WO2023103093A1 - Preparation method and application for water-based coating containing carboxymethyl modified cellulose nanofibers - Google Patents

Preparation method and application for water-based coating containing carboxymethyl modified cellulose nanofibers Download PDF

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WO2023103093A1
WO2023103093A1 PCT/CN2021/140385 CN2021140385W WO2023103093A1 WO 2023103093 A1 WO2023103093 A1 WO 2023103093A1 CN 2021140385 W CN2021140385 W CN 2021140385W WO 2023103093 A1 WO2023103093 A1 WO 2023103093A1
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coating
modified cellulose
cellulose nanofibers
water
carboxymethyl
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PCT/CN2021/140385
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French (fr)
Chinese (zh)
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卢深
金凯妍
白雪纯
陈天影
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衢州市华顺钙业有限公司
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Publication of WO2023103093A1 publication Critical patent/WO2023103093A1/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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/40—Coatings with pigments characterised by the pigments siliceous, e.g. clays
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/385—Oxides, hydroxides or carbonates
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/52—Cellulose; Derivatives thereof
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/54—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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/60—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters
    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/64—Inorganic compounds
    • 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
    • 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
    • D21H21/16—Sizing or water-repelling agents

Definitions

  • the invention relates to the field of preparation of papermaking coatings, in particular to a water-based coating containing carboxymethyl-modified cellulose nanofibers and an application thereof.
  • Cellulose nanofibers are semi-rigid polymers with diameters less than 100 nanometers. It is mainly obtained by connecting ⁇ -d-glucose rings through 1,4- ⁇ -glucosidic bonds. It has good binding properties, hydrophilicity, degree of polymerization, crystallinity, etc., and is widely used in coatings, textiles, food packaging, papermaking, etc. The field has broad application prospects.
  • cellulose nanofibers Since the surface of cellulose nanofibers contains a large number of active groups (carboxyl groups, hydroxyl groups), it has a strong ability to absorb water molecules. With the increase of cellulose nanofiber content, the water retention performance, ink absorption and barrier properties of the coatings were all significantly improved. However, due to the large number of hydroxyl groups on the surface of cellulose nanofibers, there are strong hydrogen bonds within and between molecules, which can easily lead to irreversible agglomeration, thereby affecting the dispersion stability and other related properties of the coating.
  • active groups carboxyl groups, hydroxyl groups
  • Common modification methods include surface adsorption, chemical grafting, and graft copolymerization.
  • the surface adsorption modification method (physical adsorption method) is to use physical methods to adsorb specific substances on the surface of nanocellulose, so that nanocellulose can maintain stable performance in special environments such as high temperature, high salt, and high shear.
  • the graft copolymerization method refers to the grafting of functional groups onto the surface of nanocellulose to reduce the hydrogen bonding force within and between molecules and endow it with various excellent properties.
  • Molecular grafting modification methods can generally be divided into carboxymethylation modification, silanization modification, sulfonation modification, acetylation modification, cationic modification and TEMPO oxidation modification.
  • Carboxymethyl modification is a commonly used chemical modification method.
  • Carboxymethyl is used to replace the hydrogen on the hydroxyl group of cellulose to make the cellulose surface have a higher electronegativity. properties, thereby improving the dispersion and stability of cellulose nanofibers.
  • Carboxymethyl-modified cellulose nanofibers have broad application prospects in the fields of coatings, textiles, food packaging, and papermaking.
  • the invention provides a water-based coating containing carboxymethyl-modified cellulose nanofibers and an application thereof.
  • One aspect of the present invention provides a kind of preparation method containing the water-based paint of carboxymethyl modified cellulose nanofiber, the method comprises the following steps:
  • the fixed speed is 2000rpm/min
  • the polyvinyl alcohol solution as the main adhesive is added to the above dispersion system and stirred for 5 minutes;
  • control speed is 2000rpm/min
  • cornstarch, chitosan, carboxymethyl modified cellulose nanofibers and trace defoamers are added in order, and the addition interval of each component is 5min;
  • Another aspect of the present invention also provides the application of a water-based coating containing carboxymethyl-modified cellulose nanofibers in paper.
  • the coated paper is dried at room temperature, and then dried at 50-200° C. in an electric blast drying oven to obtain the coated paper containing carboxymethyl-modified cellulose nanofibers.
  • the mass ratio of calcium carbonate to superfine kaolin is 1:1.86. Based on the total amount of calcium carbonate and superfine kaolin, the remaining components are: 0.1% sodium hydroxide, 0.8% sodium hexametaphosphate, 6% corn starch, 12% polyvinyl alcohol, and 0.5% chitosan .
  • the degree of substitution of the carboxymethyl-modified cellulose nanofibers is 0.10-0.47, preferably 0.47.
  • the added amount of carboxymethyl-modified cellulose nanofibers (based on the total amount of calcium carbonate and ultrafine kaolin added) is 0.10%-0.40%, preferably 0.20%.
  • the coating amount of the coating is 1-15g/m 2 , preferably 10g/m 2 (in order to ensure the performance, cost and coating effect of the coated paper, the effect is best at this coating amount).
  • the coating speed is 1-20m/min, preferably 5m/min (in order to ensure the coating amount and the uniformity of coating, the coating liquid with a solid content higher than 40% has the best coating effect at this speed), dry
  • the time is 50-200°C, preferably 105°C (in order to avoid excessive drying time and paper curling, the drying effect of coated paper is best at this temperature).
  • the present invention uses water as the dispersion medium, the paint components are environmentally friendly, the paint preparation process is simple, the coating process is easy to scale up, suitable for large-scale production, and the production cost is low.
  • the invention provides an effective technical solution for the high-value application of cellulose nanofibers in papermaking coatings.
  • the present invention focuses on utilizing carboxymethyl-modified cellulose nanofibers to effectively improve the rheological properties and water retention properties of papermaking coatings, and establishes a preparation method for water-based coatings containing carboxymethyl-modified cellulose nanofibers.
  • the present invention applies the paper-making coating containing carboxymethyl-modified cellulose nanofibers on the base paper to effectively improve the water-blocking performance and gas-blocking performance of the coated paper.
  • Fig. 1 is the impact of carboxymethyl modified cellulose nanofibers of different degrees of substitution on the rheological properties of coatings in the present invention
  • Fig. 2 is the impact of the carboxymethyl modified cellulose nanofibers of different consumptions on the rheological properties of coatings in the present invention
  • Fig. 3 is the impact of carboxymethyl modified cellulose nanofibers on the water retention performance of coatings in the present invention
  • Fig. 4 is the influence of carboxymethyl modified cellulose nanofibers on the water-blocking performance of coated paper in the present invention
  • Figure 5 shows the effect of carboxymethyl-modified cellulose nanofibers on the gas barrier properties of coated paper in the present invention.
  • the high-speed disperser disperses the pigment (35 parts of calcium carbonate and 65 parts of ultrafine kaolin), and adds an appropriate amount of 0.1 part of sodium hydroxide and 0.8 part of sodium hexametaphosphate, and stirs for 20 minutes at a speed of 2500 rpm/min; secondly, the fixed speed 2000rpm/min, 12 parts of polyvinyl alcohol solution as the main adhesive was added to the above dispersion system and stirred for 5min; then, the control speed was 2000rpm/min, and 6 parts of cornstarch, 0.5 parts of chitosan, 0.2 Carboxymethyl-modified cellulose nanofibers with a degree of substitution of 0.21 and a small amount of defoamer, the addition interval of each component is 5 minutes; finally, after all the additives are added to the coating system, continue stirring for 10 minutes to obtain a paper-making coating.
  • the paper-making coating was coated on the base paper surface at a speed of 5 m/min by using a coating machine, and the coating amount was 10 g/m 2 . After the coating was completed, the coated paper was dried at room temperature, and then dried at 105° C. with an electric blast drying oven.
  • the high-speed disperser disperses the pigment (35 parts of calcium carbonate and 65 parts of ultrafine kaolin), and adds an appropriate amount of 0.1 part of sodium hydroxide and 0.8 part of sodium hexametaphosphate, and stirs for 20 minutes at a speed of 2500 rpm/min; secondly, the fixed speed 2000rpm/min, 12 parts of polyvinyl alcohol solution as the main adhesive was added to the above dispersion system and stirred for 5min; then, the control speed was 2000rpm/min, and 6 parts of cornstarch, 0.5 parts of chitosan, 0.2 Parts of carboxymethyl modified cellulose nanofibers with a degree of substitution of 0.1 and a small amount of defoamer, the addition interval of each component is 5 minutes; finally, after all the additives are added to the coating system, continue stirring for 10 minutes to obtain a papermaking coating.
  • the paper-making coating was coated on the base paper surface at a speed of 5 m/min by using a coating machine, and the coating amount was 10 g/m 2 . After the coating was completed, the coated paper was dried at room temperature, and then dried at 105° C. with an electric blast drying oven.
  • the high-speed disperser disperses the pigment (35 parts of calcium carbonate and 65 parts of ultrafine kaolin), and adds an appropriate amount of 0.1 part of sodium hydroxide and 0.8 part of sodium hexametaphosphate, and stirs for 20 minutes at a speed of 2500 rpm/min; secondly, the fixed speed 2000rpm/min, 12 parts of polyvinyl alcohol solution as the main adhesive was added to the above dispersion system and stirred for 5min; then, the control speed was 2000rpm/min, and 6 parts of cornstarch, 0.5 parts of chitosan, 0.1 Carboxymethyl-modified cellulose nanofibers with a degree of substitution of 0.47 and a small amount of defoamer, the addition interval of each component is 5 minutes; finally, after all the additives are added to the coating system, continue stirring for 10 minutes to obtain a paper-making coating.
  • the paper-making coating was coated on the base paper surface at a speed of 5 m/min by using a coating machine, and the coating amount was 10 g/m 2 . After the coating was completed, the coated paper was dried at room temperature, and then dried at 105° C. with an electric blast drying oven.
  • the high-speed disperser disperses the pigment (35 parts of calcium carbonate and 65 parts of ultrafine kaolin), and adds an appropriate amount of 0.1 part of sodium hydroxide and 0.8 part of sodium hexametaphosphate, and stirs for 20 minutes at a speed of 2500 rpm/min; secondly, the fixed speed 2000rpm/min, 12 parts of polyvinyl alcohol solution as the main adhesive was added to the above dispersion system and stirred for 5min; then, the control speed was 2000rpm/min, and 6 parts of corn starch, 0.5 parts of chitosan, 0.4 Parts of carboxymethyl modified cellulose nanofibers with a degree of substitution of 0.47 and a small amount of defoamer, the addition interval of each component is 5min; finally, after all the additives are added to the coating system, continue stirring for 10min to obtain a papermaking coating.
  • the paper-making coating was coated on the base paper surface at a speed of 5 m/min by using a coating machine, and the coating amount was 10 g/m 2 . After the coating was completed, the coated paper was dried at room temperature, and then dried at 105° C. with an electric blast drying oven.
  • the high-speed disperser disperses the pigment (35 parts of calcium carbonate and 65 parts of ultrafine kaolin), and adds an appropriate amount of 0.1 part of sodium hydroxide and 0.8 part of sodium hexametaphosphate, and stirs for 20 minutes at a speed of 2500 rpm/min; secondly, the fixed speed At 2000rpm/min, 12 parts of polyvinyl alcohol solution as the main adhesive were added to the above dispersion system and stirred for 5min; then, the control speed was 2000rpm/min, and 6 parts of cornstarch, 0.5 parts of chitosan and a small amount of The defoaming agent, each component is added at an interval of 5 minutes; finally, after all the additives are added to the coating system, the stirring is continued for 10 minutes to obtain a papermaking coating.
  • the paper-making coating was coated on the base paper surface at a speed of 5 m/min by using a coating machine, and the coating amount was 10 g/m 2 . After the coating was completed, the coated paper was dried at room temperature, and then dried at 105° C. with an electric blast drying oven.
  • the high-speed disperser disperses the pigment (35 parts of calcium carbonate and 65 parts of ultrafine kaolin), and adds an appropriate amount of 0.1 part of sodium hydroxide and 0.8 part of sodium hexametaphosphate, and stirs for 20 minutes at a speed of 2500 rpm/min; secondly, the fixed speed 2000rpm/min, 12 parts of polyvinyl alcohol solution as the main adhesive was added to the above dispersion system and stirred for 5min; then, the control speed was 2000rpm/min, and 6 parts of cornstarch, 0.5 parts of chitosan, 0.2 Parts of unmodified cellulose nanofibers and a small amount of defoamer, the addition interval of each component is 5 minutes; finally, after all the additives are added to the coating system, the stirring is continued for 10 minutes to obtain a papermaking coating.
  • the paper-making coating was coated on the base paper surface at a speed of 5 m/min by using a coating machine, and the coating amount was 10 g/m 2 . After the coating was completed, the coated paper was dried at room temperature, and then dried at 105° C. with an electric blast drying oven.
  • the viscosity value of the paint containing CNF is 11.30Pa ⁇ s
  • the G' of each coating system is higher than G" which shows that the properties of papermaking coatings are closer to elastic solids.
  • the G′ and G′′ of the coating system showed a gradual upward trend.
  • the viscosity of the coating containing CNF is 22.83Pa ⁇ s, and when the amount of CMCNF is 0.20wt% and 0.40wt%, the viscosity of the coating system is 38.70Pa ⁇ s and 50.88Pa respectively s, the viscosity of the coating increases; as shown in Figure 2(b), under the action of low angular frequency, G in each system is higher than G′, which means that the coating is more like an elastic solid, but with the angular frequency The difference between G′ and G′′ decreases gradually until G′ is smaller than G′′, and the coating system gradually exhibits the properties of viscous fluid. In addition, at the same angular frequency, with the increase of CMCNF content, the G′ and G′′ of the coating system are gradually increased.
  • the water vapor transmission rate of the coated paper added with unmodified CNF is 1346.78g/m 2 ⁇ 24h
  • the water absorption value of coated paper added with unmodified CNF was 73.20g/m 2
  • the water absorption performance of the coated paper is reduced by 12.71%
  • the water vapor transmission rate and water absorption value of the coated paper without adding CMCNF are 1300.39g/m 2 ⁇ 24h and 77.30g/m 2.
  • the water vapor transmission rate and water absorption value of the coated paper added with 0.20 wt% CMCNF were 1226.47g/m 2 ⁇ 24h and 63.9g/m 2 respectively, and the water resistance performance of the coated paper increased by 5.68% and 17.34% respectively.
  • the air barrier performance of CNF-coated paper has been improved by 61.60%; as shown in Figure 5(b), the air permeability of the coated paper without CMCNF is 6.75s, and the air permeability of the coated paper with 0.20wt% CMCNF is Air permeability is 20.19s.
  • the gas barrier performance increased by 66.61%.

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  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

A preparation method and application for a water-based coating containing carboxymethyl modified cellulose nanofibers. The preparation method mainly comprises: uniformly mixing calcium carbonate, superfine kaolin, sodium hydroxide, sodium hexametaphosphate, polyvinyl alcohol, corn starch, chitosan, carboxymethyl modified cellulose nanofibers, and a defoaming agent in a certain proportion to prepare a papermaking coating; and coating the surface of raw paper with the papermaking coating by using a coating machine to prepare coated paper. According to the method, the rheological, water retention and barrier properties of the papermaking coating are effectively improved by utilizing the carboxymethyl modified cellulose nanofibers, and the application technology of the papermaking coating is developed. According to the method, water is used as a dispersion medium, the coating component is environment-friendly, the coating preparation process is simple, the coating process is suitable for large-scale production, and the production cost is relatively low.

Description

一种含羧甲基改性纤维素纳米纤维的水性涂料制备方法及应用Preparation method and application of water-based coating containing carboxymethyl modified cellulose nanofibers 技术领域technical field
本发明涉及造纸涂料的制备领域，具体涉及一种含羧甲基改性纤维素纳米纤维的水性涂料及其应用。The invention relates to the field of preparation of papermaking coatings, in particular to a water-based coating containing carboxymethyl-modified cellulose nanofibers and an application thereof.
背景技术Background technique
纤维素纳米纤维是一种可再生的绿色材料，是一种直径小于100纳米的半刚性聚合物。它主要是通过1,4-β-糖苷键连接β-d-葡萄糖环而得到的，具有良好的结合性能、亲水性、聚合度、结晶度等，在涂料、纺织、食品包装、造纸等领域有广泛的应用前景。Cellulose nanofibers, a renewable green material, are semi-rigid polymers with diameters less than 100 nanometers. It is mainly obtained by connecting β-d-glucose rings through 1,4-β-glucosidic bonds. It has good binding properties, hydrophilicity, degree of polymerization, crystallinity, etc., and is widely used in coatings, textiles, food packaging, papermaking, etc. The field has broad application prospects.
由于纤维素纳米纤维表面含有大量的活性基团(羧基、羟基)，使其具有很强的吸附水分子的能力。随着纤维素纳米纤维含量的增加，涂料的保水性能、油墨吸收性和阻隔性能均得到显著改善。但是由于纤维素纳米纤维表面含有大量的羟基，分子内部和分子之间存在强烈的氢键，很容易导致不可逆团聚，从而影响涂层的分散稳定性和其他相关性能。Since the surface of cellulose nanofibers contains a large number of active groups (carboxyl groups, hydroxyl groups), it has a strong ability to absorb water molecules. With the increase of cellulose nanofiber content, the water retention performance, ink absorption and barrier properties of the coatings were all significantly improved. However, due to the large number of hydroxyl groups on the surface of cellulose nanofibers, there are strong hydrogen bonds within and between molecules, which can easily lead to irreversible agglomeration, thereby affecting the dispersion stability and other related properties of the coating.
常用的改性方法包括表面吸附、化学接枝和接枝共聚。表面吸附改性法(物理吸附法)是利用物理方法将特定物质吸附在纳米纤维素表面，使纳米纤维素在高温、高盐、高剪切等特殊环境中保持稳定的性能。接枝共聚法是指将功能基团接枝到纳米纤维素表面，降低分子内和分子间的氢键力，赋予其多种优异性能。分子接枝改性方法一般可分为羧甲基化改性、硅烷化改性、磺化改性、乙酰化改性、阳离子化改性和TEMPO氧化改性。Common modification methods include surface adsorption, chemical grafting, and graft copolymerization. The surface adsorption modification method (physical adsorption method) is to use physical methods to adsorb specific substances on the surface of nanocellulose, so that nanocellulose can maintain stable performance in special environments such as high temperature, high salt, and high shear. The graft copolymerization method refers to the grafting of functional groups onto the surface of nanocellulose to reduce the hydrogen bonding force within and between molecules and endow it with various excellent properties. Molecular grafting modification methods can generally be divided into carboxymethylation modification, silanization modification, sulfonation modification, acetylation modification, cationic modification and TEMPO oxidation modification.
目前最有效的改性方法是改性纤维素纳米纤维，羧甲基改性是常用的化学改性方法，用羧甲基取代纤维素羟基上的氢，使纤维素表面具有更高的电负性，从而提高了纤维素纳米纤维的分散性和稳定性。羧甲基改性纤维素纳米纤维在涂料、纺织品、食品包装、造纸等领域具有广阔的应用前景。At present, the most effective modification method is to modify cellulose nanofibers. Carboxymethyl modification is a commonly used chemical modification method. Carboxymethyl is used to replace the hydrogen on the hydroxyl group of cellulose to make the cellulose surface have a higher electronegativity. properties, thereby improving the dispersion and stability of cellulose nanofibers. Carboxymethyl-modified cellulose nanofibers have broad application prospects in the fields of coatings, textiles, food packaging, and papermaking.
发明内容Contents of the invention
针对现有技术的不足，本发明提供了一种含羧甲基改性纤维素纳米纤维的水性涂料及其应用。Aiming at the deficiencies of the prior art, the invention provides a water-based coating containing carboxymethyl-modified cellulose nanofibers and an application thereof.
为实现以上的发明目的，本发明的技术方案如下：For realizing above object of the invention, technical scheme of the present invention is as follows:
本发明的一方面提供了一种含羧甲基改性纤维素纳米纤维的水性涂料的制备方法，该方法包括以下步骤：One aspect of the present invention provides a kind of preparation method containing the water-based paint of carboxymethyl modified cellulose nanofiber, the method comprises the following steps:
首先，采用高速分散机分散颜料(碳酸钙和超细高岭土)于一定量的去离子水中，并加入适 量氢氧化钠和六偏磷酸钠，在2500rpm/min的转速下搅拌20min；First, use a high-speed disperser to disperse pigments (calcium carbonate and ultrafine kaolin) in a certain amount of deionized water, and add an appropriate amount of sodium hydroxide and sodium hexametaphosphate, and stir for 20 minutes at a speed of 2500rpm/min;
其次，固定转速为2000rpm/min，聚乙烯醇溶液作为主要胶黏剂被加入到上述分散体系中搅拌5min；Secondly, the fixed speed is 2000rpm/min, and the polyvinyl alcohol solution as the main adhesive is added to the above dispersion system and stirred for 5 minutes;
随后，控制转速为2000rpm/min，按顺序加入玉米淀粉、壳聚糖、羧甲基改性纤维素纳米纤维和微量消泡剂，每个组分的加入间隔为5min；Subsequently, the control speed is 2000rpm/min, and cornstarch, chitosan, carboxymethyl modified cellulose nanofibers and trace defoamers are added in order, and the addition interval of each component is 5min;
最后，待所有助剂被加入到涂料体系后，持续搅拌10min，得到固含量高于40％的造纸涂料。Finally, after all the additives are added to the coating system, the stirring is continued for 10 minutes to obtain a papermaking coating with a solid content higher than 40%.
本发明的另一方面还提供了一种含羧甲基改性纤维素纳米纤维的水性涂料在纸张中的应用。Another aspect of the present invention also provides the application of a water-based coating containing carboxymethyl-modified cellulose nanofibers in paper.
使用涂布机将造纸涂料涂覆于原纸表面。涂布完成后，将涂布纸放置在室温下干燥，随后用电热鼓风干燥箱在50-200℃干燥，得到含羧甲基改性纤维素纳米纤维的涂布纸张。Use a coating machine to apply the papermaking coating to the surface of the base paper. After the coating is completed, the coated paper is dried at room temperature, and then dried at 50-200° C. in an electric blast drying oven to obtain the coated paper containing carboxymethyl-modified cellulose nanofibers.
优选地，碳酸钙与超细高岭土的质量比为1：1.86。以碳酸钙与超细高岭土的加入总量为基准，其余组分含量分别为：氢氧化钠0.1％、六偏磷酸钠0.8％、玉米淀粉6％、聚乙烯醇12％、壳聚糖0.5％。Preferably, the mass ratio of calcium carbonate to superfine kaolin is 1:1.86. Based on the total amount of calcium carbonate and superfine kaolin, the remaining components are: 0.1% sodium hydroxide, 0.8% sodium hexametaphosphate, 6% corn starch, 12% polyvinyl alcohol, and 0.5% chitosan .
优选地，羧甲基改性纤维素纳米纤维的取代度为0.10-0.47，优选为0.47。Preferably, the degree of substitution of the carboxymethyl-modified cellulose nanofibers is 0.10-0.47, preferably 0.47.
优选地，羧甲基改性纤维素纳米纤维的添加量(以碳酸钙与超细高岭土的加入总量为基准)为0.10％-0.40％，优选为0.20％。Preferably, the added amount of carboxymethyl-modified cellulose nanofibers (based on the total amount of calcium carbonate and ultrafine kaolin added) is 0.10%-0.40%, preferably 0.20%.
优选地，涂料的涂布量为1-15g/m 2，优选为10g/m 2(为确保涂布纸的性能、成本与涂布效果，在此涂布量下效果最佳)。 Preferably, the coating amount of the coating is 1-15g/m 2 , preferably 10g/m 2 (in order to ensure the performance, cost and coating effect of the coated paper, the effect is best at this coating amount).
涂布速度为1-20m/min，优选为5m/min(为确保涂布量及涂布的均匀性，固含量高于40％的涂布液在此速度下涂布效果最佳)，干燥时间为50-200℃，优选为105℃(为避免干燥时间过长及纸张卷曲，涂布纸在此温度下干燥效果最佳)。The coating speed is 1-20m/min, preferably 5m/min (in order to ensure the coating amount and the uniformity of coating, the coating liquid with a solid content higher than 40% has the best coating effect at this speed), dry The time is 50-200°C, preferably 105°C (in order to avoid excessive drying time and paper curling, the drying effect of coated paper is best at this temperature).
本发明的有益效果：Beneficial effects of the present invention:
其一、本发明以水为分散介质，涂料组分环境友好，涂料制备过程简单，涂布工艺易于放大，适于规模化生产，生产成本较低。本发明为纤维素纳米纤维在造纸涂料中的高值化应用提供了有效技术方案。First, the present invention uses water as the dispersion medium, the paint components are environmentally friendly, the paint preparation process is simple, the coating process is easy to scale up, suitable for large-scale production, and the production cost is low. The invention provides an effective technical solution for the high-value application of cellulose nanofibers in papermaking coatings.
其二、本发明重在利用羧甲基改性纤维素纳米纤维有效改善造纸涂料的流变性能和保水性能，建立含羧甲基改性纤维素纳米纤维的水性涂料的制备方法。Second, the present invention focuses on utilizing carboxymethyl-modified cellulose nanofibers to effectively improve the rheological properties and water retention properties of papermaking coatings, and establishes a preparation method for water-based coatings containing carboxymethyl-modified cellulose nanofibers.
其三、本发明将含有羧甲基改性纤维素纳米纤维的造纸涂料于原纸上，有效改善涂布纸的阻水性能和阻气性能等性能。Third, the present invention applies the paper-making coating containing carboxymethyl-modified cellulose nanofibers on the base paper to effectively improve the water-blocking performance and gas-blocking performance of the coated paper.
附图说明Description of drawings
图1为本发明中不同取代度的羧甲基改性纤维素纳米纤维对涂料流变性能的影响；Fig. 1 is the impact of carboxymethyl modified cellulose nanofibers of different degrees of substitution on the rheological properties of coatings in the present invention;
图2为本发明中不同用量的羧甲基改性纤维素纳米纤维对涂料流变性能的影响；Fig. 2 is the impact of the carboxymethyl modified cellulose nanofibers of different consumptions on the rheological properties of coatings in the present invention;
图3为本发明中羧甲基改性纤维素纳米纤维对涂料保水性能的影响；Fig. 3 is the impact of carboxymethyl modified cellulose nanofibers on the water retention performance of coatings in the present invention;
图4为本发明中羧甲基改性纤维素纳米纤维对涂布纸阻水性能的影响；Fig. 4 is the influence of carboxymethyl modified cellulose nanofibers on the water-blocking performance of coated paper in the present invention;
图5为本发明中羧甲基改性纤维素纳米纤维对涂布纸阻气性能的影响。Figure 5 shows the effect of carboxymethyl-modified cellulose nanofibers on the gas barrier properties of coated paper in the present invention.
具体实施方式Detailed ways
实施例1：Example 1:
含羧甲基改性纤维素纳米纤维的水性涂料的制备。首先，高速分散机分散颜料(35份碳酸钙和65份超细高岭土)，并加入适量0.1份氢氧化钠和0.8份六偏磷酸钠，在2500rpm/min的转速下搅拌20min；其次，固定转速为2000rpm/min，12份聚乙烯醇溶液作为主要胶黏剂被加入到上述分散体系中搅拌5min；随后，控制转速为2000rpm/min，按顺序加入6份玉米淀粉、0.5份壳聚糖、0.2份取代度为0.21的羧甲基改性纤维素纳米纤维和微量消泡剂，每个组分的加入间隔为5min；最后，待所有助剂被加入到涂料体系后，持续搅拌10min，得到造纸涂料。Preparation of waterborne coatings containing carboxymethyl-modified cellulose nanofibers. First, the high-speed disperser disperses the pigment (35 parts of calcium carbonate and 65 parts of ultrafine kaolin), and adds an appropriate amount of 0.1 part of sodium hydroxide and 0.8 part of sodium hexametaphosphate, and stirs for 20 minutes at a speed of 2500 rpm/min; secondly, the fixed speed 2000rpm/min, 12 parts of polyvinyl alcohol solution as the main adhesive was added to the above dispersion system and stirred for 5min; then, the control speed was 2000rpm/min, and 6 parts of cornstarch, 0.5 parts of chitosan, 0.2 Carboxymethyl-modified cellulose nanofibers with a degree of substitution of 0.21 and a small amount of defoamer, the addition interval of each component is 5 minutes; finally, after all the additives are added to the coating system, continue stirring for 10 minutes to obtain a paper-making coating.
含羧甲基改性纤维素纳米纤维的水性涂料在纸张中的应用。首先，使用涂布机将造纸涂料以5m/min的速度涂覆于原纸表面，涂布量为10g/m 2。涂布完成后，将涂布纸放置在室温下干燥，随后用电热鼓风干燥箱在105℃干燥。 Application of water-based coatings containing carboxymethyl-modified cellulose nanofibers in paper. First, the paper-making coating was coated on the base paper surface at a speed of 5 m/min by using a coating machine, and the coating amount was 10 g/m 2 . After the coating was completed, the coated paper was dried at room temperature, and then dried at 105° C. with an electric blast drying oven.
实施例2：Example 2:
含羧甲基改性纤维素纳米纤维的水性涂料的制备。首先，高速分散机分散颜料(35份碳酸钙和65份超细高岭土)，并加入适量0.1份氢氧化钠和0.8份六偏磷酸钠，在2500rpm/min的转速下搅拌20min；其次，固定转速为2000rpm/min，12份聚乙烯醇溶液作为主要胶黏剂被加入到上述分散体系中搅拌5min；随后，控制转速为2000rpm/min，按顺序加入6份玉米淀粉、0.5份壳聚糖、0.2份取代度为0.1的羧甲基改性纤维素纳米纤维和微量消泡剂，每个组分的加入间隔为5min；最后，待所有助剂被加入到涂料体系后，持续搅拌10min，得到造纸涂料。Preparation of waterborne coatings containing carboxymethyl-modified cellulose nanofibers. First, the high-speed disperser disperses the pigment (35 parts of calcium carbonate and 65 parts of ultrafine kaolin), and adds an appropriate amount of 0.1 part of sodium hydroxide and 0.8 part of sodium hexametaphosphate, and stirs for 20 minutes at a speed of 2500 rpm/min; secondly, the fixed speed 2000rpm/min, 12 parts of polyvinyl alcohol solution as the main adhesive was added to the above dispersion system and stirred for 5min; then, the control speed was 2000rpm/min, and 6 parts of cornstarch, 0.5 parts of chitosan, 0.2 Parts of carboxymethyl modified cellulose nanofibers with a degree of substitution of 0.1 and a small amount of defoamer, the addition interval of each component is 5 minutes; finally, after all the additives are added to the coating system, continue stirring for 10 minutes to obtain a papermaking coating.
含羧甲基改性纤维素纳米纤维的水性涂料在纸张中的应用。首先，使用涂布机将造纸涂料以5m/min的速度涂覆于原纸表面，涂布量为10g/m 2。涂布完成后，将涂布纸放置在室温下干燥，随后用电热鼓风干燥箱在105℃干燥。 Application of water-based coatings containing carboxymethyl-modified cellulose nanofibers in paper. First, the paper-making coating was coated on the base paper surface at a speed of 5 m/min by using a coating machine, and the coating amount was 10 g/m 2 . After the coating was completed, the coated paper was dried at room temperature, and then dried at 105° C. with an electric blast drying oven.
实施例3：Example 3:
含羧甲基改性纤维素纳米纤维的水性涂料的制备。首先，高速分散机分散颜料(35份碳酸 钙和65份超细高岭土)，并加入适量0.1份氢氧化钠和0.8份六偏磷酸钠，在2500rpm/min的转速下搅拌20min；其次，固定转速为2000rpm/min，12份聚乙烯醇溶液作为主要胶黏剂被加入到上述分散体系中搅拌5min；随后，控制转速为2000rpm/min，按顺序加入6份玉米淀粉、0.5份壳聚糖、0.1份取代度为0.47的羧甲基改性纤维素纳米纤维和微量消泡剂，每个组分的加入间隔为5min；最后，待所有助剂被加入到涂料体系后，持续搅拌10min，得到造纸涂料。Preparation of waterborne coatings containing carboxymethyl-modified cellulose nanofibers. First, the high-speed disperser disperses the pigment (35 parts of calcium carbonate and 65 parts of ultrafine kaolin), and adds an appropriate amount of 0.1 part of sodium hydroxide and 0.8 part of sodium hexametaphosphate, and stirs for 20 minutes at a speed of 2500 rpm/min; secondly, the fixed speed 2000rpm/min, 12 parts of polyvinyl alcohol solution as the main adhesive was added to the above dispersion system and stirred for 5min; then, the control speed was 2000rpm/min, and 6 parts of cornstarch, 0.5 parts of chitosan, 0.1 Carboxymethyl-modified cellulose nanofibers with a degree of substitution of 0.47 and a small amount of defoamer, the addition interval of each component is 5 minutes; finally, after all the additives are added to the coating system, continue stirring for 10 minutes to obtain a paper-making coating.
含羧甲基改性纤维素纳米纤维的水性涂料在纸张中的应用。首先，使用涂布机将造纸涂料以5m/min的速度涂覆于原纸表面，涂布量为10g/m 2。涂布完成后，将涂布纸放置在室温下干燥，随后用电热鼓风干燥箱在105℃干燥。 Application of water-based coatings containing carboxymethyl-modified cellulose nanofibers in paper. First, the paper-making coating was coated on the base paper surface at a speed of 5 m/min by using a coating machine, and the coating amount was 10 g/m 2 . After the coating was completed, the coated paper was dried at room temperature, and then dried at 105° C. with an electric blast drying oven.
实施例4：Example 4:
含羧甲基改性纤维素纳米纤维的水性涂料的制备。首先，高速分散机分散颜料(35份碳酸钙和65份超细高岭土)，并加入适量0.1份氢氧化钠和0.8份六偏磷酸钠，在2500rpm/min的转速下搅拌20min；其次，固定转速为2000rpm/min，12份聚乙烯醇溶液作为主要胶黏剂被加入到上述分散体系中搅拌5min；随后，控制转速为2000rpm/min，按顺序加入6份玉米淀粉、0.5份壳聚糖、0.4份取代度为0.47的羧甲基改性纤维素纳米纤维和微量消泡剂，每个组分的加入间隔为5min；最后，待所有助剂被加入到涂料体系后，持续搅拌10min，得到造纸涂料。Preparation of waterborne coatings containing carboxymethyl-modified cellulose nanofibers. First, the high-speed disperser disperses the pigment (35 parts of calcium carbonate and 65 parts of ultrafine kaolin), and adds an appropriate amount of 0.1 part of sodium hydroxide and 0.8 part of sodium hexametaphosphate, and stirs for 20 minutes at a speed of 2500 rpm/min; secondly, the fixed speed 2000rpm/min, 12 parts of polyvinyl alcohol solution as the main adhesive was added to the above dispersion system and stirred for 5min; then, the control speed was 2000rpm/min, and 6 parts of corn starch, 0.5 parts of chitosan, 0.4 Parts of carboxymethyl modified cellulose nanofibers with a degree of substitution of 0.47 and a small amount of defoamer, the addition interval of each component is 5min; finally, after all the additives are added to the coating system, continue stirring for 10min to obtain a papermaking coating.
含羧甲基改性纤维素纳米纤维的水性涂料在纸张中的应用。首先，使用涂布机将造纸涂料以5m/min的速度涂覆于原纸表面，涂布量为10g/m 2。涂布完成后，将涂布纸放置在室温下干燥，随后用电热鼓风干燥箱在105℃干燥。 Application of water-based coatings containing carboxymethyl-modified cellulose nanofibers in paper. First, the paper-making coating was coated on the base paper surface at a speed of 5 m/min by using a coating machine, and the coating amount was 10 g/m 2 . After the coating was completed, the coated paper was dried at room temperature, and then dried at 105° C. with an electric blast drying oven.
对比实施例1：Comparative Example 1:
含羧甲基改性纤维素纳米纤维的水性涂料的制备。首先，高速分散机分散颜料(35份碳酸钙和65份超细高岭土)，并加入适量0.1份氢氧化钠和0.8份六偏磷酸钠，在2500rpm/min的转速下搅拌20min；其次，固定转速为2000rpm/min，12份聚乙烯醇溶液作为主要胶黏剂被加入到上述分散体系中搅拌5min；随后，控制转速为2000rpm/min，按顺序加入6份玉米淀粉、0.5份壳聚糖和微量消泡剂，每个组分的加入间隔为5min；最后，待所有助剂被加入到涂料体系后，持续搅拌10min，得到造纸涂料。Preparation of waterborne coatings containing carboxymethyl-modified cellulose nanofibers. First, the high-speed disperser disperses the pigment (35 parts of calcium carbonate and 65 parts of ultrafine kaolin), and adds an appropriate amount of 0.1 part of sodium hydroxide and 0.8 part of sodium hexametaphosphate, and stirs for 20 minutes at a speed of 2500 rpm/min; secondly, the fixed speed At 2000rpm/min, 12 parts of polyvinyl alcohol solution as the main adhesive were added to the above dispersion system and stirred for 5min; then, the control speed was 2000rpm/min, and 6 parts of cornstarch, 0.5 parts of chitosan and a small amount of The defoaming agent, each component is added at an interval of 5 minutes; finally, after all the additives are added to the coating system, the stirring is continued for 10 minutes to obtain a papermaking coating.
含羧甲基改性纤维素纳米纤维的水性涂料在纸张中的应用。首先，使用涂布机将造纸涂料以5m/min的速度涂覆于原纸表面，涂布量为10g/m 2。涂布完成后，将涂布纸放置在室温下干燥，随后用电热鼓风干燥箱在105℃干燥。 Application of water-based coatings containing carboxymethyl-modified cellulose nanofibers in paper. First, the paper-making coating was coated on the base paper surface at a speed of 5 m/min by using a coating machine, and the coating amount was 10 g/m 2 . After the coating was completed, the coated paper was dried at room temperature, and then dried at 105° C. with an electric blast drying oven.
对比实施例2：Comparative example 2:
含羧甲基改性纤维素纳米纤维的水性涂料的制备。首先，高速分散机分散颜料(35份碳酸钙和65份超细高岭土)，并加入适量0.1份氢氧化钠和0.8份六偏磷酸钠，在2500rpm/min的转速下搅拌20min；其次，固定转速为2000rpm/min，12份聚乙烯醇溶液作为主要胶黏剂被加入到上述分散体系中搅拌5min；随后，控制转速为2000rpm/min，按顺序加入6份玉米淀粉、0.5份壳聚糖、0.2份未改性的纤维素纳米纤维和微量消泡剂，每个组分的加入间隔为5min；最后，待所有助剂被加入到涂料体系后，持续搅拌10min，得到造纸涂料。Preparation of waterborne coatings containing carboxymethyl-modified cellulose nanofibers. First, the high-speed disperser disperses the pigment (35 parts of calcium carbonate and 65 parts of ultrafine kaolin), and adds an appropriate amount of 0.1 part of sodium hydroxide and 0.8 part of sodium hexametaphosphate, and stirs for 20 minutes at a speed of 2500 rpm/min; secondly, the fixed speed 2000rpm/min, 12 parts of polyvinyl alcohol solution as the main adhesive was added to the above dispersion system and stirred for 5min; then, the control speed was 2000rpm/min, and 6 parts of cornstarch, 0.5 parts of chitosan, 0.2 Parts of unmodified cellulose nanofibers and a small amount of defoamer, the addition interval of each component is 5 minutes; finally, after all the additives are added to the coating system, the stirring is continued for 10 minutes to obtain a papermaking coating.
含羧甲基改性纤维素纳米纤维的水性涂料在纸张中的应用。首先，使用涂布机将造纸涂料以5m/min的速度涂覆于原纸表面，涂布量为10g/m 2。涂布完成后，将涂布纸放置在室温下干燥，随后用电热鼓风干燥箱在105℃干燥。 Application of water-based coatings containing carboxymethyl-modified cellulose nanofibers in paper. First, the paper-making coating was coated on the base paper surface at a speed of 5 m/min by using a coating machine, and the coating amount was 10 g/m 2 . After the coating was completed, the coated paper was dried at room temperature, and then dried at 105° C. with an electric blast drying oven.
如图1中(a)所示，含有CNF的涂料粘度值为11.30Pa·s，而含有DS＝0.21和0.47CMCNF的涂料粘度值分别为15.30Pa·s和26.30Pa·s，进而导致涂料粘度增大；如图1中(b)所示，由图可知，在低角频率作用下，各个涂料体系的G′均高于G″，这表明造纸涂料的性质更接近于弹性固体。在同一角频率下，随着CMCNF取代度的提高，涂料体系的G′和G″均呈现逐渐上升的趋势。As shown in Figure 1(a), the viscosity value of the paint containing CNF is 11.30Pa·s, while the viscosity value of the paint containing DS=0.21 and 0.47CMCNF is 15.30Pa·s and 26.30Pa·s, respectively, which in turn leads to the viscosity increase; as shown in (b) in Figure 1, it can be seen from the figure that under the action of low angular frequency, the G' of each coating system is higher than G", which shows that the properties of papermaking coatings are closer to elastic solids. In the same Under the angular frequency, with the increase of CMCNF substitution degree, the G′ and G″ of the coating system showed a gradual upward trend.
如图2中(a)所示，含有CNF的涂料粘度值为22.83Pa·s，而CMCNF的用量为0.20wt％和0.40wt％时，其涂料体系的粘度分别为38.70Pa·s和50.88Pa·s，涂料粘度增大；如图2中(b)所示，在低角频率作用下，各个体系中的G均高于G′，这意味着涂料更像弹性固体，但随着角频率的不断增加，G′与G″的差值逐渐减小直至G′小于G″，涂料体系逐渐展现出黏性流体的性质。此外，在同一角频率下，随着CMCNF用量的增多，涂料体系的G′和G″均逐渐提高。As shown in Figure 2 (a), the viscosity of the coating containing CNF is 22.83Pa·s, and when the amount of CMCNF is 0.20wt% and 0.40wt%, the viscosity of the coating system is 38.70Pa·s and 50.88Pa respectively s, the viscosity of the coating increases; as shown in Figure 2(b), under the action of low angular frequency, G in each system is higher than G′, which means that the coating is more like an elastic solid, but with the angular frequency The difference between G′ and G″ decreases gradually until G′ is smaller than G″, and the coating system gradually exhibits the properties of viscous fluid. In addition, at the same angular frequency, with the increase of CMCNF content, the G′ and G″ of the coating system are gradually increased.
如图3中(a)所示，当CMCNF的取代度为0.47，保水值仅为195g/m 2，相较于含有未改性CNF的造纸涂料，保水性能提升了74.43％；如图3中(b)所示，当CMCNF的用量为0.40wt％，涂料保水值仅为195g/m 2，相较于未添加CMCNF的涂料，保水性能提升了86.1％。 As shown in (a) in Figure 3, when the substitution degree of CMCNF is 0.47, the water retention value is only 195g/m 2 , compared with the papermaking coating containing unmodified CNF, the water retention performance is improved by 74.43%; as shown in Figure 3 As shown in (b), when the amount of CMCNF is 0.40wt%, the water retention value of the coating is only 195g/m 2 , which is 86.1% higher than that of the coating without adding CMCNF.
如图4中(a)所示，添加未改性CNF的涂布纸水蒸气透过量为1346.78g/m 2·24h，添加DS＝0.47CMCNF的涂布纸水蒸气透过量为1202.47g/m 2·24h，阻止水蒸气透过的能力提升了8.95，添加未改性CNF的涂布纸吸水值为73.20g/m 2，添加DS＝0.47CMCNF的涂布纸吸水值为63.90g/m 2，涂布纸的吸水性能降低了12.71％；如图4中(b)所示，未添加CMCNF的涂布纸水蒸气透过量和吸水值分别为1300.39g/m 2·24h和77.30g/m 2，添加0.20 wt％CMCNF的涂布纸水蒸气透过量和吸水值分别为1226.47g/m 2·24h和63.9g/m 2，涂布纸的阻水性能分别提升了5.68％和17.34％。 As shown in (a) of Figure 4, the water vapor transmission rate of the coated paper added with unmodified CNF is 1346.78g/m 2 ·24h, and the water vapor transmission rate of the coated paper added with DS=0.47CMCNF is 1202.47g/m 2 ·24h, the ability to prevent water vapor permeation increased by 8.95, the water absorption value of coated paper added with unmodified CNF was 73.20g/m 2 , and the water absorption value of coated paper added with DS=0.47CMCNF was 63.90g/m 2 , the water absorption performance of the coated paper is reduced by 12.71%; as shown in Figure 4 (b), the water vapor transmission rate and water absorption value of the coated paper without adding CMCNF are 1300.39g/m 2 ·24h and 77.30g/m 2. The water vapor transmission rate and water absorption value of the coated paper added with 0.20 wt% CMCNF were 1226.47g/m 2 ·24h and 63.9g/m 2 respectively, and the water resistance performance of the coated paper increased by 5.68% and 17.34% respectively.
如图5中(a)所示，添加未改性CNF的涂布纸空气透气度为7.75s，添加DS＝0.47CMCNF的涂布纸的空气透气度为20.18s，相较于添加未改性CNF的涂布纸，阻气性能提升了61.60％；如图5中(b)所示，未添加CMCNF的涂布纸空气透气度为6.75s，添加0.20wt％的CMCNF，涂布纸的空气透气度为20.19s。相较于未添加CMCNF的涂布纸，阻气性能增加了66.61％。As shown in (a) of Figure 5, the air permeability of the coated paper added with unmodified CNF is 7.75s, and the air permeability of the coated paper added with DS=0.47CMCNF is 20.18s. The air barrier performance of CNF-coated paper has been improved by 61.60%; as shown in Figure 5(b), the air permeability of the coated paper without CMCNF is 6.75s, and the air permeability of the coated paper with 0.20wt% CMCNF is Air permeability is 20.19s. Compared with the coated paper without adding CMCNF, the gas barrier performance increased by 66.61%.

Claims (5)

  1. 一种含羧甲基改性纤维素纳米纤维的水性涂料制备方法，其特征在于，包括如下步骤：A kind of water-based paint preparation method containing carboxymethyl modified cellulose nanofiber, it is characterized in that, comprises the steps:
    首先，采用高速分散机分散颜料于一定量的去离子水中，并加入适量氢氧化钠和六偏磷酸钠，在2500rpm/min的转速下搅拌20min；First, use a high-speed disperser to disperse the pigment in a certain amount of deionized water, add an appropriate amount of sodium hydroxide and sodium hexametaphosphate, and stir for 20 minutes at a speed of 2500 rpm/min;
    其次，固定转速为2000rpm/min，聚乙烯醇溶液作为主要胶黏剂，加入到上述分散体系中搅拌5min；Secondly, the fixed speed is 2000rpm/min, and the polyvinyl alcohol solution is used as the main adhesive, which is added to the above dispersion system and stirred for 5 minutes;
    随后，控制转速为2000rpm/min，按顺序加入玉米淀粉、壳聚糖、羧甲基改性纤维素纳米纤维和微量消泡剂，每个组分的加入间隔为5min；Subsequently, the control speed is 2000rpm/min, and cornstarch, chitosan, carboxymethyl modified cellulose nanofibers and trace defoamers are added in order, and the addition interval of each component is 5min;
    最后，待所有助剂加入到涂料体系后，持续搅拌10min，得到固含量高于40％的造纸涂料。Finally, after all the additives are added to the coating system, the stirring is continued for 10 minutes to obtain a papermaking coating with a solid content higher than 40%.
  2. 根据权利要求1所述的一种含羧甲基改性纤维素纳米纤维的水性涂料制备方法，其特征在于：所述分散颜料为碳酸钙和超细高岭土，其中碳酸钙与超细高岭土的质量比为1：1.86；以碳酸钙与超细高岭土的加入总量为基准，其余组分含量分别为：氢氧化钠为0.1％、六偏磷酸钠为0.8％、玉米淀粉为6％、聚乙烯醇为12％、壳聚糖为0.5％、羧甲基改性纤维素纳米纤维为0.10％-0.40％。A kind of water-based paint preparation method containing carboxymethyl modified cellulose nanofiber according to claim 1, is characterized in that: described dispersed pigment is calcium carbonate and superfine kaolin, wherein the quality of calcium carbonate and superfine kaolin The ratio is 1:1.86; based on the total amount of calcium carbonate and superfine kaolin, the contents of the remaining components are: 0.1% sodium hydroxide, 0.8% sodium hexametaphosphate, 6% corn starch, polyethylene Alcohol content is 12%, chitosan content is 0.5%, and carboxymethyl modified cellulose nanofiber content is 0.10%-0.40%.
  3. 根据权利要求1所述的一种含羧甲基改性纤维素纳米纤维的水性涂料制备方法，其特征在于：所述羧甲基改性纤维素纳米纤维的取代度为0.10-0.47。The method for preparing a water-based paint containing carboxymethyl-modified cellulose nanofibers according to claim 1, wherein the degree of substitution of the carboxymethyl-modified cellulose nanofibers is 0.10-0.47.
  4. 根据权利要求1所述的一种含羧甲基改性纤维素纳米纤维的水性涂料制备方法，其特征在于：所述羧甲基改性纤维素纳米纤维的取代度为0.47，含量为0.20％。A method for preparing a water-based coating containing carboxymethyl-modified cellulose nanofibers according to claim 1, characterized in that: the degree of substitution of the carboxymethyl-modified cellulose nanofibers is 0.47, and the content is 0.20% .
  5. 根据权利要求1至4中任一项所述的一种含羧甲基改性纤维素纳米纤维的水性涂料在纸张中的应用。The application of a water-based coating containing carboxymethyl modified cellulose nanofibers in paper according to any one of claims 1 to 4.
PCT/CN2021/140385 2021-12-10 2021-12-22 Preparation method and application for water-based coating containing carboxymethyl modified cellulose nanofibers WO2023103093A1 (en)

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