CN1268810C - Filler composition, preparing method and use thereof - Google Patents

Filler composition, preparing method and use thereof Download PDF

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Publication number
CN1268810C
CN1268810C CN 02118915 CN02118915A CN1268810C CN 1268810 C CN1268810 C CN 1268810C CN 02118915 CN02118915 CN 02118915 CN 02118915 A CN02118915 A CN 02118915A CN 1268810 C CN1268810 C CN 1268810C
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composition
weight portion
paper
surfactant
weight parts
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CN1455044A (en
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詹剑峤
袁志伦
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JIAXUN DEVELOPING CO Ltd
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JIAXUN DEVELOPING CO Ltd
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Priority to CN 02118915 priority Critical patent/CN1268810C/en
Priority to AU2003236169A priority patent/AU2003236169A1/en
Priority to PCT/CN2003/000308 priority patent/WO2003093578A1/en
Publication of CN1455044A publication Critical patent/CN1455044A/en
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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
    • D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
    • D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material
    • 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
    • C09C1/40—Compounds of aluminium
    • 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
    • C09C1/40—Compounds of aluminium
    • C09C1/42—Clays
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • 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
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • 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
    • 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
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/22—Agents rendering paper porous, absorbent or bulky
    • D21H21/24—Surfactants

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Paper (AREA)

Abstract

The present invention discloses a filler composition. The composition mainly has the following chemical components of 30 to 38 weight parts of SiO2, 15 to 21 weight parts of CaO, 17 to 21 weight parts of MgO, 2 to 3 weight parts of Al2O3, 3.9 to 5.9 weight parts of SO4<2->, 8.8 to 31 weight parts of crystal water, Fe2O3, Na2O and K2O, wherein the total weight parts of Fe2O3, Na2O and K2O are fewer than 1 % of the weight parts of the entire composition. The composition is mainly prepared from (1) talcum, (2) natural calcium metasilicate, (3) bentonite, (4) magnesium oxide or magnesium carbonate and (5) a surface active agent; the surface active agent mainly has the following chemical components of 10 to 12 weight parts of SiO2, 7 to 11 weight parts of Al2O3, 36 to 39 weight parts of SO4<2->, 27 to 38 weight parts of crystal water, Fe2O3, CaO, Na2O and K2O; the total weight parts of Fe2O3, CaO, Na2O and K2O are fewer than 7.2 % of the weight parts of the entire surface active agent. The present invention also discloses a method for manufacturing the filler composition and an application of the filler composition to paper manufacture.

Description

Fill composition, Preparation Method And The Use
Technical field
The present invention relates to a kind of fill composition, Preparation Method And The Use relates in particular to a kind of paper grade (stock) fill composition, its preparation method and the application in papermaking.
Background technology
The main raw material of papermaking is a string, and string is woven into a mesh structure in paper, thereby gives paper various performances.For the consumption of saving string and some performance of improving paper, in papermaking, add usually and fill out multiple filler, in the paper-making industry as calcium carbonate, talcum powder, carclazyte (Kaoline) etc.International Patent Application WO 01/44573 discloses by at least a aluminium compound of adding and at least a silicate in paper pulp and has prepared paper products.US5300147 has disclosed the preparation method of the magnesium silicate SLR filler of low-light level, the low-light level paper that contains this filler and this filler and the application in papermaking.
On the other hand, the papermaking industry generally acknowledges, it is very limited that the adding of filler fills out, and every technical indicator severe exacerbation, the especially mechanical strength (as breaking length, tearing strength etc.) that can cause paper filled out in excessive adding.Can influence machine hand plant index and printing performance index in addition.Therefore, the actual amount of filling out that adds is 20-35% usually, and some goods (as newsprint) then are not add substantially to fill out.
Summary of the invention
An object of the present invention is to provide a kind of fill composition, it can add the higher actual retention of filling out in the paper and keeping 75-85% with the higher amount of filling out that adds, and makes every index of paper satisfy related standards simultaneously, and some indexs are optimized.
A further object of the invention provides a kind of method for preparing fill composition.
The present invention has a purpose to provide the purposes of fill composition again.
The invention provides a kind of fill composition, the main chemical composition of said composition is as follows: 30-38 weight portion SiO 2, 15-21 weight portion CaO, 17-21 weight portion MgO, 2-3 weight portion Al 2O 3, 3.9-5.9 weight portion SO 4 2-With the 8.8-31 weight portion crystallization water.
Fill composition of the present invention also contains Fe 2O 3, Na 2O and K 2O, its total weight parts is less than 1% of whole composition weight umber.
Fill composition of the present invention is mainly by (i) talcum, (ii) natural calcium metasilicate, (iii) bentonite, (iv) magnesia or magnesium carbonate and (v) surfactant makes, and the main chemical composition of described surfactant is as follows: 10-12 weight portion SiO 2, 7-11 weight portion Al 2O 3, 36-39 weight portion SO 4 2-With the 27-38 weight portion crystallization water.Also has Fe in the chemical composition of described surfactant 2O 3, CaO, Na 2O and K 2O, its total weight parts is less than 7.2% of whole surfactant parts by weight.
Fill composition of the present invention also comprises one or more raw materials that are selected from gypsum, zeolite, aluminum sodium sulfate, polyaluminum sulfate alumina silicate and the hydrated magnesium silicate.
Fill composition of the present invention is white powder, its whiteness 〉=85%, and particle mean size is the 5-10 micron, wherein the weight percentage of fibrous particle is 36-60%, the draw ratio of described fibrous particle 〉=10.
The present invention also provides a kind of method for preparing fill composition, and this method may further comprise the steps:
Mixed material talcum, natural calcium metasilicate, bentonite and magnesia or magnesium carbonate are milled to fine grained powder in advance;
Surfactant is milled to fine grained powder in advance, and perhaps one or more raw materials in mixed surfactant and optional gypsum, zeolite, aluminum sodium sulfate, polyaluminum sulfate alumina silicate and the hydrated magnesium silicate are milled to fine grained powder in advance;
Above-mentioned two kinds of fine grained powders are mixed, and further to be ground to granularity be the 5-10 micron,
Described surfactant can followingly make: add sulfuric acid solution and carry out acidolysis in aluminium hydroxide, add sodium metasilicate and optional calcium carbonate and/or sodium sulphate and/or potassium sulfate and/or cationic starch again, fully stir, crystallisation by cooling is also dry.
The present invention also provides the application of fill composition in papermaking.
The present invention also provides the paper products that comprise fill composition, for example writing paper, offset paper etc.
Fill composition of the present invention can add the higher actual retention of filling out in the paper and keeping 75-85% with the higher amount of filling out that adds, and makes every index of paper satisfy related standards simultaneously, and some indexs are optimized.This fill composition has certain purifying water effect, still has higher drainability under the condition of filling out in higher adding; And help to brighten, applying glue; Stable performance is suitable for long time stored.This fill composition is applicable to various main paper kinds (as writing paper, printing paper, sole paperboard and speciality paper), and its application need not existing paper making equipment and technology are made big adjustment.In addition, fill composition cost of the present invention is lower, and reproducible utilization has no side effect, and the preparation method is simple, is easy to apply.
Description of drawings
Fig. 1 a-1e is the microphoto of reflection fill composition structure of the present invention, and Fig. 1 a illustrates the structure that talcum, bentonite and calcium silicates are formed; Fig. 1 b illustrate bentonite with talcum, calcium silicates sticking be unified into netted; Newborn Subnano-class alumina silicate is shown Fig. 1 c and entringite (claim again to forge in vain, its whiteness is very high, and absorption affinity is strong) is adsorbed on calcium silicates and the talcum sheet; Fig. 1 d illustrates the Subnano-class alumina silicate and is adsorbed on talcum and the calcium silicates; The mutual embedding that Fig. 1 e illustrates on talcum, bentonite, the calcium silicates level is given birth to.
Fig. 2 a-2f is the microphoto of reflection fill composition of the present invention and the fibrous structure of paper, and Fig. 2 a illustrates the fibroplastic mutual network structure of talcum and natural calcium metasilicate and paper, and natural calcium metasilicate is shown Fig. 2 b and talcum invests on the fiber; Natural calcium metasilicate is shown Fig. 2 c and talcum (sheet) is coated on the fiber by bentonite; Fig. 2 d illustrates newborn cationic starch silica sol and twines the paper fiber, and natural calcium metasilicate and talcum net group are hung on the paper fiber; Fig. 2 e illustrates natural calcium metasilicate (needle-like) and talcum and is unified into nettedly by bentonite is sticking, is filled between the paper fiber; It is bonding by Subnano-class bentonite and cationic starch silica sol that Fig. 2 f is illustrated in the junction of paper fiber.
Fig. 3 is the X-ray diffractogram of fill composition of the present invention.
Fig. 4 is the ash X-ray diffractogram that contains the paper of fill composition of the present invention.
The specific embodiment
The main chemical composition of fill composition of the present invention is expressed as with oxide form: 30-38 weight portion SiO 2, 15-21 weight portion CaO, 17-21 weight portion MgO, 2-3 weight portion Al 2O 3, 3.9-5.9 weight portion SO 4 2-With the 8.8-31 weight portion crystallization water; Also can contain Fe 2O 3, Na 2O and K 2O, its total weight parts is less than 1% of whole composition weight umber.
The raw material of fill composition of the present invention mainly is (i) talcum, (ii) natural calcium metasilicate, (iii) bentonite, (iv) magnesia or magnesium carbonate and (v) surfactant.Talcum for example can derive from the Wenchuan, Sichuan, also is commercially available, and the nonmetallic ore company of Yingkou, Liaoning and Liuzhou for example, but be not limited thereto.Natural calcium metasilicate for example can derive from the places of production such as Yunnan Tengchong, Jilin Da Dingshan, Dayu, Jiangxi, also is commercially available, and for example Jilin pear tree wollastonite mining industry company commodity are called the product of big ancient cooking vessel mountain board, but are not limited thereto.Bentonite for example can derive from the Sichuan double fluid, also is commercially available, and for example Sichuan double fluid bentonite factory, Foshan bentonite factory, but be not limited thereto.Magnesia among the present invention is meant activated magnesia, and promptly the light calcined magnesia that forms in 600-700 ℃ of low-firing of magnesite (magnesium carbonate) is mainly used in coating, rubber, plastics, papermaking filler (pigment) usually.Described magnesia and magnesium carbonate for example can originate in Dashiqiao, Liaoning Province, for example by the nonmetal company in Dashiqiao, Liaoning product sold.
The main chemical composition of surfactant is 10-12 weight portion SiO 2, 7-11 weight portion Al 2O 3, 36-39 weight portion SO 4 2-With the 27-38 weight portion crystallization water.Also contain Fe in the chemical composition of described surfactant 2O 3, CaO, Na 2O and K 2O, its total weight parts is less than 7.2% of whole surfactant parts by weight.
Fill composition of the present invention also can randomly comprise one or more raw materials that are selected from gypsum, zeolite, aluminum sodium sulfate, polyaluminum sulfate alumina silicate and the hydrated magnesium silicate.
In fill composition of the present invention, talcum is the flat crystal of natural output, and is higher because of its whiteness, hardness is low thereby can be used for improving the smoothness and the printability of paper product.
In fill composition of the present invention, natural calcium metasilicate is the fibrous agrregate of natural generation, and after the ultra-fine grinding, granularity is the 5-10 micron, and draw ratio 〉=10 have good elongated fibers characteristic, can partly replace short paper fiber.Conventional filler is low-durometer material (for example the hardness of talcum, kaolin etc. is 1), but seldom uses hardness greater than 3 filler.And the hardness of the fibrous calcium metasilicate that the present invention adopts is 4.5-5, and these calcium metasilicate particles make elongated piece overlap mutually in the effect lower surface activation of surfactant.Positively charged micelle (as hydrated magnesium silicate, cationic starch etc.) when adding a large amount of hydrolysis in fill composition wraps up (as shown in Figure 1) layer by layer with needle-like calcium metasilicate particle.These particles are easy to parallel paper owing to the effect of laminar flow water body when copying paper aspect is arranged and the paper fiber forms level and smooth paper together.Therefore, the calcium metasilicate of high rigidity also just becomes a kind of functional filler.
In fill composition of the present invention, bentonite is as the surperficial clad material of talcum, natural calcium metasilicate or magnesium carbonate, makes itself and electronegative lumber fibre form the extensive chemical bonding, improves its retention and adhesive force.Improve the homogeneity that wet strength and composition disperse when becoming paper, formation has certain flexible binding agent when dry solidification, and filler and paper fiber are firmly bondd, and improves paper product intensity.In addition, bentonite also can be used as good flocculant and decolorizer.
In fill composition of the present invention, magnesia or magnesium carbonate are as the dispersant and the retention agent of filler.And normally used in prior art be the organic polymer retention agent.Magnesia or magnesium carbonate can help it to be distributed to paper pulp equably when fill composition is used for papermaking, make this fill composition combine and be difficult to the paper fiber and come off from fiber.Even if carry out secondary making beating, copy paper again and still can keep high retention rate and high evenness.
In fill composition of the present invention, surfactant is retrofited and surface modification to raw materials used, when the hydration process of fill composition, impels the formation of multiple new silicate compound.Surfactant can followingly make: add sulfuric acid solution in aluminium hydroxide, stir 1-2 hour to carry out acidolysis in 70-80 ℃, and then add sodium metasilicate and optional calcium carbonate and/or sodium sulphate and/or potassium sulfate, stirred crystallisation by cooling and drying 30-60 minute in 70-80 ℃.When preparing described surfactant, also can add cationic starch, form the cationic starch silica sol of nanometer or Subnano-class, be used for the tensile strength that papermaking can improve paper product.The content of cationic starch accounts for the 8-9.8 weight % of surfactant.
Adopt the method for mechanical mixture to prepare fill composition of the present invention.The raw material of fill composition of the present invention can be divided into two parts, and first is talcum, natural calcium metasilicate, bentonite and magnesia or magnesium carbonate; Second portion is surfactant, optional gypsum, zeolite, aluminum sodium sulfate, polyaluminum sulfate alumina silicate and hydrated magnesium silicate, the preparation method of this fill composition mixes the raw material of first and second portion respectively and levigate, and then with two kinds of powder evenly and further to be ground to granularity be the 5-10 micron.
The gained fill composition is white powder, its whiteness 〉=85%, and particle mean size is the 5-10 micron, the weight percentage 〉=36-60% of fibrous particle wherein, the draw ratio of described fibrous particle (L/D) 〉=10.
Fill composition of the present invention is compared with the filler of prior art, the Structure Mechanism difference.The filler particles of prior art mostly is sheet, granular, is difficult to form reasonably pile up, and its filling form is mainly mechanical stowing between the paper fiber, and is loosely organized.Thereby with the increase that adds the amount of filling out, the mechanical strength index of gained paper can sharply descend.And shape is fibrous, needle-like, sheet and granular outside the main raw material of fill composition of the present invention, they are when hydrolysis, and the various raw materials that constitute product at first are that sheet and granular solid matter are made skeleton commissure formation Rational structure (referring to Fig. 1) each other with raphioid fiber.Behind paper fibre chemistry bonding, the mutual embedding of the network structure of paper fiber and fill composition network structure is given birth to, and constitutes the Rational structure (referring to Fig. 2) of paper jointly.Fill composition of the present invention has the effect of structural material, therefore adds under the situation of filling out higher, and mechanical strength is declined to a great extent.
The bonding mechanism of fill composition of the present invention and paper fiber also is different from the filler of prior art.The filler of prior art is a kind of thing suction-operated with combining of paper fiber, and the applying glue in promptly natural filling and the paper technology is fixed, and its bond strength is limited.And fill composition of the present invention mainly is a kind of chemisorption with combining of paper fiber, and its bond strength is stronger.The specific surface energy of superfine powder of the present invention is very high, makes the stronger positive charge of powder granule band when hydrolysis under the strong effect of surfactant, with the stronger chemical bonding (Fig. 1 and Fig. 2) of paper fiber formation of the strong negative electrical charge of band.The sodium magnesium alumino metasilicate colloidal sol of the polyaluminum sulfate alumina silicate that generates after the fill composition hydrolysis, hydrated magnesium silicate, higher suspension and zeolite and cationic starch silica sol isoreactivity molecule take place powerful bonding to powder and paper fiber.Dehydrating and curing and produce the Subnano-class new mineral in the drying course of papermaking is bonded together powder and paper fiber firmly.Above-mentioned physical chemical process makes fill composition of the present invention can keep higher " retention " and " wet strength " on paper, still keeps higher mechanical strength behind the one-tenth paper.
Further specify the present invention by the following examples.
The preparation of surfactant
Surfactant 1
Adding 42.9 gram concentration in 13.9 gram aluminium hydroxides is the sulfuric acid solution of 60 weight %, stirs 1.5 hours carrying out acidolysis in about 80 ℃, and then adds 15.4 gram sodium metasilicate, stirred 45 minutes in about 80 ℃, crystallisation by cooling, dry in about 120 ℃, pulverize then and make surfactant 1.
The chemical composition that records surfactant 1 with international complete chemical analysis method is: 10.1 weight portion SiO 2, 7.2 weight portion Al 2O 3, 35.8 weight portion SO 4 2-, the 27.1 weight portion crystallizations water and 0.30 weight portion Fe 2O 3Fe wherein 2O 3Bring by impurities in raw materials used.
Surfactant 2
Adding 46.0 gram concentration in 15.0 gram aluminium hydroxides is the sulfuric acid solution of 60 weight %, stirs 1 hour carrying out acidolysis in about 70 ℃, and then adds 16.7 gram sodium metasilicate, stirred 60 minutes in about 70 ℃, crystallisation by cooling, dry in about 100 ℃, pulverize then and make surfactant 2.
The chemical composition that records surfactant 2 with international complete chemical analysis method is: 12.3 weight portion SiO 2, 10.9 weight portion Al 2O 3, 39.1 weight portion SO 4 2-, the 38.2 weight portion crystallizations water and 0.37 weight portion Fe 2O 3Fe wherein 2O 3Bring by impurities in raw materials used.
Surfactant 3
Adding 39.9 gram concentration in 12.9 gram aluminium hydroxides is the sulfuric acid solution of 60 weight %, stir 2 hours to carry out acidolysis in about 75 ℃, and then add 14.0 gram sodium metasilicate, 1.5 gram calcium carbonate, 13.8 gram sodium sulphate and 4.4 gram potassium sulfates, 9.9 gram cationic starch and 1000 ml waters, stirred 30 minutes in about 75 ℃, crystallisation by cooling, dry in about 150 ℃, pulverize then and make 111.0 gram surfactants 3.
The chemical composition that records surfactant 3 with international complete chemical analysis method is: 11.2 weight portion SiO 2, 8.6 weight portion Al 2O 3, 37.4 weight portion SO 4 2-, the 33.4 weight portion crystallizations water, 1.2 weight portion CaO, 3.7 weight portion Na 2O, 1.5 weight portion K 2O and 0.35 weight portion Fe 2O 3
The preparation of fill composition
Embodiment 1
Restrain natural calcium metasilicate (available from Jilin pear tree wollastonite company with plastics mixer mixed material 37 gram talcums (available from Yingkou, Liaoning nonmetallic ore company), 40, commodity big ancient cooking vessel mountain by name board), 11 gram bentonites (available from Sichuan double fluid bentonite powder factory), 6 gram magnesia (available from the nonmetal company in Dashiqiao, Liaoning), be milled to fine grained powder in advance; With C * 132 type ultrafine crushers 7 gram surfactants 2 are milled to fine grained powder in advance; With plastics mixer above-mentioned two kinds of fine grained powders are mixed, and further to be ground to particle mean size be 7 microns.
Resulting composition is white powder, and its whiteness is 90%.Record with international complete chemical analysis method, the weight percentage of fibrous particle is 60%, records with the S-530 of HIT type Electronic Speculum, and the draw ratio of fiber grain is 11.With the chemical composition of international complete chemical analysis method measurement said composition powder, the result is 30.2 weight portion SiO 2, 15.2 weight portion CaO, 17.1 weight portion MgO, 1.9 weight portion Al 2O 3, 3.9 weight portion SO 4 2-, the 8.9 weight portion crystallizations water and 0.5 weight portion Fe 2O 3
Embodiment 2
Restrain natural calcium metasilicate (available from Jilin pear tree wollastonite company with plastics mixer mixed material 39 gram talcums (available from Yingkou, Liaoning nonmetallic ore company), 45, commodity big ancient cooking vessel mountain by name board), 13 gram bentonites (available from Sichuan double fluid bentonite powder factory), 8 gram magnesia (available from the nonmetal company in Dashiqiao, Liaoning), be milled to fine grained powder in advance; With C * 132 type ultrafine crushers 9 gram surfactants 1 are milled to fine grained powder in advance; With plastics mixer above-mentioned two kinds of fine grained powders are mixed, and further to be ground to particle mean size be 5 microns.
Resulting composition is white powder, and its whiteness is 88%.Record with international complete chemical analysis method, the weight percentage of fibrous particle is 52%, records with the S-530 of HIT type Electronic Speculum, and the draw ratio of fiber grain is 11.With the chemical composition of international complete chemical analysis method measurement said composition powder, the result is 38.1 weight portion SiO 2, 21.0 weight portion CaO, 21.1 weight portion MgO, 3.1 weight portion Al 2O 3, 5.9 weight portion SO 4 2-, the 31.0 weight portion crystallizations water and 0.7 weight portion Fe 2O 3
Embodiment 3
With plastics mixer mixed material 35 gram talcums (available from Yingkou, Liaoning nonmetallic ore company)), the natural calcium metasilicate of 35 grams is (available from Jilin pear tree wollastonite company, commodity big ancient cooking vessel mountain by name board), 9 gram bentonites (available from Sichuan double fluid bentonite powder factory), 4 gram magnesium carbonate (available from the nonmetal company in Dashiqiao, Liaoning), be milled to fine grained powder in advance; Mix 5 gram surfactants 3 and 4.2 gram gypsum, 3.8 gram zeolites, 9.9 gram aluminum sodium sulfates, 4.8 gram polyaluminum sulfate alumina silicate, 13.2 gram hydrated magnesium silicates and be milled to fine grained powder in advance with C * 132 type ultrafine crushers; With plastics mixer above-mentioned two kinds of fine grained powders are mixed, and further to be ground to granularity be 10 microns.
Resulting composition is white powder, and its whiteness is 85%.Record with international complete chemical analysis method, the weight percentage of fibrous particle is 36%, records with the S-530 of HIT type Electronic Speculum, and the draw ratio of fiber grain is 10.With the chemical composition of international complete chemical analysis method measurement said composition powder, the result is 35.2 weight portion SiO 2, 18.2 weight portion CaO, 20.1 weight portion MgO, 2.7 weight portion Al 2O 3, 4.8 weight portion SO 4 2-, the 25.1 weight portion crystallizations water, 0.4 weight portion Fe 2O 3, 0.56 weight portion Na 2O and 0.07 weight portion K 2O.
Papermaking and test
The fill composition of gained is used for papermaking, and the gained paper is tested.
Fill composition is wanted earlier slurrying when being used for papermaking, promptly add in the fill composition with 4 times the clean water that papermaking requires that meets, and is heated to 50-60 ℃ and stirred 40 minutes, and keeping the pH value is 6.5-7.5.
Conventional papermaking process flow is a pulp beating → size mixing → dilute → copy paper, adds the fill composition slurries that as above make when sizing mixing, and paper technology is made offset printing paper routinely again, measures the key technical indexes of gained paper.
Writing paper
The fill composition of embodiment 1 is used for making 55g/m 2Writing paper, products material is needle slurry (15 weight %), broad-leaved slurry (40 weight %) and fill composition (45 weight %).The ash of gained finished paper is 29.1%, and retention is 76%.The testing result of gained paper sees the following form 1.
Table 1
Test item Unit Product standard GB12654-90 A level Assay
Quantitatively g/m 2 50±2.5 54.5
Whiteness ％ ≥80 83.2
Opacity ％ ≥75 87.4
Degree of sizing mm ≥0.75 0.75
Smoothness S ≥25 53
Positive and negative difference ％ ≥30 36.9
Folding strength (laterally) Inferior ≥6 8
Dirt count Individual/m 2 0.3-1.5mm 2 ≤80 28
Moisture ％ 6±2.0 6.8
Ash ％ --- 29.1
Fracture length m --- 2400
Fig. 3 and Fig. 4 show the X-ray diffractogram of the fill composition of the present invention and the ash of the paper that contains said composition respectively, and as seen both are consistent.This shows that the chemical composition of fill composition of the present invention in paper-making process and molecular structure have obtained good maintenance.
Offset paper
The fill composition of embodiment 2 is used for making 70g/m 2Offset paper, products material is import Russia softwood pulp (25 weight %), pinus khasys bleached pulp (35 weight %), blue by slurry (10 weight %) and fill composition (30 weight %), the testing result of gained paper sees the following form 2.
Table 2
Test item Unit Product standard QB/T1211-1911A level Assay
Quantitatively g/m 2 70±3.0 71
Fracture length Vertical m 4130
Horizontal m 2560
On average m ≥3000 3345
Whiteness ％ ≥70-75 90
Tightness g/m 3 ≤0.85 0.80
Moisture ％ 4.0-8.0 5.96
Degree of sizing mm ≥0.25 1.10
Folding strength Inferior ≥5 13
Opacity ％ ≥82 89
Dirt count Individual/m 2 ≤100 (0.3-2.0mm 2) 40
Ash ％ --- 25.94
Tear index mn·m 2/g --- 5.90
The pond ash of sizing mixing ％ --- 33.21
The water purification performance test
The fill composition of embodiment 3 is used for making 55g/m 2Writing paper, and the gained paper tested, obtain and the similar testing result of the foregoing description 1 fill composition.In addition, paper waste to the paper making water in this paper-making process and total floss hole carries out water analysis, the result shows that paper-making process does not cause the influence of significant adverse to water quality, the content of most of pollutant elements (as mercury, cadmium, arsenic, lead, nickel, phenol, cyanide, sulfide, formaldehyde, zinc, magnesium etc.) does not all increase in the water, in addition, the content of total suspended matter, chromium, copper and calcium obviously descends.
Add at the foregoing description 1 fill composition and to fill out writing paper and embodiment 2 fill compositions and add in the process of filler seal papers for books and periodicals, equally paper making water and paper waste are carried out water analysis, obtain the result roughly the same with last table.
Therefore, fill composition of the present invention is used for papermaking and has shown good water purification function.Conventional filler has only the mechanical filter effect to paper making water, so a little less than the water purification effect.And fill composition of the present invention is a superfine powder, has the colloid feature, when the powder hydrolysis, under the strong effect of modifier (as surfactant), particulates such as polyaluminum sulfate alumina silicate, hydrated magnesium silicate, high activity Magnesiumaluminumsilicate colloidal sol and the zeolite of newborn ultra micro and cationic starch silica sol, various heavy metal ion in the strong adsorption water as harmful elements such as copper, cadmium, mercury, arsenic, chromium, lead, have good purification, sterilization and antisepsis to paper making water.
Find also in the test that fill composition of the present invention has dehydrating function preferably.Conventional filler is more single, so how much pile up not too rationally, the filler filling has been stopped up the drainage passage in the network structure of paper fiber, and water filtering function is poor.And fill composition of the present invention is the compounded mix that plurality of raw materials is formed.Needle-like, sheet, granular material form rationally when hydrolysis to be piled up (as shown in Figure 1), combines the common reasonable network structure (as Fig. 2) that constitutes paper in back with fiber.Thereby, even still have drainage and dehydration preferably under the situation of filling out in higher adding.
The durability height of fill composition of the present invention helps to make full use of and economize on resources.A little less than conventional filler and the paper fibrous binding force, filler and fiber hightail during regeneration, are consumed totally in pulping process.And it is stronger because of filler and paper fibrous binding force in the regeneration process to add the paper that is filled with fill composition of the present invention, thereby recovery utilization rate 〉=73% of fill composition the time not with retention agent.Its mechanism of action is: waste paper is under aqueous medium and mechanism's stirring action, and the modified Portland that plays bonding action is reduced to positively charged particle cluster once again.After fill composition and the paper fiber separation, still rely on self surface charge difference to keep combination.
Add the paper of filling out fill composition of the present invention, indexs such as its whiteness, opacity, folding strength and absorbency all have clear improvement.Fill composition of the present invention has higher natural whiteness (being not less than 85% usually), and this filler combination powder relies on the surface electrical potential difference attached on the paper, produces physics " bleaching " effect.
In addition, in the fill composition the higher fibrous material of hardness when aquation and other component materials form mesh skeleton structures, the mutual each other embedding life of the network structure of this structure and paper fiber has improved deflection, folding strength, water permeability and the air permeability of paper product.

Claims (10)

1. paper grade (stock) fill composition, the main chemical composition of said composition is as follows: 30-38 weight portion SiO 2, 15-21 weight portion CaO, 17-21 weight portion MgO, 2-3 weight portion Al 2O 3, 3.9-5.9 weight portion SO 4 2-With the 8.8-31 weight portion crystallization water.
2. composition as claimed in claim 1 is characterized in that said composition also contains Fe 2O 3, Na 2O and K 2O, its total weight parts is less than 1% of whole composition weight umber.
3. composition as claimed in claim 1 or 2, it is characterized in that said composition is mainly by (i) talcum, (ii) natural calcium metasilicate, (iii) bentonite, (iv) magnesia or magnesium carbonate and (v) surfactant makes, and the main chemical composition of described surfactant is as follows: 10-12 weight portion SiO 2, 7-11 weight portion Al 2O 3, 36-39 weight portion SO 4 2-With the 27-38 weight portion crystallization water.
4. composition as claimed in claim 3 is characterized in that also having Fe in the chemical composition of described surfactant 2O 3, CaO, Na 2O and K 2O, its total weight parts is less than 7.2% of whole surfactant parts by weight.
5. composition as claimed in claim 3 is characterized in that said composition also comprises one or more raw materials that are selected from gypsum, zeolite, aluminum sodium sulfate, polyaluminum sulfate alumina silicate and the hydrated magnesium silicate.
6. composition as claimed in claim 1 or 2 is characterized in that said composition is white powder, its whiteness 〉=85%.
7. composition as claimed in claim 1 or 2, the particle mean size that it is characterized in that said composition is the 5-10 micron, wherein the weight percentage of fibrous particle is 36-60%, the draw ratio of described fibrous particle 〉=10.
8. method for preparing each described paper grade (stock) fill composition among the claim 1-7, this method may further comprise the steps:
Mixed material talcum, natural calcium metasilicate, bentonite and magnesia or magnesium carbonate are milled to fine grained powder in advance;
Surfactant is milled to fine grained powder in advance, and perhaps one or more raw materials in mixed surfactant and optional gypsum, zeolite, aluminum sodium sulfate, polyaluminum sulfate alumina silicate and the hydrated magnesium silicate are milled to fine grained powder in advance;
Above-mentioned two kinds of fine grained powders are mixed, and further to be ground to granularity be the 5-10 micron,
Described surfactant can followingly make: add sulfuric acid solution and carry out acidolysis in aluminium hydroxide, add sodium metasilicate and optional calcium carbonate and/or sodium sulphate and/or potassium sulfate and/or cationic starch again, fully stir, crystallisation by cooling is also dry.
9. as each described fill composition application in papermaking among the claim 1-7.
10. the paper products that comprise each described fill composition among the claim 1-7.
CN 02118915 2002-04-30 2002-04-30 Filler composition, preparing method and use thereof Expired - Fee Related CN1268810C (en)

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CN 02118915 CN1268810C (en) 2002-04-30 2002-04-30 Filler composition, preparing method and use thereof
AU2003236169A AU2003236169A1 (en) 2002-04-30 2003-04-28 A filter composition, a process of making the composition and the use of the same
PCT/CN2003/000308 WO2003093578A1 (en) 2002-04-30 2003-04-28 A filter composition, a process of making the composition and the use of the same

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CN1323211C (en) * 2004-06-21 2007-06-27 徐清明 Paper making mineral composite retention aid and preparing process and application thereof
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