-zementaussparungen bei mit zement umhuellten rohren |
| US4611015A (en) | 1984-12-13 | 1986-09-09 | The Dow Chemical Company | Polymer concrete compositions containing water absorbent polymers |
| EP0463866A3 (en) * | 1990-06-27 | 1993-04-28 | Mitsubishi Kasei Corporation | A fiber-reinforced resin composition |
| DE4410785A1 (de) * | 1994-03-28 | 1995-10-05 | Hoechst Ag | Amin-modifizierte Epoxidharz-Zusammensetzung |
| US20010023276A1 (en) * | 1995-07-05 | 2001-09-20 | Uwe Schoenfeld | Polymeric material, method for its manufacture, and its utilization |
| IT1288566B1 (it) | 1996-01-29 | 1998-09-23 | Marcello Toncelli | Procedimento ed impianto per la produzione di lastre di granulati e/o sabbie di materiale lapideo legato con una resina induribile |
| US6218701B1 (en) * | 1999-04-30 | 2001-04-17 | Intersil Corporation | Power MOS device with increased channel width and process for forming same |
| DE10148672A1 (de) | 2001-10-02 | 2003-04-24 | Cognis Deutschland Gmbh | Polyester |
| ITTV20020080A1 (it) | 2002-07-09 | 2004-01-09 | Luca Toncelli | Struttura di macchina mescolatrice resistente all'abrasione |
| ITTV20030134A1 (it) * | 2003-09-29 | 2005-03-30 | Dario Toncelli | Procedimento per la realizzazione di manufatti in lastra o pannello a due strati, e manufatti in lastre o pannelli con esso ottenibili. |
| ITTV20040057A1 (it) | 2004-05-18 | 2004-08-18 | Luca Toncelli | Procedimento per realizzare un manufatto leggero di materiale conglomerato e relativo pannello composito. |
| ITTV20050068A1 (it) | 2005-05-19 | 2006-11-20 | Luca Toncelli | Procedimento ed impianto per la fabbricazione di blocchi di conglomerato in materiale lapideo o ceramico. |
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2006
- 2006-05-31 IT IT000092A patent/ITTV20060092A1/it unknown
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- 2007-05-23 TR TR2019/00876T patent/TR201900876T4/tr unknown
- 2007-05-23 CA CA2652760A patent/CA2652760C/en active Active
- 2007-05-23 EP EP07735998.2A patent/EP2027077B1/en active Active
- 2007-05-23 KR KR1020087028344A patent/KR101333470B1/ko active IP Right Grant
- 2007-05-23 RU RU2008152375/05A patent/RU2440386C2/ru active
- 2007-05-23 US US12/300,907 patent/US9199415B2/en not_active Expired - Fee Related
- 2007-05-23 PT PT07735998T patent/PT2027077T/pt unknown
- 2007-05-23 ES ES07735998T patent/ES2710664T3/es active Active
- 2007-05-23 CN CN201510508098.6A patent/CN105198277A/zh active Pending
- 2007-05-23 CN CNA2007800199070A patent/CN101454258A/zh active Pending
- 2007-05-23 AU AU2007266666A patent/AU2007266666B2/en not_active Ceased
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| US4293681A (en) * | 1980-02-21 | 1981-10-06 | Buffalo Color Corporation | Liquid anhydride blends |
| US5264168A (en) * | 1989-01-13 | 1993-11-23 | Marcello Toncelli | Plate product of ceramic material and process for the manufacturing thereof |
| US5728790A (en) * | 1994-08-11 | 1998-03-17 | Mitsui Toatsu Chemicals, Inc | Thermosetting powder paint, coating method using said paint, and article coated with said paint |
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| CN108882780A (zh) * | 2016-03-31 | 2018-11-23 | Ykk株式会社 | 聚酯制拉链 |
Also Published As
| Publication number | Publication date |
|---|---|
| TR201900876T4 (tr) | 2019-02-21 |
| WO2007138529A2 (en) | 2007-12-06 |
| ITTV20060092A1 (it) | 2007-12-01 |
| IL195286A (en) | 2013-11-28 |
| RU2008152375A (ru) | 2010-07-10 |
| US20090253829A1 (en) | 2009-10-08 |
| AU2007266666B2 (en) | 2012-08-30 |
| US20160002109A1 (en) | 2016-01-07 |
| BRPI0712798A2 (pt) | 2012-10-02 |
| PT2027077T (pt) | 2019-02-06 |
| CA2652760A1 (en) | 2007-12-06 |
| KR101333470B1 (ko) | 2013-11-26 |
| EP2027077B1 (en) | 2018-11-14 |
| EP2027077A2 (en) | 2009-02-25 |
| KR20090013787A (ko) | 2009-02-05 |
| RU2440386C2 (ru) | 2012-01-20 |
| US9199415B2 (en) | 2015-12-01 |
| CN101454258A (zh) | 2009-06-10 |
| AU2007266666A1 (en) | 2007-12-06 |
| ES2710664T3 (es) | 2019-04-26 |
| IL195286A0 (en) | 2009-08-03 |
| CA2652760C (en) | 2015-10-20 |
| WO2007138529A3 (en) | 2008-02-14 |
| BRPI0712798B1 (pt) | 2018-06-19 |
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