Nothing Special   »   [go: up one dir, main page]

WO2017177349A1 - 用于纸张/纸板生产的三元填料体系及其制备方法 - Google Patents

用于纸张/纸板生产的三元填料体系及其制备方法 Download PDF

Info

Publication number
WO2017177349A1
WO2017177349A1 PCT/CN2016/000203 CN2016000203W WO2017177349A1 WO 2017177349 A1 WO2017177349 A1 WO 2017177349A1 CN 2016000203 W CN2016000203 W CN 2016000203W WO 2017177349 A1 WO2017177349 A1 WO 2017177349A1
Authority
WO
WIPO (PCT)
Prior art keywords
starch
filler
paper
flocculant
ternary
Prior art date
Application number
PCT/CN2016/000203
Other languages
English (en)
French (fr)
Inventor
赵明川
赵迎辉
Original Assignee
合肥信拓高分子技术有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 合肥信拓高分子技术有限公司 filed Critical 合肥信拓高分子技术有限公司
Priority to PCT/CN2016/000203 priority Critical patent/WO2017177349A1/zh
Publication of WO2017177349A1 publication Critical patent/WO2017177349A1/zh

Links

Classifications

    • 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
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • 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
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • 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

Definitions

  • the invention belongs to the field of papermaking additives.
  • the present invention relates to a ternary filler system for improving the ash content and strength properties of paper or paperboard used in the manufacture of paper/cardboard, a process for the preparation thereof, and the production of the ternary filler system in paper or paperboard The purpose of simultaneously improving the ash content and strength properties of paper or paperboard.
  • filler In the production of paper and paperboard, in order to reduce the cost and improve the optical properties of the paper, it is widely used to add a relatively inexpensive filler to the paper.
  • Currently more commonly used fillers include calcium carbonate (ground calcium carbonate (GCC) and deposited calcium carbonate (PCC)), talc, titanium dioxide, kaolin and diatomaceous earth. Due to the limited nature of the filler itself, excessive addition can have many negative effects, which can cause a decrease in the physical strength of the paper and can affect the operation of the paper machine. This is due to the inherent physical properties that the filler itself cannot form an effective bond with the fibers, and it also affects the hydrogen bonding between the fibers, resulting in a paper strength that is lower than that of the unfilled paper.
  • Excessive addition can also cause problems such as powder loss; and because the particle size of the filler particles is generally only a few micrometers, the bonding force between the filler and the fiber is poor, and the first-pass retention rate is low during the papermaking process, resulting in the filler in the paper.
  • the retention rate is not high, causing a large amount of filler to accumulate in the white water system, which has a negative impact on the wet end operation of the paper machine.
  • the traditional way of filling in the papermaking process is to increase the first-pass retention of the filler through the paper machine retention system.
  • the reduction in paper strength caused by the addition of fillers can only be solved by increasing the amount of paper reinforcing agent.
  • the surface modification of the filler is the main research direction to increase the amount of paper filler. Because the surface of the filler is modified to reduce or eliminate the adverse effect of the bond strength between the fibers due to the presence of the filler, it provides a way to improve the ash content in the paper.
  • U.S. Patent No. 2,949,397 A describes a method of pretreating a filler coated with calcium carbonate with polymannose galactose gum (carot gum, guar gum, etc.).
  • U.S. Patent No. 5,147,507 describes a method of pretreating a calcium carbonate filler using a cationic polymer to reduce the amount of sizing agent in the wet end sizing process, and to improve filler retention and paper optical properties and tensile strength.
  • U.S. Patent No. 5,527,430 describes a method for pretreating a calcium carbonate filler using a hydrophobic compound (sodium stearate, etc.) to reduce the amount of sizing agent in the wet end sizing process and to increase the sizing efficiency.
  • a hydrophobic compound sodium stearate, etc.
  • U.S. Patent Application No. US20090020250A1 describes a method of pretreating calcium carbonate fillers with anionic polysaccharides and cationic or amphoteric polyacrylamides to increase the amount of filler.
  • Chinese patent CN103397561A describes a method for first modifying a filler by mixing a cationic coagulant with a filler and then mixing it with an anionic synthetic latex to obtain a higher ash content.
  • modified starch especially cationic starch or amphoteric starch
  • modified starch can be used for papermaking after cooking to obtain ideal effects such as reinforcement, retention, and sizing agent emulsification.
  • modified starch is one of the most widely used and most cost-effective reinforcement and retention aids.
  • the study of surface modification of fillers using modified starch is also found in many patent documents.
  • U.S. Patent No. 3,873,336 describes a method of pretreating a calcium carbonate filler using a mixture of a cationically modified starch and an anionically modified starch to enhance the stability of the filler under acidic papermaking conditions.
  • U.S. Patent 4,115,187 describes a process for pretreating a calcium carbonate filler using an organic polymer, modified starch or sodium alginate salt to increase the stability of the filler under acidic papermaking conditions.
  • U.S. Patent 7,074,845 B2 describes a process for modifying a filler using an anionic polymer latex and a cationically swelled starch to achieve higher internal bond strength and tensile strength.
  • Chinese patent CN102363932A describes a method for performing on-line modification of a filler using a modified starch paste liquid and a retention aid to obtain a higher ash content of the paper.
  • Chinese patent CN103352395A describes a method for modifying a filler using a cationic starch and a cationic starch crosslinker to obtain a higher amount of filler. .
  • the modified starch described in the above prior art documents is mainly used for surface modification of the filler after steaming and aging, and most of them only by surface modification method, the filler is increased in amount while minimizing the influence on the strength of the paper. . None of the disclosed filler systems mention a system which increases the amount of filler while increasing the strength of the paper.
  • the present invention provides a filler-starch-flocculant ternary filler system additive used in the production of paper (or paperboard), which can simultaneously increase the ash content of paper/cardboard. And strength properties.
  • the present invention discloses a ternary filler system for paper/cardboard production that simultaneously increases the ash content and strength properties of paper (or paperboard).
  • a ternary filler system for paper/cardboard production comprising the following components: 1) a filler; 2) starch; and 3) a flocculant wherein the dry weight ratio of the filler to starch is about 200:1 to 1 : 10, the flocculant is added in an amount of the filler and starch
  • the dry weight basis is about 0.05% to 5%.
  • the fillers used in the present invention are any well known, commercially available fillers for papermaking.
  • Examples of representative fillers include calcium carbonate, kaolin, talc, titanium dioxide, aluminum hydroxide, and the like.
  • calcium carbonate mainly includes ground calcium carbonate (GCC) and deposited calcium carbonate (PCC).
  • GCC ground calcium carbonate
  • PCC deposited calcium carbonate
  • the calcium carbonate may be dispersible calcium carbonate or non-dispersive calcium carbonate.
  • Dispersible GCC and PCC are typically prepared using a polyacrylic acid polymer dispersant or a sodium polyphosphate dispersant. These dispersants impart a significant anionic charge to the calcium carbonate particles.
  • dispersible calcium carbonate GCC and PCC
  • the single flocculant in the case of non-dispersible calcium carbonate (GCC and PCC), it is especially suitable to use the two opposite charges Flocculant combination.
  • the filler is usually prepared to be used in an amount of from about 1 to 30% by weight of the aqueous suspension of the filler.
  • the starch used in the present invention is an original starch which has not been subjected to any modification treatment (including cationization, anionization or amphoteric modification), or has not been subjected to retort gelatinization; or an oxidized starch which has not been subjected to cooking and gelatinization.
  • the raw material of the raw starch or oxidized starch is selected from one or a combination of corn starch, tapioca starch, potato starch, and wheat starch.
  • the starch is usually prepared so that about 0.5 to 5% by weight of the aqueous starch suspension is used without being subjected to retort.
  • the flocculating agent used is a single flocculating agent or a combination of two flocculating agents of opposite charges.
  • the flocculating agent is a cationic polymer having a weight average molecular weight of 1,000,000 or more and an anionic polymer having a weight average molecular weight of 1,000,000 or more.
  • Suitable cationic and anionic polymers generally have a charge content of less than 50 mol%.
  • Cationic polymers suitable for use in the present invention include (meth)acrylamide and dimethylaminoethyl methacrylate (DMAEM), dimethylaminoethyl acrylate (DMAEA), diethylaminoethyl methacrylate (DEAEA), Copolymers and terpolymers in the form of diethylaminoethyl methacrylate (DEAEM) or its quaternary ammonium salt.
  • DMAEM dimethylaminoethyl methacrylate
  • DAEA dimethylaminoethyl acrylate
  • DEAEA diethylaminoethyl methacrylate
  • DEAEM diethylaminoethyl methacrylate
  • Anionic polymers suitable for use in the present invention include copolymers of acrylamide with sodium acrylate and/or 2-acrylamido-2-methylpropanesulfonic acid (AMPS) or have been hydrolyzed to convert a portion of the acrylamide groups to acrylic acid. Acrylamide homopolymer.
  • the flocculating agent is usually prepared as an emulsion and then diluted to 0.2 to 2% by weight for use.
  • the invention further relates to a process for the preparation of a ternary filler system according to the invention comprising the steps of:
  • step 2) Mixing the two aqueous suspensions obtained in step 1) with the flocculating agent in different mixing modes to obtain a ternary filler system under suitable shear conditions.
  • the shearing condition is selected according to the solid content of the stirring device and the filler, and the stirring time is usually 5 seconds to 5 minutes, the stirring rate is 100 rpm to 3000 rpm, and the temperature is usually 0 to 50 degrees.
  • the flocculating agent may be added in a manner such that a single flocculating agent is added to the mixture of the two aqueous suspensions obtained in the step 1), wherein the dry weight ratio of the filler to the starch is from about 200:1 to 1:10; or two a flocculant carrying opposite charges in turn Adding to the mixture of the two aqueous suspensions obtained in the step 1); or mixing the two oppositely charged flocculants with the mixture of the aqueous suspension obtained in the step 1) in a ratio of 20:80 to 80:20 for pre-flocculation Then, the two pre-flocs are further mixed; or the two oppositely charged flocculants are separately mixed with the two aqueous suspensions obtained in the step 1) for pre-flocculation, and then the two pre-flocs are mixed.
  • the method comprises the steps of:
  • a process for the preparation of a ternary filler system additive according to the invention comprises the steps of:
  • a cationic flocculant is added to the product obtained in the step 2), and the mixture is flocculated to prepare a ternary filler system.
  • the process for the preparation of a ternary filler system additive according to the invention comprises the steps of:
  • the mixture prepared in the step 1) is divided into two parts, the ratio of the two parts is preferably between 20:80 and 80:20, and an anionic flocculant is added to one part, and mixed for pre-flocculation; a cationic flocculant is added to the mixture and mixed for pre-flocculation;
  • the two pre-flocs obtained in the step 2) are mixed and flocculated to obtain a ternary filler system.
  • the process for the preparation of a ternary filler system additive according to the invention comprises the steps of:
  • the preparation method according to the present invention can be carried out in an online manner or offline, that is, it can be carried out in synchronization with the operation of the paper machine or pre-fabricated before the operation of the paper machine.
  • the ternary filler system according to the present invention is added via a conventional filler inlet of a paper machine which simultaneously increases the ash content and strength properties of the paper/paperboard.
  • most of the starch used in the prior art is modified starch and needs to be added as a dry strength agent after cooking and gelatinization.
  • the starch concentration is limited to 2-4% due to the cooking gelatinization process, and the ternary filler system of the present invention is directly With the original unmodified starch or oxidized starch, the concentration is not limited to more than 30% by the cooking process.
  • the price of the original unmodified starch or oxidized starch is much lower than that of the modified starch, and the method of the present invention does not involve the running cost of the cooking process, so the production cost is greatly reduced.
  • the invention further relates to the use of a ternary filler system according to the invention for increasing the ash content and strength properties of paper/paperboard in the production of paper and/or paperboard.
  • the mechanism of action should be that in the ternary filler system, the filler is not only modified by the surface of the flocculant, but also can produce co-flocs with the original starch or oxidized starch by the preparation of two oppositely charged double flocculants. In co-flocs, the filler can be effectively encapsulated by the original starch or oxidized starch to produce a stable shear-resistant co-floc. After adding to the wet end of the paper machine, the starch and the fiber wrapped can form a good bond, thereby solving the contradiction between the paper strength and the filling amount, and can simultaneously increase the filling amount (ash content) and the paper strength. Effect.
  • the original starch or the uncooked gelatinized oxidized starch without any modification treatment and cooking and swelling may rely on the filler and the formation of stable co-flocs under the action of two oppositely charged double flocculants.
  • the higher first-pass retention rate and better uniformity are retained in the paper forming section, so that the retained original starch or oxidized starch can obtain sufficient gelation heat from the dryer section of the paper machine and finally mature to stabilize.
  • Enhancer The paper reinforcing effect thus obtained is better than that obtained by using spray starch in the prior art. Since most of the sprayed starch is concentrated between the layers of paper and paper, it is difficult to achieve an effect of enhancing the overall reinforcement of the original starch or oxidized starch of the present invention.
  • the prior art generally uses modified starch and is added to the slurry after cooking and gelatinization because the raw starch or oxidized starch which has not been cooked and gelatinized is directly added to the slurry, and the first pass retention rate is poor, resulting in a large amount of addition into the slurry.
  • the uncooked gelatinized raw starch or oxidized starch passes through the forming section of the paper machine into the white water of the sump, causing the white water concentration to be too high, which causes the paper machine to operate difficult and adversely affects the use of sizing and other chemicals. .
  • the original starch or oxidized starch which has not been cooked and gelatinized directly on the basis of the prior art must use a large amount of retention aid, which causes difficulty in forming the paper, affects the uniformity of the paper, and the amount of the starch is also greatly increased. limit.
  • the raw starch or oxidized starch and the filler which have not been cooked and gelatinized can form shear-stable co-pre-flocs under suitable shearing conditions under the action of a suitable flocculating agent, and the particles thereof
  • the size is an order of magnitude larger than the particle size of the individual uncooked gelatinized raw starch or oxidized starch and filler.
  • the formed ternary filler can have a very high head in the forming part of the paper machine without increasing the amount of retention aid.
  • the process retention rate, and the amount of starch added can determine the amount of entry according to the requirements of the strength of the paper.
  • the fillers and starches used in the examples of the present invention are commercially available.
  • the bleached softwood kraft pulp and the bleached broad-leaved kraft pulp were slurried in a ratio of 30:70 to prepare a mixed pulp of 1% concentration.
  • the above prepared filler system was separately added to the two pulps according to the 25% dry weight ratio and the 35% absolute dry weight ratio, and then uniformly stirred, and then the cation retention was added at 0.5 kg/ton (dry weight ratio).
  • Additives BASF PERCOL 182, Germany
  • the two different fillers are tested by pressing, drying, balancing and other steps. Relevant physical indicators such as ash content (GB/T463-1989) and tensile index (GB/T453-89). The experimental results are shown in Tables 1 and 2.
  • the filler is made of dispersible PCC slurry (Guangdong Powerful New Material Technology Co., Ltd., product model 6150), and diluted with tap water to prepare a suspension with a solid content of 10%.
  • the original starch is selected from tapioca starch, and is prepared into a suspension having a solid content of 2.5% by tap water.
  • Single flocculant using cationic polyacrylamide with a weight average molecular weight of 4 million and 25% molar charge Hefei Xintuo Polymer Technology Co., Ltd. XT81400 (copolymer of acrylamide and dimethyldipropenyl ammonium chloride)
  • Tap water is formulated into a 0.5% solids solution for use.
  • the filler was selected from ground calcium carbonate (GCC) with a mesh number of 400 mesh, and was prepared by using tap water to prepare a suspension having a solid content of 10%.
  • the original starch is selected from tapioca starch, and is prepared into a suspension having a solid content of 2.5% by tap water.
  • One type of flocculant is a cationic polyacrylamide with a weight average molecular weight of 4 million and 25% molar charge (Hefei Xintuo Polymer Technology Co., Ltd. XT81400); the other is a weight average molecular weight of 7 million, 20% molar charge.
  • Anionic polyacrylamide Hefei Xintuo Polymer Technology Co., Ltd. XT80700 (copolymer of acrylamide and acrylic acid)). Both flocculants were formulated with tap water to prepare a 0.5% solids solution.
  • 250 ml of the above 10% GCC suspension was added in a 1000 ml beaker at a stirring speed of 100 rpm, then 250 ml of the above 2.5% tapioca starch suspension was added, stirred and mixed uniformly, first at 30 rpm stirring speed at 30 20 ml of the above 0.5% anionic polyacrylamide solution was added to the above-mentioned 0.5% anionic polyacrylamide solution for pre-flocculation at a constant rate, and then stirring was continued for 30 seconds, and then 20 ml of the above 0.5% cationic polyacrylamide solution was uniformly added at a stirring speed of 1000 rpm for 30 seconds. The preparation is completed by stirring for at least one minute.
  • the bleached softwood kraft pulp and the bleached broad-leaved kraft pulp were slurried in a ratio of 30:70 to prepare a mixed pulp of 1% concentration.
  • the above prepared ternary fillers were separately added to the two pulps according to the 25% absolute dry weight ratio and the 35% absolute dry weight ratio, and then uniformly stirred, and then added according to 0.5 kg/ton (dry weight ratio).
  • the cation retention aid is finally prepared by separately copying the two prepared pastes in a laboratory handsheet forming machine, and testing the ash content after the steps of pressing, dehydrating, drying and balancing the two different filler amounts. /T463-1989) and related physical indicators such as tensile index (GB/T453-89). The experimental results are shown in Tables 1 and 2.
  • the filler was selected from ground calcium carbonate (GCC) with a mesh number of 400 mesh, and was prepared by using tap water to prepare a suspension having a solid content of 10%.
  • Starch was selected from corn oxidized starch (Runyuan brand, Shandong Dezhou Runde Starch Co., Ltd.), and prepared into a suspension with a solid content of 2.5% by tap water.
  • One type of flocculant is a cationic polyacrylamide with a weight average molecular weight of 4 million and 25% molar charge (Hefei Xintuo Polymer Technology Co., Ltd. XT81400); the other is a weight average molecular weight of 7 million, 20% molar charge.
  • Anionic polyacrylamide Hefei Xintuo Polymer Technology Co., Ltd., XT80700. Both flocculants were formulated with tap water to prepare a 0.5% solids solution.
  • 250 ml of the above 10% GCC suspension was added to a 1000 ml beaker at a stirring rate of 100 rpm, then 250 ml of the above 2.5% corn oxidized starch suspension was added, stirred and mixed, and divided into 250 ml two aliquots.
  • One of them was pre-flocculated by adding 20 ml of the above 0.5% anionic polyacrylamide solution at a constant rate of 1000 rpm for 30 seconds, and stirring was continued for 30 seconds.
  • Another 250 ml was added to the above-mentioned 0.5% cationic polyacrylamide solution 20 ml at a stirring speed of 1000 rpm for 30 seconds to carry out pre-flocculation, and then stirring was continued for 30 seconds.
  • 250 ml of each of the above two pre-flocs was stirred at 1000 rpm for at least one minute to complete the preparation.
  • the above prepared ternary fillers were separately added to the two pulps according to the 25% absolute dry weight ratio and the 35% absolute dry weight ratio, and then uniformly stirred, and then added according to 0.5 kg/ton (dry weight ratio).
  • the cation retention aid is finally prepared by separately copying the two prepared pastes in a laboratory handsheet forming machine, and testing the ash content after the steps of pressing, dehydrating, drying and balancing the two different filler amounts. /T463-1989) and related physical indicators such as tensile index (GB/T453-89). The experimental results are shown in Tables 1 and 2.
  • the filler is selected from deposited calcium carbonate (PCC), and is prepared by using tap water to prepare a suspension having a solid content of 10%.
  • the original starch is selected from tapioca starch, and is prepared into a suspension having a solid content of 2.5% by tap water.
  • One type of flocculant is a cationic polyacrylamide with a weight average molecular weight of 4 million and 25% molar charge (Hefei Xintuo Polymer Technology Co., Ltd. XT81400); the other is a weight average molecular weight of 7 million, 20% molar charge.
  • Anionic polyacrylamide Hefei Xintuo Polymer Technology Co., Ltd. XT80700. Both flocculants were formulated with tap water to prepare a 0.5% solids solution.
  • 250 ml of the above 10% PCC suspension was added to a 1000 ml beaker, and 20 ml of the above 0.5% anionic polyacrylamide solution was added at a constant rate of 1000 rpm for 30 seconds to carry out pre-flocculation, and then stirring was continued for 30 seconds.
  • 250 ml of the above 2.5% tapioca starch suspension was added to another 1000 ml cake, and 20 ml of the above 0.5% cationic polyacrylamide solution was added at a constant rate of 1000 rpm for 30 seconds, and stirring was continued for 30 seconds.
  • 250 ml of each of the above two pre-flocs was stirred at 1000 rpm for at least one minute to complete the preparation.
  • the above prepared ternary fillers were separately added to the two pulps according to the 25% absolute dry weight ratio and the 35% absolute dry weight ratio, and then uniformly stirred, and then added according to 0.5 kg/ton (dry weight ratio).
  • the cation retention aid is finally prepared by separately copying the two prepared pastes in a laboratory handsheet forming machine, and testing the ash content after the steps of pressing, dehydrating, drying and balancing the two different filler amounts. /T463-1989) and related physical indicators such as tensile index (GB/T453-89). The experimental results are shown in Tables 1 and 2.
  • the filler selected in the present embodiment, the original starch and the two flocculants and the preparation method were the same as those in Example 4 except that the ratio of the filler to the original starch was improved in this example compared with Example 4.
  • the above prepared ternary fillers were separately added to the two pulps according to the 25% absolute dry weight ratio and the 35% absolute dry weight ratio, and then uniformly stirred, and then added according to 0.5 kg/ton (dry weight ratio).
  • the cation retention aid is finally prepared by separately copying the two prepared syrups in a laboratory handsheet forming machine.
  • the ash content and resistance are tested after the steps of pressing, drying, and balancing the two different filler amounts.
  • Zhang index and other related physical indicators such as ash content (GB/T463-1989) and tensile index (GB/T453-89). The experimental results are shown in Tables 1 and 2.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)

Abstract

一种在纸张/纸板制造中使用的三元填料体系，包括用于纸张/纸板生产的三元填料体系，包括如下组分：1)填料；2)淀粉；和3)絮凝剂。以及在纸张/纸板制造中使用的所述三元填料体系的制备方法和所述三元填料体系用于提高纸张/纸板的灰分含量和强度性能的用途。

Description

用于纸张/纸板生产的三元填料体系及其制备方法 技术领域
本发明属于造纸添加剂领域。具体来说，本发明涉及一种在纸张/纸板制造中使用的用于提高纸张或纸板的灰分含量和强度性能的三元填料体系、其制备方法以及所述三元填料体系在纸张或纸板生产中用于同时提高纸张或纸板的灰分含量和强度性能的用途。
背景技术
在纸和纸板的生产中，为了降低成本和改善纸张的光学性能，广泛采用向纸张中加入价格相对低廉的填料。目前较常用的填料包括碳酸钙(研磨碳酸钙(GCC)和沉积碳酸钙(PCC))、滑石粉、二氧化钛、高岭土和硅藻土等。由于填料自身的特性使其用量受限，过度加入会带来很多负面影响，会造成纸张的物理强度的下降并且会影响纸机运行。这是由于固有的物理特性，填料自身无法与纤维之间形成有效的结合，而且还会影响纤维之间的氢键结合，从而导致抄造出来的纸张强度低于未添加填料抄造出来的纸张强度，过度加入还会造成掉粉等问题；并且由于填料颗粒的粒径一般只有几微米，填料与纤维之间的结合力差，在纸张抄造的过程中首程保留率低，导致填料在纸张中的留着率不高，造成大量的填料积累在白水系统中，对纸机湿部运行产生负面影响。造纸过程中的传统填料方式是通过纸机助留系统提高填料的首程保留率。对填料加入造成的纸强度的下降则只能通过增加纸张增强剂用量的方法来解决。
如何提高填料的用量降低生产成本并且同时尽可能地减小对纸张强度性能以及纸机运行的影响，一直是造纸添加剂领域的重点研究领域。填料表面改性是增加造纸填料用量的主要研究方向，因为对填料表面进行改性，降低或消除因为填料存在使得纤维间难形成结合强度的不利影响，为提高纸张中的灰分含量提供了途径。
美国专利US2949397A介绍了一种用聚甘露糖半乳糖胶(角豆荚胶，瓜尔胶等)包裹碳酸钙的填料预处理方法。
美国专利US5147507介绍了一种使用阳离子聚合物对碳酸钙填料进行预处理以降低湿部施胶过程中施胶剂用量，提高填料保留和纸张光学性能及抗张强度的方法。
美国专利US5527430介绍了一种使用憎水化合物(硬脂酸钠等)对碳酸钙填料进行预处理以降低湿部施胶过程中施胶剂用量，提高施胶效率的方法。
美国专利US8088213B2，US8172983B2，US8747617B2介绍了一种使用阳离子和阴离子 双重聚合物体系对碳酸钙填料进行所谓可控的预絮凝处理以达到提高填料的用量和减少抗张强度下降的方法。
美国专利申请US20090020250A1介绍了一种使用阴离子聚多糖和阳离子或两性聚丙烯酰胺对碳酸钙填料进行预处理以增加填料用量的方法。
中国专利CN103397561A介绍了一种首先用阳离子混凝剂与填料混合，然后再和阴离子的合成乳胶进行混合对填料进行改性处理的方法，以获得更高的灰分含量。
众所周知，改性淀粉尤其是阳离子淀粉或两性淀粉经过蒸煮后用于造纸可以取得较为理想的增强、助留、施胶剂乳化等效果。作为纸张增强剂，改性淀粉是应用最为广泛且成本最为经济的增强和助留剂之一。使用改性淀粉对填料进行表面改性的研究亦见于诸多专利文献。
美国专利US3873336介绍了一种使用阳离子改性淀粉和阴离子改性淀粉混合物对碳酸钙填料进行预处理以提高填料在酸性造纸条件下稳定性的方法。
美国专利US4115187介绍了一种使用有机聚合物、改性淀粉或海藻酸钠盐，对碳酸钙填料进行预处理以提高填料在酸性造纸条件下稳定性的方法。
美国专利7074845B2介绍了一种使用阴离子聚合物胶乳与阳离子润涨淀粉对填料进行改性处理以获得更高的内结合强度和抗张强度的方法。
中国专利CN102363932A介绍了一种使用改性淀粉糊液和助留剂对填料进行在线改性处理以获得更高的纸张灰分含量的方法。
中国专利CN103352395A介绍了一种使用阳离子淀粉和阳离子淀粉交联剂对填料进行改性处理，可以获得更高的填料用量的方法。。
以上现有技术文献所述的改性淀粉主要是在蒸煮熟化后用于填料表面改性，其中大多只是通过表面改性的方法使得填料在提高用量的同时尽可能地减小对纸张强度的影响。所公开的填料体系中均未提及提高填料用量的同时可以提高纸张强度的体系。
针对现有技术的问题，本发明提供了一种在纸张(或纸板)生产中使用的填料-淀粉-絮凝剂三元填料体系添加剂，所述三元填料体系可以同时提高纸张/纸板的灰分含量和强度性能。
发明内容
本发明公开了一种用于纸张/纸板生产的三元填料体系，其可以同时提高纸张(或纸板)的灰分含量和强度性能。
一种用于纸张/纸板生产的三元填料体系，包括如下组分：1)填料；2)淀粉；和3)絮凝剂，其中所述填料与淀粉的干重比为大约200∶1至1∶10，所述絮凝剂的加入量以所述填料与淀粉 的干重重量之和为基础计为大约0.05％-5％。
本发明所使用的填料是众所周知、商业可得的任何造纸用填料。代表性填料的实例包括碳酸钙、高岭土、滑石粉、二氧化钛、氢氧化铝等等。其中碳酸钙主要包括研磨碳酸钙(GCC)和沉积碳酸钙(PCC)。碳酸钙可以为分散性碳酸钙或非分散性碳酸钙。分散性GCC和PCC通常是用聚丙烯酸聚合物分散剂或聚磷酸钠分散剂制备。这些分散剂赋予碳酸钙颗粒显著的阴离子电荷。在分散性碳酸钙(GCC和PCC)的情况下，尤其适合使用所述的单一絮凝剂；在非分散性碳酸钙(GCC和PCC)的情况下，尤其适合使用所述的相反电荷的两种絮凝剂组合。
在本发明中，所述填料通常制备成大约1～30重量％的填料水悬浮液使用。
本发明使用的淀粉是没有经过任何改性处理(包括阳离子化、阴离子化或两性改性)，也没有经过蒸煮糊化的原始淀粉；或者是未经蒸煮糊化的氧化淀粉。所述原始淀粉或氧化淀粉的原料选自玉米淀粉、木薯淀粉、马铃薯淀粉和小麦淀粉的其中一种或几种组合。
在本发明中，所述淀粉通常制备成大约0.5～5重量％的淀粉水悬浮液不经过蒸煮糊化直接使用。
在本发明中，所使用的絮凝剂为单一絮凝剂或相反电荷的两种絮凝剂组合。
所述絮凝剂为重均分子量100万以上的阳离子聚合物和重均分子量100万以上的阴离子聚合物。适宜的阳离子和阴离子聚合物的电荷含量一般小于50mol％。
适用于本发明的阳离子聚合物包括(甲基)丙烯酰胺与甲基丙烯酸二甲氨基乙酯(DMAEM)、丙烯酸二甲氨基乙酯(DMAEA)、甲基丙烯酸二乙氨基乙酯(DEAEA)、甲基丙烯酸二乙氨基乙酯(DEAEM)或其季铵盐形式的共聚物和三聚物。
适用于本发明的阴离子聚合物包括丙烯酰胺与丙烯酸钠和/或2-丙烯酰氨基-2-甲基丙磺酸(AMPS)的共聚物或已经被水解以将部分丙烯酰胺基团转化为丙烯酸的丙烯酰胺均聚物。
在本发明中，所述絮凝剂通常制备成乳液然后稀释到0.2-2重量％使用。
本发明进一步涉及用于制备根据本发明的三元填料体系的方法，包括如下步骤：
1)预先制备填料的水悬浮液和预先制备淀粉的水悬浮液；
2)把步骤1)所得的两种水悬浮物与絮凝剂用不同混合方式进行混合，在适宜的剪切条件下得到三元填料体系。
其中剪切条件根据搅拌设备与填料的固含量选择，搅拌时间通常为5秒-5分钟，搅拌速率为速率100rpm-3000rpm，温度通常为0到50度。
其中所述絮凝剂的加入方式例如可以是单絮凝剂加入到步骤1)中所得两种水悬浮物的混合物中，其中填料与淀粉的干重比为大约200∶1至1∶10；或两种携带相反电荷的絮凝剂依次 加入到步骤1)中所得两种水悬浮物的混合物中；或者两种携带相反电荷的絮凝剂与比例为20∶80至80∶20步骤1)中所得水悬浮物的混合物分别混合进行预絮凝，然后将两种预絮凝物再进行混合；或者两种携带相反电荷的絮凝剂分别与步骤1)所得的两种水悬浮物分别混合进行预絮凝，然后将两种预絮凝物进行混合。
在根据本发明的方法的一个实施方案中，所述方法包括如下步骤：
1)把预先制备的1～30％浓度的填料水悬浮液，和预先制备的0.5～5重量％浓度的原始淀粉或氧化淀粉水悬浮液，混合均匀；
2)在上述混合液中加入单一的阳离子絮凝剂或阴离子絮凝剂或两性离子絮凝剂，混合絮凝制备得到三元填料体系。
在根据本发明的方法的另一个实施方案中，用于制备根据本发明的三元填料体系添加剂的方法，包括如下步骤：
1)把预先制备的1～30％浓度的填料水悬浮液，和预先制备的0.5～5％浓度的原始淀粉或氧化淀粉水悬浮液，混合均匀；
2)在上述混合液中加入阴离子絮凝剂，混合进行预絮凝；
3)然后在步骤2)获得的产物中加入阳离子絮凝剂，混合絮凝制备得到三元填料体系。
在根据本发明的方法的又一个实施方案中，用于制备根据本发明的三元填料体系添加剂的方法，包括如下步骤：
1)把预先制备的1～30％浓度的填料水悬浮液，和预先制备的0.5～5％浓度的原始淀粉或氧化淀粉水悬浮液，混合均匀；
2)把步骤1)中制得的混合物分成两份，两份的比例在20∶80至80∶20之间为宜，在其中一份中加入阴离子絮凝剂，混合进行预絮凝；在另外一份中加入阳离子絮凝剂，混合进行预絮凝；
3)然后把步骤2)中得到的两种预絮凝物，混合絮凝制备得到三元填料体系。
在根据本发明的方法的又一个实施方案中，用于制备根据本发明的三元填料体系添加剂的方法，包括如下步骤：
1)在预先制备的1～30％浓度的填料水悬浮液中加入第一种絮凝剂，混合进行预絮凝；
2)在预先制备的0.5～5％浓度的原始淀粉或氧化淀粉水悬浮液中加入与第一种絮凝剂携带电荷相反的第二种絮凝剂，(就是说，如果第一种絮凝剂是阳离子的，那么第二种是阴离子的，反之亦然)，混合进行预絮凝；
3)然后把1)和2)制得的两种预絮凝物，混合絮凝制备完成。
根据本发明的制备方法可以采取在线方式，也可以为离线式，即可以与纸机操作同步进行或者在纸机操作前先预制好。
在纸张/纸板生产过程中，将根据本发明的三元填料体系经由纸机的通常填料加入口加入，其可以同时提高纸张/纸板的灰分含量和强度性能。并且，现有技术使用的淀粉绝大多数是改性淀粉同时需要蒸煮糊化后作为干强剂加入，淀粉浓度由于蒸煮糊化工艺所限最多2-4％，本发明的三元填料体系直接用原始未改性淀粉或氧化淀粉，浓度不受蒸煮工艺限制最高可在30％以上。另外，原始未改性淀粉或氧化淀粉的价格远远低于改性淀粉，并且本发明的方法也不涉及蒸煮工艺的运行成本，所以大大降低了生成成本。
因此，本发明进一步涉及根据本发明的三元填料体系用于在纸张和/或纸板生产中提高纸张/纸板的灰分含量和强度性能的用途。
所述作用的机理应该是在所述三元填料体系中，填料不仅被絮凝剂表面改性，而且可以通过两种相反电荷的双絮凝剂的制备方法得以和原始淀粉或氧化淀粉产生共絮凝物，在共絮凝物中，填料可以被原始淀粉或氧化淀粉有效包裹产生稳定的具有抗剪切能力的共絮凝物。在加入纸机湿部后，由于包裹在外的淀粉与纤维可以形成很好的键合，从而解决了纸张强度和加填量的矛盾关系，可以达到同时提高加填量(灰分含量)和纸张强度的效果。
另外，没有经过任何改性处理和蒸煮溶胀糊化的原始淀粉或未经蒸煮糊化的氧化淀粉，可以依靠和填料在两种相反电荷的双絮凝剂的作用下形成稳定的共絮凝物而在纸板的生产过程中得以比较高的首程保留率和比较好的匀度保留在纸张成形部，这样保留的原始淀粉或氧化淀粉能够从纸机烘缸部位获得足够的胶化热量最后熟化成稳定的增强剂。这样得到的纸张增强效果比现有技术中使用喷淋淀粉得到的增强效果更好。因为喷淋淀粉多数集中分布在纸与纸的层间，难以达到提高本发明原始淀粉或氧化淀粉对纸张整体增强的效果。
现有技术一般使用改性淀粉且经过蒸煮糊化后再加入浆料，是因为未经蒸煮糊化的原始淀粉或氧化淀粉直接加入浆料的首程保留率很差，导致大量的加入浆内的未经蒸煮糊化的原始淀粉或氧化淀粉穿过纸机的成形部进入网坑白水，造成白水浓度过高，从而导致纸机操作困难且对施胶和其他化学品的使用带来不利影响。因此在现有技术基础上直接加入未经蒸煮糊化的原始淀粉或氧化淀粉必须大量使用保留助剂，这会造成纸张成形困难，影响纸张匀度，同时所述淀粉的加入量也受到极大限制。在本发明的三元体系中，未经蒸煮糊化的原始淀粉或氧化淀粉和填料在适宜的絮凝剂作用下，在适宜的剪切条件下可以形成剪切稳定的共预絮凝物，其颗粒尺寸比单独的未经蒸煮糊化的原始淀粉或氧化淀粉以及填料的颗粒尺寸大一个数量级。所形成的三元填料可以在不提高保留助剂用量的情况下在纸机的成形部有很高的首 程保留率，并且淀粉的加入量可以根据纸张强度的要求而确定进入量。
具体实施方式
以下结合实施例对本发明作进一步详细描述，这些实施例仅为说明的目的，而不是要限制本发明的范围。
本发明的实施例中使用的填料与淀粉均可市购得到。
对比实施例1
将目数为400目的研磨碳酸钙(GCC)(广东强大化工有限公司CAZ-400)用自来水配制成固含量10％的悬浮液备用，和将木薯淀粉(中山市弘益工业原料有限公司，HONGYI，细度200目以上)用自来水配制成固含量为2.5％的悬浮液备用。
在1000毫升的烧杯中在100rmp搅拌速度下加入250毫升上述的10％的GCC悬浮液，然后加入250毫升上述的2.5％的木薯淀粉悬浮液，搅拌混合均匀后，在1000rmp搅拌速度下最后搅拌至少一分钟完成制备。
漂白针叶硫酸盐木浆和漂白阔叶硫酸盐木浆按30∶70的比例共同疏解打浆，制备成1％浓度的混合纸浆。将上述制备好的填料体系按照25％绝干重量比和35％绝干重量比两种不同加入量分别加入两份纸浆中搅拌均匀，然后分别按照0.5千克/吨(干重比)加入阳离子保留助剂(德国巴斯夫PERCOL 182)，最后将两份配好的浆料在实验室手抄纸成型机中分别抄造成型，两种不同填料用量的纸样经压榨脱水、干燥、平衡等步骤后测试灰分含量(GB/T463-1989)与抗张指数(GB/T453-89)等相关物理指标。实验结果见表1和表2。
实施例1
填料选用分散性PCC浆料(广东强大新材料科技有限公司，产品型号6150)，用自来水稀释配制成固含量10％的悬浮液备用。原始淀粉选用木薯淀粉，用自来水配制成固含量为2.5％的悬浮液备用。单一絮凝剂选用重均分子量400万，25％摩尔电荷量的阳离子聚丙烯酰胺(合肥信拓高分子技术有限公司XT81400(丙烯酰胺与二甲基二丙烯基氯化铵的共聚物))；用自来水配制成固含量为0.5％溶液备用。
在1000毫升的烧杯中在100rmp搅拌速度下加入250毫升上述的10％的PCC悬浮液，然后加入250毫升上述的2.5％的木薯淀粉悬浮液，搅拌混合均匀后，在1000rmp搅拌速度下在30秒内匀速加入上述的0.5％阴离子聚丙烯酰胺溶液40毫升进行絮凝，最后搅拌至少一分钟完成制备。
漂白针叶硫酸盐木浆和漂白阔叶硫酸盐木浆按30∶70的比例共同疏解打浆，制备成1％ 浓度的混合纸浆。将上述制备好的三元填料物按照25％绝干重量比和35％绝干重量比两种不同加入量分别加入两份纸浆中搅拌均匀，然后分别按照0.5千克/吨(干重比)加入阳离子保留助剂，最后将两份配好的浆料在实验室手抄纸成型机中分别抄造成型，两种不同填料用量的纸样经压榨脱水、干燥、平衡等步骤后测试灰分含量(GB/T463-1989)与抗张指数(GB/T453-89)等相关物理指标。实验结果见表1和表2。
实施例2
填料选用研磨碳酸钙(GCC)，目数为400目，用自来水配制成固含量10％的悬浮液备用。原始淀粉选用木薯淀粉，用自来水配制成固含量为2.5％的悬浮液备用。两种絮凝剂一种选用重均分子量400万，25％摩尔电荷量的阳离子聚丙烯酰胺(合肥信拓高分子技术有限公司XT81400)；另外一种选用重均分子量700万，20％摩尔电荷量的阴离子聚丙烯酰胺(合肥信拓高分子技术有限公司XT80700(丙烯酰胺与丙烯酸的共聚物))。这两种絮凝剂都用自来水配制成固含量为0.5％溶液备用。
在1000毫升的烧杯中在100rmp搅拌速度下加入250毫升上述的10％的GCC悬浮液，然后加入250毫升上述的2.5％的木薯淀粉悬浮液，搅拌混合均匀后，在1000rmp搅拌速度下首先在30秒内匀速加入上述的0.5％阴离子聚丙烯酰胺溶液20毫升进行预絮凝，然后继续搅拌30秒后，在1000rmp搅拌速度下在30秒内匀速加入上述的0.5％阳离子聚丙烯酰胺溶液20毫升，最后搅拌至少一分钟完成制备。
漂白针叶硫酸盐木浆和漂白阔叶硫酸盐木浆按30∶70的比例共同疏解打浆，制备成1％浓度的混合纸浆。将上述制备好的三元填料物按照25％绝干重量比和35％绝干重量比两种不同加入量分别加入两份纸浆中搅拌均匀，然后分别按照0.5千克/吨(干重比)加入阳离子保留助剂，最后将两份配好的浆料在实验室手抄纸成型机中分别抄造成型，两种不同填料用量的纸样经压榨脱水、干燥、平衡等步骤后测试灰分含量(GB/T463-1989)与抗张指数(GB/T453-89)等相关物理指标。实验结果见表1和表2。
实施例3
填料选用研磨碳酸钙(GCC)，目数为400目，用自来水配制成固含量10％的悬浮液备用。淀粉选用玉米氧化淀粉(润源牌，山东德州润德淀粉有限公司)，用自来水配制成固含量为2.5％的悬浮液备用。两种絮凝剂一种选用重均分子量400万，25％摩尔电荷量的阳离子聚丙烯酰胺(合肥信拓高分子技术有限公司XT81400)；另外一种选用重均分子量700万，20％摩尔电荷量的阴离子聚丙烯酰胺(合肥信拓高分子技术有限公司，XT80700)。这两种絮凝剂都用自来水配制成固含量为0.5％溶液备用。
在1000毫升的烧杯中在100rmp搅拌速度下加入250毫升上述的10％的GCC悬浮液，然后加入250毫升上述的2.5％的玉米氧化淀粉悬浮液，搅拌混合均匀后分成各250毫升两等份，其中一份在1000rmp搅拌速度下在30秒内匀速加入上述的0.5％阴离子聚丙烯酰胺溶液20毫升进行预絮凝，然后继续搅拌30秒。另外一份250毫升在1000rmp搅拌速度下在30秒内匀速加入上述的0.5％阳离子聚丙烯酰胺溶液20毫升进行预絮凝，然后继续搅拌30秒。最后以上两种预絮凝物各250毫升在1000rmp搅拌速度下搅拌至少一分钟完成制备。
将上述制备好的三元填料物按照25％绝干重量比和35％绝干重量比两种不同加入量分别加入两份纸浆中搅拌均匀，然后分别按照0.5千克/吨(干重比)加入阳离子保留助剂，最后将两份配好的浆料在实验室手抄纸成型机中分别抄造成型，两种不同填料用量的纸样经压榨脱水、干燥、平衡等步骤后测试灰分含量(GB/T463-1989)与抗张指数(GB/T453-89)等相关物理指标。实验结果见表1和表2。
实施例4
填料选用沉积碳酸钙(PCC)，用自来水配制成固含量10％的悬浮液备用。原始淀粉选用木薯淀粉，用自来水配制成固含量为2.5％的悬浮液备用。两种絮凝剂一种选用重均分子量400万，25％摩尔电荷量的阳离子聚丙烯酰胺(合肥信拓高分子技术有限公司XT81400)；另外一种选用重均分子量700万，20％摩尔电荷量的阴离子聚丙烯酰胺(合肥信拓高分子技术有限公司XT80700)。这两种絮凝剂都用自来水配制成固含量为0.5％溶液备用。
在1000毫升的烧杯中加入250毫升上述的10％的PCC悬浮液，在1000rmp搅拌速度下，30秒内匀速加入上述的0.5％阴离子聚丙烯酰胺溶液20毫升进行预絮凝，然后继续搅拌30秒。在另外一个1000毫升的烧饼中加入250毫升上述的2.5％的木薯淀粉悬浮液，在1000rmp搅拌速度下在30秒内匀速加入上述的0.5％阳离子聚丙烯酰胺溶液20毫升，然后继续搅拌30秒。最后以上两种预絮凝物各250毫升在1000rmp搅拌速度下搅拌至少一分钟完成制备。
将上述制备好的三元填料物按照25％绝干重量比和35％绝干重量比两种不同加入量分别加入两份纸浆中搅拌均匀，然后分别按照0.5千克/吨(干重比)加入阳离子保留助剂，最后将两份配好的浆料在实验室手抄纸成型机中分别抄造成型，两种不同填料用量的纸样经压榨脱水、干燥、平衡等步骤后测试灰分含量(GB/T463-1989)与抗张指数(GB/T453-89)等相关物理指标。实验结果见表1和表2。
实施例5
本实施例选用的填料，原始淀粉和两种絮凝剂以及制备方法与实施例4相同，不同之处在于本实施例与实施例4相比提高了填料和原始淀粉的比例。
在1000毫升的烧杯中加入250毫升的10％的PCC悬浮液，在1000rmp搅拌速度下，30秒内匀速加入0.5％阴离子聚丙烯酰胺溶液20毫升进行预絮凝，然后继续搅拌30秒。在另外一个500毫升的烧饼中加入125毫升的2.5％的木薯淀粉悬浮液，在1000rmp搅拌速度下在30秒内匀速加入上述的0.5％阳离子聚丙烯酰胺溶液10毫升，然后继续搅拌30秒。最后以上两种预絮凝物共325毫升在1000rmp搅拌速度下搅拌至少一分钟完成制备。
将上述制备好的三元填料物按照25％绝干重量比和35％绝干重量比两种不同加入量分别加入两份纸浆中搅拌均匀，然后分别按照0.5千克/吨(干重比)加入阳离子保留助剂，最后将两份配好的浆料在实验室手抄纸成型机中分别抄造成型，两种不同填料用量的纸样经压榨脱水、干燥、平衡等步骤后测试灰分含量与抗张指数等灰分含量(GB/T463-1989)与抗张指数(GB/T453-89)等相关物理指标。实验结果见表1和表2。
表1.实施例1-5与对比实施例1的三元填料物按照25％绝干重量比加入量的手抄纸灰分含量与抗张指数等灰分含量与抗张指数等相关物理指标
  灰分含量(％) 抗张指数(N.m/g)
对比实施例1 16.1 27.2
实施例1 18.5 35.8
实施例2 18.9 36.1
实施例3 18.8 36.7
实施例4 18.6 35.5
实施例5 21.0 29.2
表2.实施例1-5与对比实施例1的三元填料物按照35％绝干重比加入量的手抄纸灰分含量与抗张指数等灰分含量与抗张指数等相关物理指标
  灰分含量(％) 抗张指数(N.m/g)
对比实施例1 21.1 23.9
实施例1 24.7 30.7
实施例2 25.6 30.9
实施例3 25.9 30.7
实施例4 25.5 30.0
实施例5 27.6 25.2
由表1和表2的实验数据可以看出，依据本发明所提供的三元填料体系实施方法所抄造出来的纸张的填料的留着率、纸张的灰分含量以及纸张的强度性能参数上均有显著的提高。
以上对本发明做了详尽的描述，其目的在于让本领域技术人员能够了解本发明的内容并加以实施，并不能以此限制本发明的保护范围，凡根据本发明的精神实质所作的等效变化或改变，都应涵盖在本发明的保护范围内。

Claims (13)

  1. 一种用于纸张/纸板生产的三元填料体系，包括如下组分：1)填料；2)淀粉；和3)絮凝剂。
  2. 根据权利要求1所述的用于纸张/纸板生产的三元填料体系，其中所述填料与所述淀粉的干重比为200∶1至1∶10，所述絮凝剂的加入量以所述填料与淀粉的干重总重量为基础计为0.05％-5％。
  3. 根据权利要求1所述的用于纸张/纸板生产的三元填料体系，其中所述填料为任何造纸填料，其选自碳酸钙、高岭土、滑石粉、二氧化钛和氢氧化铝中的一种或几种组合；所述碳酸钙优选研磨碳酸钙和沉积碳酸钙；和所述碳酸钙可以是分散性的或非分散性的。
  4. 根据权利要求1所述的用于纸张/纸板生产的三元填料体系，其中所述淀粉是没有经过任何改性处理，也没有经过蒸煮糊化的原始淀粉，或者是没有经过蒸煮糊化的氧化淀粉。
  5. 根据权利要求4所述的用于纸张/纸板生产的三元填料体系，其中所述未经蒸煮糊化的原始淀粉或氧化淀粉的淀粉原料选自玉米淀粉、木薯淀粉、马铃薯淀粉和小麦淀粉其中的一种或几种组合。
  6. 根据权利要求1所述的用于纸张/纸板生产的三元填料体系，其中所述絮凝剂为单一絮凝剂或相反电荷的两种絮凝剂组合；所述絮凝剂重均分子量为100万以上，其电荷含量小于50mol％；在填料为分散性碳酸钙的情况下，所述絮凝剂优选为单一絮凝剂，在填料为非分散性碳酸钙的情况下，所述絮凝剂优选为带有相反电荷的两种絮凝剂组合。
  7. 根据权利要求6所述的用于纸张/纸板生产的三元填料体系，其中所述单一絮凝剂可以为阳离子絮凝剂，或阴离子絮凝剂，或两性絮凝剂；所述相反电荷的两种絮凝剂组合的其中一种为阳离子絮凝剂，另外一种为阴离子絮凝剂；例如，所述阳离子聚合物优选包括(甲基)丙烯酰胺与甲基丙烯酸二甲氨基乙酯、丙烯酸二甲氨基乙酯、甲基丙烯酸二乙氨基乙酯、甲基丙烯酸二乙氨基乙酯(DEAEM)或其季铵盐形式的共聚物和三聚物；所述阴离子聚合物优选包括丙烯酰胺与丙烯酸钠和/或2-丙烯酰氨基-2-甲基丙磺酸(AMPS)的共聚物或已经被水解以将部分丙烯酰胺基团转化为丙烯酸的丙烯酰胺均聚物。
  8. 前面权利要求1-7中任一项所述的用于纸张/纸板生产的三元填料体系的制备方法，包括如下步骤：
    1)把预先制备的填料水悬浮液和预先制备的淀粉水悬浮液混合均匀；
    2)在上述混合液中加入单一的阳离子絮凝剂或阴离子絮凝剂或两性离子絮凝剂，进行混 合和絮凝制备得到三元填料体系。
  9. 前面权利要求1-7中任一项所述的用于纸张/纸板生产的三元填料体系的制备方法，包括如下步骤：
    1)把预先制备的填料水悬浮液和预先制备的淀粉水悬浮液混合均匀；
    2)在上述混合液中加入阴离子絮凝剂，进行混合和预絮凝；
    3)然后在2)中加入阳离子絮凝剂，进行混合和絮凝制备得到三元填料体系。
  10. 前面权利要求1-7中任一项所述的用于纸张/纸板生产的三元填料体系的制备方法，包括如下步骤：
    1)把预先制备的填料水悬浮液和预先制备的淀粉水悬浮液混合均匀；
    2)把1)中制得的混合物分成两份，两份的比例在20∶80至80∶20之间；在其中一份中加入阴离子絮凝剂，进行混合和预絮凝；在另外一份中加入阳离子絮凝剂，进行混合和预絮凝；
    3)然后把2)中得到的两种预絮凝物混合絮凝制备得到三元填料体系。
  11. 前面权利要求1-7中任一项所述的用于纸张/纸板生产的三元填料体系的制备方法，包括如下步骤：
    1)在预先制备的填料水悬浮液中加入第一种絮凝剂，进行混合和预絮凝；
    2)在预先制备的淀粉水悬浮液中加入与第一种絮凝剂携带电荷相反的第二种絮凝剂，进行混合和预絮凝；
    3)然后将1)和2)制得的两种预絮凝物进行混合絮凝制备完成。
  12. 根据权利要求8-10中任一项所述的制备方法，其中所述填料水悬浮液的浓度为1-30重量％，所述淀粉水悬浮液的浓度为0.5-5重量％，所述絮凝剂以0.2-2重量％的乳液使用。
  13. 根据权利要求1-7任一项所述的用于纸张/纸板生产的三元填料体系在纸张/纸板生产过程中用于提高纸张/纸板的灰分含量和强度性能的用途。
PCT/CN2016/000203 2016-04-15 2016-04-15 用于纸张/纸板生产的三元填料体系及其制备方法 WO2017177349A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2016/000203 WO2017177349A1 (zh) 2016-04-15 2016-04-15 用于纸张/纸板生产的三元填料体系及其制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2016/000203 WO2017177349A1 (zh) 2016-04-15 2016-04-15 用于纸张/纸板生产的三元填料体系及其制备方法

Publications (1)

Publication Number Publication Date
WO2017177349A1 true WO2017177349A1 (zh) 2017-10-19

Family

ID=60042730

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2016/000203 WO2017177349A1 (zh) 2016-04-15 2016-04-15 用于纸张/纸板生产的三元填料体系及其制备方法

Country Status (1)

Country Link
WO (1) WO2017177349A1 (zh)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114561833A (zh) * 2022-02-28 2022-05-31 山东博汇纸业股份有限公司 一种单层白浆挂面白面牛卡纸的生产方法
CN115491931A (zh) * 2021-11-11 2022-12-20 京准化工技术(上海)有限公司 一种无氟纸浆模塑产品及其制备方法
CN115584006A (zh) * 2022-12-12 2023-01-10 山东奥赛新材料有限公司 一种三元结合干强剂、制备方法及应用

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4609432A (en) * 1981-05-21 1986-09-02 Brooks Rand Ltd. Method of making paper having improved tearing strength
GB2223038A (en) * 1988-09-26 1990-03-28 Blue Circle Ind Plc Starch-flocculant compositions for papaermaking
US5876563A (en) * 1994-06-01 1999-03-02 Allied Colloids Limited Manufacture of paper
CN1238019A (zh) * 1996-11-19 1999-12-08 西巴特殊化学水处理有限公司 纸的生产方法
CN101802304A (zh) * 2007-09-12 2010-08-11 纳尔科公司 使用双聚合物系统的可控制的填料预絮凝
CN104755673A (zh) * 2012-11-01 2015-07-01 纳尔科公司 用于造纸中的填料的预絮凝
CN104781469A (zh) * 2012-10-05 2015-07-15 特种矿物（密歇根）有限公司 填料悬浮液及其在造纸中的应用

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4609432A (en) * 1981-05-21 1986-09-02 Brooks Rand Ltd. Method of making paper having improved tearing strength
GB2223038A (en) * 1988-09-26 1990-03-28 Blue Circle Ind Plc Starch-flocculant compositions for papaermaking
US5876563A (en) * 1994-06-01 1999-03-02 Allied Colloids Limited Manufacture of paper
CN1238019A (zh) * 1996-11-19 1999-12-08 西巴特殊化学水处理有限公司 纸的生产方法
CN101802304A (zh) * 2007-09-12 2010-08-11 纳尔科公司 使用双聚合物系统的可控制的填料预絮凝
CN104781469A (zh) * 2012-10-05 2015-07-15 特种矿物（密歇根）有限公司 填料悬浮液及其在造纸中的应用
CN104755673A (zh) * 2012-11-01 2015-07-01 纳尔科公司 用于造纸中的填料的预絮凝

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115491931A (zh) * 2021-11-11 2022-12-20 京准化工技术(上海)有限公司 一种无氟纸浆模塑产品及其制备方法
CN114561833A (zh) * 2022-02-28 2022-05-31 山东博汇纸业股份有限公司 一种单层白浆挂面白面牛卡纸的生产方法
CN115584006A (zh) * 2022-12-12 2023-01-10 山东奥赛新材料有限公司 一种三元结合干强剂、制备方法及应用
CN115584006B (zh) * 2022-12-12 2023-02-28 山东奥赛新材料有限公司 一种三元结合干强剂、制备方法及应用

Similar Documents

Publication Publication Date Title
RU2311507C2 (ru) Составы набухшего крахмала-латекса, применяемые при изготовлении бумаги
TWI515348B (zh) 填料組合物
RU2585785C1 (ru) Обработка материалов, содержащих карбонат кальция, для повышения количества наполнителя в бумаге
US20150197892A1 (en) Filler suspension and its use in the manufacture of paper
EP2938783B1 (en) Method of increasing paper strength by using natural gums and dry strength agent in the wet end
CN107675556B (zh) 一种造纸填料的现场包覆预絮聚改性方法
JP6122103B2 (ja) 製紙における脱水、シート湿潤ウエブ強度および湿潤強度を向上させる方法
CN103038419A (zh) 造纸中提高填料含量的方法
CA2934998C (en) Filler aggregate composition and its production
KR20150085762A (ko) 건조 단부 강도용 습윤 단부 화학물질
WO2017177349A1 (zh) 用于纸张/纸板生产的三元填料体系及其制备方法
EP1395703B1 (en) Aqueous composition
CN104831580A (zh) 一种改性碳酸钙的制备方法
JP2720460B2 (ja) 製紙方法
JPH04281094A (ja) 紙の製造方法
JP2751238B2 (ja) 製紙方法
AU2006201187B2 (en) Swollen starch compositions for use in papermaking
CA3037000A1 (en) Increased drainage performance in papermaking systems using microfibrillated cellulose
WO2001051707A1 (en) The use of inorganic sols in the papermaking process

Legal Events

Date Code Title Description
NENP Non-entry into the national phase

Ref country code: DE

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16898169

Country of ref document: EP

Kind code of ref document: A1

122 Ep: pct application non-entry in european phase

Ref document number: 16898169

Country of ref document: EP

Kind code of ref document: A1