CN1196075A - 表面改性的碳酸钙组合物和其用途 - Google Patents
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/675—Oxides, hydroxides or carbonates
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/021—Calcium carbonates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/021—Calcium carbonates
- C09C1/022—Treatment with inorganic compounds
- C09C1/024—Coating
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/90—Other properties not specified above
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Abstract
一种改进的可以作为填料在制备中性至弱酸性纸中使用的耐酸碳酸钙,和一种制备这种耐酸碳酸钙的方法。该耐酸性的碳酸钙包括一种碳酸钙和以碳酸钙的干重计至少约0.5～10%的阳离子盐以及以碳酸钙的干重计至少约0.5～10%的阴离子盐。
Description
总的来说本发明涉及在造纸和相关工业中使用的碳酸钙，更确切地说，涉及一种具有耐酸性能的碳酸钙。
通常在中性和弱酸性纸的制备中使用二氧化钛和煅烧的粘土作为填料以提高所得到的制品的光学性能特别是亮度。然而，这些材料特别是二氧化钛的缺陷是非常昂贵，从而导致较高的生产成本和纸制品在价格上无竞争性。
碳酸钙，特别是沉淀碳酸钙在碱性纸的制备中作为填料。这种用法导致纸的光学性能的提高，而无使用二氧化钛填料所引起的花费，产生一种花费更低的产品。然而，通常碳酸钠不能作为填料在酸性纸中使用，因为在酸性环境下碳酸钙分解。结果，长期以来一直需要研制一种碳酸钙组合物，其具有酸性稳定性和在低pH值下具有抗分解性，这样它可以在酸性纸例如细磨木浆纸的制备中作为填料使用，这里碱性填料的使用将对最终纸的性能产生副作用。
U.S.专利5,043,017公开和要求一种酸性稳定的能够在适度的酸性环境下抗分解的碳酸钙，其包括钙螯合剂或共轭碱和弱酸的混合物，这样碳酸钙被钙螯合剂或共轭碱和弱酸涂覆并与它们相平衡。优选所述碳酸钙组合物包含六偏磷酸钠和磷酸。
U.S.专利5,164,006公开和要求一种耐酸性的碳酸钙，其是这样制备的，即制备一种碳酸钙的含水浆体，加热该浆体至约75～80℃，缓慢地加入约5～10重量％的硅酸钠溶液，加入气态的二氧化碳，冷却该浆体，并在该浆体中加入氯化锌使pH值在约7.5～8.0的范围中。
本发明的目的是提供一种特别适合于在造纸中使用的耐酸碳酸钙组合物。
本发明的目的还在于提供一种制备上述碳酸钙组合物的方法。
本发明的又一目的是提供一种使用本发明的碳酸钙制备的改进了光学性能的纸。
本发明涉及一种改进的可以作为填料在制备中性至弱酸性纸中使用的耐酸性碳酸钙，和涉及一种制备这种耐酸性碳酸钙的方法。更精确地说，本发明涉及一种耐酸性的碳酸钙，其包括一种碳酸钙和以碳酸钙的干重计至少约0.5～10％的阳离子盐以及以碳酸钙的干重计至少约0.5～10％的阴离子盐。已经令人惊奇地发现，与未处理的碳酸钙组合物相比，在纤维浆体的存在下，包括阳离子盐和阴离子盐这二者的碳酸钙使碳酸钙具有较高程度的耐酸性和长期的低pH值的稳定性。
附图1表示使用各种不同浓度的六偏磷酸钠和硫酸铝制备的本发明磨细碳酸钙组合物的24小时老化曲线。
附图2表示使用各种不同浓度的六偏磷酸钠和氯化铝制备的磨细碳酸钙的24小时老化曲线。
附图3表示使用各种不同浓度的六偏磷酸钠和氯化铝制备的磨细碳酸钙的老化。
附图4表示使用聚丙烯酸钠和各种不同浓度的聚氯化铝制备的偏三角面体的沉淀碳酸钙的老化。
通过本发明制备的改进的碳酸钙形式是耐酸性的，可以作为填料在中性～弱酸性纸的制备中使用。因为就本发明的可操作性而论不希望受任何特殊的理论的束缚，所以认为赋予本发明的耐酸性是通过加入弱碱和弱酸导致碳酸钙的表面无活性的结果。
在本发明的实施中，碳酸钙组合物是通过包含以碳酸钙的干重计至少约0.5～约10％的阳离子盐和以碳酸钙的干重计至少约0.5～约10％的阴离子盐而具有耐酸性的。
在本发明的组合物中使用的阳离子盐一般是一种铝盐。所包括的铝盐是硫酸铝铵、硫酸铝钾、硫酸铬钾、氯化铝、聚氯化铝和硫酸铬铵。优选地，使用硫酸铝、氯化铝和聚氯化铝作为阳离子盐。
以碳酸钙的干重计阳离子盐的使用量是至少0.5～约10％，优选是以碳酸钙的干重计约2～约7％。
在本发明的组合物中使用的阴离子盐是弱碱盐，例如六偏磷酸盐、有机聚合酸盐、乙酸盐、草酸盐、磷酸盐、偏磷酸盐、柠檬酸盐、硼酸盐、亚硫酸盐、乙二胺四乙酸(EDTA)盐、聚马来酸盐、聚羧酸盐和它们的混合物。优选的阴离子盐是六偏磷酸钠、聚丙烯酸钠和聚马来酸钠。
以碳酸钙的干重计阴离子盐的使用量是至少0.5～约10％，优选是以碳酸钙的干重计约2～约7％。
所使用的碳酸钙优选是磨细的，并且可以是一种沉淀碳酸钙或一种天然的磨细石灰石。
与上述US专利5164006中描述的工序相比，制备这种耐酸碳酸钙的工序是非常简单的，其包括首先制成一种碳酸钙和以碳酸钙的干重计至少约0.5～10％的阴离子盐的混合物以供使用。然后，在这种所得到的混合物中加入以碳酸钙的干重计至少约0.5～10％的所希望的阳离子盐。最后，将所得到混合物混合足够长的时间以确保均匀地混合组分。
在上述工序中可以使用的碳酸钙或者是一种干粉末或者是一种固体含量达约60重量％的含水浆体。
在该工序中使用的阳离子盐或者是一种干燥的固体或一种含水溶液。当以干燥粉末的形式使用碳酸钙时，优选使用一种弱碱的含水溶液以便便于均匀地进行混合。在使用碳酸钙的浆体的地方，固体阳离子盐易于溶解在其中，这样含水溶液是不需要的。
在制备过程中可以以纯的浓缩形式或作为含水溶液使用阴离子盐。
可以使用本发明的组合物即在标准的制备过程期间将本发明的组合物加入中性至弱酸性纸中以改进该纸的光学性能。通常，将本发明的碳酸钙组合物加入含制备酸性纸所需的组分的纸的第一配料中并因此制成纸的第二配料。
通过下面的被认为是对本发明进行说明的实施例进一步描述本发明，并且本发明并不限于所示的确切的实施方案。实施例1
磨细碳酸钙组合物
通过加入一种阴离子盐例如六偏磷酸钠和一种阳离子盐例如硫酸铝可以得到耐酸性的磨细碳酸钙浆体。最初，在初始pH值为8.01的磨细碳酸钙浆体中加入以碳酸钙的干重计1～5％的六偏磷酸钠。在混合之后，加入以碳酸钙的干重计1～7％的硫酸铝。在老化24小时之后测量每种试样的pH值曲线图，结果显示在附图1所示的曲线图中。从附图1可以看出，连接圆形点的线表明由1％六偏磷酸钠和3％硫酸铝(以碳酸钙的干重计)制备的碳酸钙浆体产生的产品在24小时老化之后的pH值是6.24。
实施例2
磨细碳酸钙组合物
通过电中性涂料与氯化铝和六偏磷酸钠同样可以得到耐酸性的磨细碳酸钙浆体。磨细碳酸钙浆体的pH值为8.01。在开始时，加入以碳酸钙的干重计1％、3％和5％的六偏磷酸钠，随后加入以碳酸钙的干重计5％的氯化铝。在老化24小时之后测量每种试样的pH值曲线图，结果显示在附图2或3中。从结果可以看出，以碳酸钙的干重计加入2％六偏磷酸钠。在混合之后，以碳酸钙的干重计加入5％氯化铝。起初磨细碳酸钙浆体的pH值是5.70，在24小时老化之后的得到稳定的pH值5.85。
实施例3
磨细碳酸钙组合物
磨细碳酸钙浆体的pH值为8.01。首先，加入以碳酸钙的干重计3％的聚丙烯酸钠，随后加入以碳酸钙的干重计5％的聚氯化铝。起初磨细碳酸钙浆体的pH值是6.12，在116小时老化之后的得到稳定的pH值6.60。
实施例4
偏三角面体的沉淀碳酸钙组合物
通过电中性涂料与氯化铝和聚丙烯酸钠同样可以得到耐酸性的偏三角面体的沉淀碳酸钙浆体。偏三角面体碳酸钙浆体的pH值为9.05。在开始时，加入以碳酸钙的干重计1％的聚丙烯酸钠，随后加入以碳酸钙的干重计2％、4％和6％的聚氯化铝。在老化24小时之后测量每种试样的pH值曲线图，结果显示在附图4中。从结果可以看出，在使用以碳酸钙的干重计1％聚丙烯酸钠/6％聚氯化铝处理的情况下，偏三角面体的沉淀碳酸钙浆体的pH值是6.02，并且浆体在68小时老化之后的最终pH值是6.44。
实施例5
菱形沉淀碳酸钙组合物
通过加入一种阴离子盐例如聚丙烯酸钠和一种阳离子盐例如硫酸铝可以得到耐酸性的菱形沉淀碳酸钙浆体。最初，在初始pH值为8.09的菱形沉淀碳酸钙浆体中加入以碳酸钙的干重计2％的聚丙烯酸钠。在混合之后，加入以碳酸钙的干重计4％的硫酸铝。起初该组合物的pH值是6.41，在24小时老化之后的pH值是6.59。
Claims (9)
1、一种耐酸碳酸钙，其包括一种碳酸钙和以碳酸钙的干重计至少约0.5～10％的阳离子盐以及以碳酸钙的干重计至少约0.5～10％的阴离子盐。
2、根据权利要求1的耐酸碳酸钙，其中阳离子盐是硫酸铝、硫酸铝铵、硫酸铝钾、硫酸铬钾、氯化铝、聚氯化铝和硫酸铬铵。
3、根据权利要求2的耐酸碳酸钙，其中阳离子盐是硫酸铝。
4、根据权利要求1的耐酸碳酸钙，其中阴离子盐是一种选自由六偏磷酸盐、硼酸盐、亚硫酸盐和它们的混合物组成的组中的弱碱盐。
5、根据权利要求1的耐酸碳酸钙，其中阴离子盐是六偏磷酸钠。
6、根据权利要求1的耐酸碳酸钠，其中以碳酸钙的干重计阳离子盐的使用量是约2～约7％。
7、根据权利要求1的耐酸碳酸钠，其中以碳酸钙的干重计阴离子盐的使用量是约1～约5％。
8、通过加入权利要求1的碳酸钙组合物以改进中性至弱酸性纸的光学性能的方法。
9、一种中性至酸性纸，其包含权利要求1的碳酸钙组合物。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/518,757 | 1995-08-24 | ||
| US08/518,757 US5531821A (en) | 1995-08-24 | 1995-08-24 | Surface modified calcium carbonate composition and uses therefor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1196075A true CN1196075A (zh) | 1998-10-14 |
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ID=24065372
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96196995.4A Pending CN1196075A (zh) | 1995-08-24 | 1996-08-23 | 表面改性的碳酸钙组合物和其用途 |
Country Status (8)
| Country | Link |
|---|---|
| US (2) | US5531821A (zh) |
| EP (1) | EP0871680A4 (zh) |
| JP (1) | JPH11512067A (zh) |
| CN (1) | CN1196075A (zh) |
| AR (1) | AR003357A1 (zh) |
| AU (1) | AU701251B2 (zh) |
| CA (1) | CA2230054A1 (zh) |
| WO (1) | WO1997008248A1 (zh) |
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| US4115187A (en) * | 1970-03-31 | 1978-09-19 | Welwyn Hall Research Association | Agglomerated fillers used in paper |
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| US5221435A (en) * | 1991-09-27 | 1993-06-22 | Nalco Chemical Company | Papermaking process |
-
1995
- 1995-08-24 US US08/518,757 patent/US5531821A/en not_active Expired - Fee Related
-
1996
- 1996-04-01 US US08/625,937 patent/US5584923A/en not_active Expired - Fee Related
- 1996-08-23 WO PCT/US1996/013647 patent/WO1997008248A1/en not_active Application Discontinuation
- 1996-08-23 CN CN96196995.4A patent/CN1196075A/zh active Pending
- 1996-08-23 EP EP96929728A patent/EP0871680A4/en not_active Withdrawn
- 1996-08-23 AU AU69011/96A patent/AU701251B2/en not_active Ceased
- 1996-08-23 CA CA002230054A patent/CA2230054A1/en not_active Abandoned
- 1996-08-23 JP JP9510461A patent/JPH11512067A/ja active Pending
- 1996-08-26 AR ARP960104117A patent/AR003357A1/es unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0871680A4 (en) | 1999-06-16 |
| AU6901196A (en) | 1997-03-19 |
| JPH11512067A (ja) | 1999-10-19 |
| EP0871680A1 (en) | 1998-10-21 |
| AU701251B2 (en) | 1999-01-21 |
| WO1997008248A1 (en) | 1997-03-06 |
| AR003357A1 (es) | 1998-07-08 |
| CA2230054A1 (en) | 1997-03-06 |
| US5584923A (en) | 1996-12-17 |
| US5531821A (en) | 1996-07-02 |
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