CN115233493A - Water vapor barrier coating and preparation method thereof, water vapor barrier coated paper and preparation method thereof - Google Patents
Water vapor barrier coating and preparation method thereof, water vapor barrier coated paper and preparation method thereof Download PDFInfo
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- CN115233493A CN115233493A CN202210877852.3A CN202210877852A CN115233493A CN 115233493 A CN115233493 A CN 115233493A CN 202210877852 A CN202210877852 A CN 202210877852A CN 115233493 A CN115233493 A CN 115233493A
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- 239000011701 zinc Substances 0.000 claims description 6
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229920005610 lignin Polymers 0.000 claims description 4
- 229920001909 styrene-acrylic polymer Polymers 0.000 claims description 4
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Classifications
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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
- D21H19/02—Metal coatings
-
- 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
-
- 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
-
- 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
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/10—Packing paper
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/80—Packaging reuse or recycling, e.g. of multilayer packaging
Landscapes
- Laminated Bodies (AREA)
- Paints Or Removers (AREA)
- Paper (AREA)
Abstract
The invention relates to a water vapor barrier coating and a preparation method thereof, and water vapor barrier coated paper and a preparation method thereof. The solid content of the coating comprises 20-45% of nano metal sheets, 45-75% of adhesive, 1-10% of nano cellulose and 0-5% of additive by mass percentage; and coating the paper base material with the water-vapor barrier coating paper, and drying and curing to obtain the water-vapor barrier coating paper. The technical problem to be solved is that the paper base has excellent water vapor barrier property, and the paper only needs one-time coating, so that the coating amount is small, the material cost is low, the preparation process is simple, and the popularization and the application are easy.
Description
Technical Field
The invention belongs to the technical field of coated paper, and particularly relates to a water vapor barrier coating and a preparation method thereof, and water vapor barrier coated paper and a preparation method thereof.
Background
With the upgrading of the consumption of residents, the requirements on high performance, multiple functions and environmental friendliness of the packaging material are higher and higher. In the industries of food, medicine and the like, the components of the articles need to be ensured not to be oxidized and deteriorated, the storage life is prolonged, and the packaging material needs to have certain barrier property, particularly, the water vapor permeation is prevented. The application of plastic-based packaging materials is limited with the enhancement of national environmental protection policies. Paper prepared from natural plant fiber raw materials becomes one of the most widely applied packaging materials at present due to the characteristics of good reproducibility, recyclability and sustainability. However, the water vapor barrier property of the paper base material is poor, certain products with specific requirements cannot be met, and at present, plastics and paper are compounded mainly in a film spraying mode, so that the barrier property of the composite paper is improved. Coating a barrier coating on the surface of a paper-based material to improve the barrier properties of the paper is one of the most effective and rapid ways to improve the properties of existing packaging materials.
In the prior art, a high-barrier packaging film is reported, which sequentially comprises a paper base, a polyester film layer, a barrier inorganic oxide layer, a polyamide film layer and a heat sealing layer; firstly plating a barrier inorganic oxide layer on a polyester film layer, then compounding a paper base with the polyester film layer, and finally compounding a polyamide film layer and a heat sealing layer by laminating a composite film; the above materials have high water vapor barrier properties, but they have the following disadvantages: one is that the number of layers is large, the production cost is high, and the recycling of paper is not facilitated; secondly, the preparation process is complex, the film coating technology needs a specific film coating machine, and the technology popularization is not facilitated.
The prior art also reports a moisture and oxygen resistant material with two-side coating kraft paper base, which is formed by compounding the paper base and a coating film layer; the paper base is firstly dipped in modified acrylic acid, and after being dried, the front surface of the paper base is sequentially coated with a zein coating layer, a polyvinyl alcohol coating layer and an acrylic acid coating layer; the back of the paper base is coated with a single-layer modified acrylic acid coating layer. The method enhances the moisture and oxygen resistance of the kraft paper, but the preparation process needs multiple coating, the coating amount is large, and the cost is high.
Disclosure of Invention
The invention mainly aims to provide a water vapor barrier coating and a preparation method thereof, water vapor barrier coated paper and a preparation method thereof, and aims to solve the technical problem that a paper base has excellent water vapor barrier property (the water vapor transmission rate is less than or equal to 5 g/m) 2 24 h), and the paper only needs to be coated once, and the coating weight is small (3-15 g/m) 2 ) The material cost is low, the preparation process is simple, and the method is easy to popularize and apply, thereby being more practical.
The purpose of the invention and the technical problem to be solved are realized by adopting the following technical scheme. According to the water vapor barrier coating provided by the invention, the solid content of the water vapor barrier coating comprises the following components in percentage by mass: 20-45% of nano metal sheet; 45 to 75 percent of adhesive; 1-10% of nano cellulose; and 0-5% of additive.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, the water vapor barrier coating is prepared by mixing the aluminum nano-sheet, the zinc nano-sheet, the copper nano-sheet and the titanium nano-sheet; wherein the average radial dimension of the nano metal sheet is 5-60 mu m, the length-diameter ratio is more than 50, and the thickness is less than 100nm.
Preferably, the water vapor barrier coating material is prepared by mixing a water-soluble polymer and a water-soluble polymer, wherein the water-soluble polymer is a polymer selected from the group consisting of ethylene-acrylic acid copolymer emulsion, styrene-butadiene emulsion, acrylic acid emulsion, polyvinylidene chloride emulsion, styrene-acrylic emulsion, cellulose derivative and lignin adhesive.
Preferably, the aforementioned water vapor barrier coating, wherein the nanocellulose is selected from at least one of unmodified cellulose nanofibrils, 2,2,6,6-tetramethylpiperidine-nitrogen-oxide oxidized cellulose nanofibrils, quaternary ammonium salt modified cellulose nanofibrils, and carboxymethylated cellulose nanofibrils; wherein the diameter of the nano-cellulose is 10-40 nm, the length is more than 1 mu m, and the crystallinity is 40-60%.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. The preparation method of the water vapor barrier coating provided by the invention comprises the following steps:
1) Adding nano-cellulose into water under the condition of stirring, stirring until no agglomeration exists, and performing ultrasonic treatment to obtain a nano-cellulose suspension;
2) Preparing the nano metal sheet into suspension under the condition of high-speed shearing;
3) Adding an adhesive, a nano-cellulose suspension and an additive into the suspension obtained in the step 2) under a high-speed shearing condition, and keeping the high-speed shearing condition for 1-2 hours to obtain a water vapor barrier coating; wherein the solid content of the water vapor barrier coating comprises the following components in percentage by mass: 20 to 45 percent of nano metal sheet, 45 to 75 percent of adhesive, 1 to 10 percent of nano cellulose and 0 to 5 percent of additive.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, in the preparation method, the solid content of the water vapor barrier coating is 20 to 50% by mass.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. According to the preparation method of the water vapor barrier coating paper, the water vapor barrier coating is coated on a paper base material and dried and cured.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, the aforementioned method of making, wherein said paper-based material is selected from single-sided glossy paperAny one of paper, ivory board and kraft paper; the water vapor barrier coating is coated on the front surface of the paper base material; the coating weight of the water vapor barrier coating is 3-15 g/m 2 The dry film thickness of the coating is 3-14 μm.
The object of the present invention and the technical problem to be solved are also achieved by the following technical means. The invention provides a water vapor barrier coating paper, which comprises the following components: a paper based material; the water vapor barrier coating is coated on the front surface of the paper base material; wherein the solid content of the water vapor barrier coating comprises the following components in percentage by mass: 20 to 45 percent of nano metal sheet, 45 to 75 percent of adhesive, 1 to 10 percent of nano cellulose and 0 to 5 percent of additive.
The object of the present invention and the technical problems solved thereby can be further achieved by the following technical measures.
Preferably, the water vapor barrier coated paper has a water vapor transmission rate of less than or equal to 5g/m 2 ·24h。
By the technical scheme, the water vapor barrier coating and the preparation method thereof, provided by the invention, have the following advantages:
the invention provides a water vapor barrier coating and a preparation method thereof, and relates to water vapor barrier coated paper and a preparation method thereof, wherein nano metal sheets and nano cellulose are introduced into the coating; the nano metal sheet is a sheet material of a metal material, and is bonded by an adhesive and then laminated together to form a compact coating, so that the coating has excellent water vapor barrier property, and the water vapor transmission rate of the coating is less than or equal to 5g/m 2 24h, that is, the nano metal sheet is the key of the coating with excellent water vapor barrier property; meanwhile, the nanocellulose is added to form a net structure and is filled in gaps of the nano metal sheet, so that the water vapor barrier property of the coating is further promoted; that is, the water vapor barrier coating provided by the invention has the advantages that on one hand, the nano metal sheet is bonded by the adhesive to form a compact coating, on the other hand, the nano cellulose is filled in the gap of the nano metal sheet to enhance the compactness between the nano metal sheet and the sheet, and the water vapor barrier coating is realized by reasonably designing the proportion of various raw materialsThe insulating coating has the technical effect of excellent water vapor barrier property.
Furthermore, the water vapor barrier coating and the water vapor barrier coated paper provided by the invention are mainly based on metal materials and nano-cellulose, so that the using amount of petroleum-based high polymer materials is greatly reduced, and the water vapor barrier coating and the water vapor barrier coated paper are more environment-friendly.
Furthermore, compared with a laminating method for preparing the barrier composite paper, the method for preparing the water vapor barrier coating and the water vapor barrier coated paper provided by the invention only needs one-time coating and has small coating amount (3-15 g/m) 2 ) The material cost is low; the preparation process is simple and easy to popularize and apply; and the coated paper has excellent degradation performance and repulping performance, and is beneficial to harmless treatment or recycling.
Furthermore, the water vapor barrier coating paper provided by the invention has ultrahigh water vapor barrier performance, and meets the high-end packaging requirements of food, medicine, electronics and the like.
The foregoing is a summary of the present invention, and in order to provide a clear understanding of the technical means of the present invention and to be implemented in accordance with the present specification, the following is a detailed description of the preferred embodiments of the present invention.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description will be given to a water vapor barrier coating and a preparation method thereof, a water vapor barrier coated paper and a preparation method thereof according to the present invention, and specific embodiments, structures, characteristics and effects thereof.
The invention provides a water vapor barrier coating, which comprises the following solid components in percentage by mass: 20 to 45 percent of nano metal sheet, 45 to 75 percent of adhesive, 1 to 10 percent of nano cellulose and 0 to 5 percent of additive.
According to the technical scheme, the nano metal sheet and the nano cellulose are introduced into the coating, so that the effect of high water vapor barrier of the coating is realized under the action of the adhesive. The nano-metal sheet is a sheet material of a metal material, which isThe coating is bonded by the adhesive and then laminated together to form a compact coating, so that the coating has excellent water vapor barrier property, and the water vapor transmission rate of the coating is less than or equal to 5g/m 2 24h, that is, the nano metal sheet is the key of the coating with excellent water vapor barrier property; meanwhile, the nanocellulose is added to form a net structure and can be filled in gaps of the nano metal sheet, so that the water vapor barrier property of the coating is further promoted; that is, the water vapor barrier coating provided by the invention has the advantages that on one hand, a compact coating is formed by bonding the nano metal sheets by the adhesive, on the other hand, the nano cellulose is filled in the gaps of the nano metal sheets to enhance the compactness between the nano metal sheets, and the water vapor barrier coating has the technical effect of excellent water vapor barrier performance by reasonably designing the proportion of various raw materials.
It should be noted that: conventional cellulose-based thickeners are cellulose derivatives, such as carboxymethyl cellulose, hydroxyethyl cellulose, and the like, which are soluble in water and act as thickeners. The cellulose adopted by the invention is nano-cellulose which cannot be dissolved in water but is uniformly dispersed in the water, and the cellulose can only play a slight thickening role, but the thickening role is very limited. In fact, the technical scheme of the invention introduces the nano-cellulose, and the main function of the nano-cellulose is to enable the nano-cellulose to be filled between nano metal sheets to enhance the compactness between the sheets so as to improve the water vapor barrier property of the coating.
Preferably, the nano metal sheet is selected from at least one of a nano aluminum sheet, a nano zinc sheet, a nano copper sheet and a nano titanium sheet; wherein the average radial dimension of the nano metal sheet is 5-60 mu m, the length-diameter ratio is more than 50, and the thickness is less than 100nm.
Proper sizing of the nano-metal sheets may be more advantageous for the nano-metal sheets to form a dense stack of coatings. If the particle size of the nano metal sheet is too small, the particle size of the nano metal sheet is relatively close to the thickness of the nano metal sheet, that is, the length-diameter ratio of the metal sheet is small, at this time, the metal sheet may not be kept in a horizontal state during lamination, so that a compact laminated coating cannot be formed, that is, the bonding angle of the metal sheet is relatively random, and the water vapor blocking effect of the coating may be affected; similar problems may occur if the nano-metal sheets are too large in size, resulting in too large gaps between the nano-metal sheets and thus insufficient densification of the coating as a whole, resulting in a decrease in the water vapor barrier properties of the coating.
Preferably, the adhesive is mainly used for forming a continuous coating and bonding the nano metal sheet and the nano cellulose; typically, the adhesive is selected from at least one of ethylene-acrylic acid copolymer emulsion, styrene-butadiene emulsion, acrylic acid emulsion, polyvinylidene chloride emulsion, styrene-acrylic emulsion, cellulose derivative, and lignin adhesive.
Preferably, the nanocellulose is selected from at least one of unmodified cellulose nanofibrils, 2,2,6,6-tetramethylpiperidine-nitrogen-oxide oxidized cellulose nanofibrils, quaternary ammonium salt modified cellulose nanofibrils and carboxymethylated cellulose nanofibrils; wherein the diameter of the nano-cellulose is 10-40 nm, the length is more than 1 mu m, and the crystallinity is 40-60%.
As described above, the purpose of introducing the nanocellulose in the invention is to fill the nanocellulose between the nano metal sheets to enhance the compactness of the coating, so as to improve the water vapor barrier property of the coating. If the length of the nano-cellulose is long enough, it is easier to form a network structure, and when the nano-cellulose is filled between nano-metal sheets, the nano-cellulose can have more remarkable action with the adhesive, so that the coating is more compact.
The crystallinity of the cellulose also has obvious influence on the compactness and the water vapor barrier property of the coating. When the nano-cellulose has higher crystallinity, cellulose chain molecules are arranged more regularly, and the bonding force between the molecules is stronger, so that water vapor molecules are more difficult to pass through the coating, the permeation of water vapor is more favorably blocked, and the water vapor blocking property of the coating is improved.
Preferably, various functional auxiliaries can be selectively added into the water vapor barrier coating according to needs so as to introduce various effects, so that the coating is endowed with better comprehensive performance. For example, the thickening agent is added into the coating to adjust the rheological characteristics such as the viscosity of the coating and the like, so that the coating is suitable for different coating processing modes; the addition of a defoamer to the coating helps to form a more uniform coating; the bactericide is added into the coating to prevent the coating from deteriorating and facilitate long-term storage. The present invention is not particularly limited with respect to the kind of additives to be incorporated into the coating material.
The invention also provides a preparation method of the water vapor barrier coating, which comprises the following steps:
1) Adding the nano-cellulose into water under the stirring condition, and stirring until no obvious agglomeration exists; the invention is not particularly limited with respect to the specific stirring manner; in one embodiment of the invention, a magnetic stirrer may be used for stirring; then carrying out ultrasonic treatment to obtain a nano cellulose suspension; by adopting a combined process of stirring and ultrasonic treatment, the nanocellulose can be dispersed uniformly enough, so that the subsequent doping into the coating is facilitated, and the obtained coating is more uniform and compact;
2) Preparing the nano metal sheet into suspension under the high-speed shearing condition, generally 400-800 rpm; the rest materials can be added after high-speed shearing for 30min generally;
3) Adding an adhesive, a nano cellulose suspension and an additive into the suspension obtained in the step 2) under a high-speed shearing condition, and keeping the high-speed shearing condition for 1-2 hours to obtain a water vapor barrier coating; wherein the solid content of the water vapor barrier coating comprises the following components in percentage by mass: 20 to 45 percent of nano metal sheet, 45 to 75 percent of adhesive, 1 to 10 percent of nano cellulose and 0 to 5 percent of additive.
Preferably, the mass concentration of the nano-cellulose suspension is 1 to 5%. When the concentration of the nano-cellulose suspension is too low, more water can be contained in the nano-cellulose suspension, so that the nano-cellulose suspension is inconvenient to add when a composite coating is prepared subsequently; meanwhile, the concentration of the nano-cellulose suspension is too low, and high doping amount of nano-cellulose in the coating can not be realized; too high a concentration of the nanocellulose suspension may result in a non-uniform dispersion of the nanocellulose.
Preferably, the ultrasonic treatment process condition is ultrasonic treatment for 0.5-1.5 h under 80-100 Hz; the limitation of the ultrasonic frequency and the process time aims to provide a proper stirring for the nano-cellulose so as to uniformly disperse the nano-cellulose without obvious agglomeration; if the ultrasonic time is too long, on one hand, the dispersibility is not improved more by prolonging the ultrasonic time, and the energy consumption is high, the time is long, and the cost performance is not high; meanwhile, the high length-diameter ratio structure of the nano-cellulose can be damaged by longer ultrasonic time, so that the effect of the nano-cellulose on improving the compactness of the nano-metal sheets filled with the nano-cellulose is influenced.
Preferably, the solid content of the water vapor barrier coating is 20-50% by mass; the coating is at least one of knife coating, curtain coating, spraying or brushing; the solid content of the water vapor barrier coating has certain influence on the construction mode, generally, the coating method is selected according to the solid content of the coating, for example, the solid content of the coating required by blade coating is 40-60%, the solid content of the coating required by curtain coating is 15-30%, the solid content of the final coating in the embodiment and the comparative example is mostly lower, and the construction of the curtain coating mode is generally preferred.
The invention also provides a preparation method of the water vapor barrier coating paper, which comprises the steps of coating the water vapor barrier coating on a paper base material, drying and curing; the water vapor barrier coating paper is mainly based on metal materials and nano-cellulose, greatly reduces the using amount of petroleum-based high polymer materials, and is more environment-friendly.
Preferably, the paper-based material is selected from any one of single-sided glossy paper, white cardboard and kraft paper; the water vapor barrier coating is coated on the front surface of the paper base material.
Preferably, the coating weight of the water vapor barrier coating is 3-15 g/m 2 The dry film thickness of the coating is 3-14 mu m; the method prepares the coated paper through coating processing, only needs one-time coating, and has small coating amount and low material cost; the preparation process is simple and easy to popularize and apply; and the coated paper has excellent degradation performance and repulping performance, and is beneficial to harmless treatment or recycling.
The invention also provides water vapor barrier coating paper which comprises a paper base material and water vapor barrier coating; the water vapor barrier coating is coated onA front side of the paper based material; wherein the solid content of the water vapor barrier coating comprises the following components in percentage by mass: 20 to 45 percent of nano metal sheet, 45 to 75 percent of adhesive, 1 to 10 percent of nano cellulose and 0 to 5 percent of additive; the water vapor barrier coating paper has excellent water vapor barrier performance, and the water vapor transmission rate is less than or equal to 5g/m 2 24h; the water vapor barrier coating paper provided by the invention has ultrahigh water vapor barrier performance, and meets the high-end packaging requirements of food, medicine, electronics and the like.
The present invention will be further described with reference to the following examples, which should not be construed as limiting the scope of the invention, but rather as providing those skilled in the art with the necessary understanding that certain insubstantial modifications and variations of the invention can be made without departing from the spirit and scope of the invention as defined above.
Unless otherwise specified, the following materials, reagents and the like are commercially available products well known to those skilled in the art; unless otherwise specified, all methods are well known in the art. Unless defined otherwise, technical or scientific terms used herein shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention belongs.
Example 1
Preparing a water vapor barrier coating:
2,2,6,6-tetramethylpiperidine-nitrogen-oxide (TEMPO) oxidized cellulose nanofibrils (length 5-10 μm, diameter 10-20 nm, crystallinity 40.8%) are added into deionized water to prepare a suspension with concentration of 5%, and the suspension is stirred by magnetic force until no obvious agglomeration exists, and is treated by ultrasonic for 1h at 90 Hz. Dispersing 20g of nano aluminum sheets (solid content is 50%) with the particle size of 7 mu m in 13.33g of deionized water, dispersing the nano aluminum sheets into suspension under a high-speed shearing condition (400-800 rpm), adding 66.67g of ethylene-acrylic acid copolymer emulsion (solid content is 30%), 8g of the nano cellulose suspension and 1g of defoaming agent after 30min, and continuously maintaining the high-speed shearing condition for 2h to prepare the barrier coating.
Preparing water vapor barrier coating paper:
coating the composite coating on the front surface of the single-sided glossy paper by a coating machine at a coating speed of 70m/min,the single-sided glossy paper has the quantitative weight of 28g/m 2 Thickness of 40 μm and coating weight of 9g/m 2 And the thickness of the dry film of the coating is 6 mu m, drying and curing are carried out for 60min at the temperature of 100 ℃, and the barrier paper is obtained after drying and storing. The water vapor transmission of the barrier paper was measured as standard and the results are shown in table 1.
Example 2
Preparing a water vapor barrier coating:
2,2,6,6-tetramethylpiperidine-nitrogen-oxide (TEMPO) oxidized cellulose nanofibrils (length 5-10 μm, diameter 10-20 nm, crystallinity 40.8%) are added into deionized water to prepare a suspension with concentration of 5%, and the suspension is stirred by magnetic force until no obvious agglomeration exists, and is treated by ultrasonic for 1h at 90 Hz. Dispersing 15g of nano aluminum sheets (solid content is 50%) with the particle size of 7 mu m in 10g of deionized water, dispersing the nano aluminum sheets into suspension under a high-speed shearing condition (400-800 rpm), adding 75g of ethylene-acrylic acid copolymer emulsion (solid content is 30%), 8g of the nano cellulose suspension and 1g of defoaming agent after 30min, and continuously maintaining the high-speed shearing condition for 2h to prepare the barrier coating.
Preparing water vapor barrier coating paper:
coating the composite coating on the front surface of the single-sided glossy paper by a coating machine at a coating speed of 70m/min, wherein the quantitative amount of the single-sided glossy paper is 28g/m 2 Thickness of 40 μm and coating weight of 9g/m 2 And the thickness of the dry film of the coating is 6 mu m, drying and curing are carried out for 60min at the temperature of 100 ℃, and the barrier paper is obtained after drying and storing. The water vapor transmission of the barrier paper was measured according to the standard, and the results are shown in Table 1.
Example 3
Preparing a water vapor barrier coating:
adding quaternary ammonium salt modified cellulose nano-fibrils (the length is 1-10 mu m, the diameter is less than 20nm, and the crystallinity is 55.8%) into deionized water to prepare suspension with the concentration of 5%, stirring by magnetic force until no obvious agglomeration exists, and carrying out ultrasonic treatment for 1h at 90 Hz. Dispersing 13.33g of nano zinc sheets (solid content is 75%) with the particle size of 9 mu m in 46.67g of deionized water, dispersing the nano zinc sheets into suspension under a high-speed shearing condition (400-800 rpm), adding 40g of acrylic emulsion (solid content is 50%), 8g of the nano cellulose suspension and 1g of bactericide after 30min, and continuously maintaining the high-speed shearing condition for 2h to prepare the barrier coating.
Preparing water vapor barrier coating paper:
coating the composite coating on the front surface of the white cardboard by a coating machine at the coating speed of 70m/min and the fixed quantity of 236g/m 2 A thickness of 318 μm and a coating weight of 15g/m 2 And the thickness of the dry film of the coating is 11 mu m, drying and curing are carried out for 80min at the temperature of 110 ℃, and the barrier paper is obtained after drying and storing. The water vapor transmission of the barrier paper was measured according to the standard, and the results are shown in Table 1.
Example 4
Preparing a water vapor barrier coating:
carboxymethylated cellulose nanofibrils (with the length of 3-10 mu m, the diameter of 10-15 nm and the crystallinity of 56.5%) are added into deionized water to prepare suspension with the concentration of 5%, and the suspension is stirred by magnetic force until no obvious agglomeration exists and is treated by ultrasonic for 1h under 90 Hz. Dispersing 12.3g of nano copper sheets (solid content is 55%) with the particle size of 5 mu m into 18.1g of deionized water, dispersing the nano copper sheets into suspension under a high-speed shearing condition (400-800 rpm), adding 30.77g of polyvinylidene chloride emulsion (solid content is 65%), 8g of the nano cellulose suspension and 1g of thickening agent after 30min, and continuously maintaining the high-speed shearing condition for 2h to prepare the barrier coating.
Preparing water vapor barrier coating paper:
coating the composite coating on the front surface of kraft paper by a coating machine at a coating speed of 70m/min, wherein the kraft paper has a quantitative amount of 115g/m 2 Thickness of 151 μm and coating weight of 12g/m 2 And the thickness of the dry film of the coating is 9 mu m, drying and curing are carried out for 70min at 105 ℃, and the barrier paper is obtained after drying and storing. The water vapor transmission of the barrier paper was measured according to the standard, and the results are shown in Table 1.
Example 5
Preparing a water vapor barrier coating:
adding unmodified cellulose nano-fibrils (with the length of 5-13 mu m, the diameter of 10-30 nm and the crystallinity of 59.5%) into deionized water to prepare suspension with the concentration of 5%, stirring by magnetic force until no obvious agglomeration exists, and carrying out ultrasonic treatment for 1h at 90 Hz. Dispersing 16.67g of nano titanium sheet (solid content 60%) with the particle size of 8 mu m in 43.33g of deionized water, dispersing into suspension under a high-speed shearing condition (400-800 rpm), adding 40g of styrene-acrylic emulsion (solid content 50%), 8g of the nano cellulose suspension and 1g of defoaming agent after 30min, and continuously maintaining the high-speed shearing condition for 2h to prepare the barrier coating.
Preparing water vapor barrier coating paper:
coating the composite coating on the front surface of the single-sided glossy paper by a coating machine at a coating speed of 70m/min, wherein the quantitative amount of the single-sided glossy paper is 28g/m 2 Thickness of 40 μm and coating weight of 9g/m 2 And the thickness of the dry film of the coating is 6 mu m, drying and curing are carried out for 60min at the temperature of 100 ℃, and the barrier paper is obtained after drying and storing. The water vapor transmission of the barrier paper was measured as standard and the results are shown in table 1.
Example 6
Preparing a water vapor barrier coating:
2,2,6,6-tetramethylpiperidine-nitrogen-oxide (TEMPO) oxidized cellulose nanofibrils (length 5-10 μm, diameter 10-20 nm, crystallinity 40.8%) are added into deionized water to prepare a suspension with concentration of 5%, and the suspension is stirred by magnetic force until no obvious agglomeration exists, and is treated by ultrasonic for 1h at 90 Hz. Dispersing 20g of nano aluminum sheets (solid content is 50%) with the particle size of 7 mu m in 30g of deionized water, dispersing the nano aluminum sheets into suspension under a high-speed shearing condition (400-800 rpm), adding 50g of lignin adhesive (solid content is 40%), 8g of the nano cellulose suspension and 1g of defoaming agent after 30min, and continuously maintaining the high-speed shearing condition for 2h to prepare the barrier coating.
Preparing water vapor barrier coating paper:
coating the composite coating on the front surface of the single-sided glossy paper by a coating machine at a coating speed of 70m/min, wherein the quantitative amount of the single-sided glossy paper is 28g/m 2 Thickness of 40 μm and coating weight of 9g/m 2 And the thickness of the dry film of the coating is 6 mu m, drying and curing are carried out for 60min at the temperature of 100 ℃, and the barrier paper is obtained after drying and storing. The water vapor transmission of the barrier paper was measured according to the standard, and the results are shown in Table 1.
Example 7
Preparing a water vapor barrier coating:
adding quaternary ammonium salt modified cellulose nano-fibril (length is 1-10 μm, diameter is less than 20nm, crystallinity is 55.8%) into deionized water to prepare suspension with concentration of 5%, stirring by magnetic force until no obvious agglomeration occurs, and carrying out ultrasonic treatment for 1h at 90 Hz. 20g of nano aluminum sheets (solid content is 50%) with the particle size of 7 mu m are dispersed in 22.86g of deionized water and dispersed into suspension under the high-speed shearing condition (400-800 rpm), 57.14g of cellulose derivative (solid content is 35%), 8g of the nano cellulose suspension, 0.5g of defoaming agent and 0.5g of bactericide are added after 30min, and the high-speed shearing condition is continuously maintained for 2h to prepare the barrier coating.
Preparing water vapor barrier coating paper:
coating the composite coating on the front surface of the single-sided glossy paper by a coating machine at a coating speed of 70m/min, wherein the quantitative amount of the single-sided glossy paper is 28g/m 2 Thickness of 40 μm and coating weight of 9g/m 2 And the thickness of the dry film of the coating is 6 mu m, drying and curing are carried out for 60min at the temperature of 100 ℃, and the barrier paper is obtained after drying and storing. The water vapor transmission of the barrier paper was measured according to the standard, and the results are shown in Table 1.
Example 8
Example 1
Preparing a water vapor barrier coating:
2,2,6,6-tetramethylpiperidine-nitrogen-oxide (TEMPO) oxidized cellulose nanofibrils (length 5-10 μm, diameter 10-20 nm, crystallinity 40.8%) are added into deionized water to prepare a suspension with concentration of 5%, and the suspension is stirred by magnetic force until no obvious agglomeration exists, and is treated by ultrasonic for 1h at 90 Hz. Dispersing 17g of nano aluminum sheets (solid content is 50%) with the particle size of 7 mu m in 13.33g of deionized water, dispersing the nano aluminum sheets into suspension under a high-speed shearing condition (400-800 rpm), adding 31g of ethylene-acrylic acid copolymer emulsion (solid content is 30%), 37.5g of the nano cellulose suspension and 1g of defoaming agent after 30min, and continuously maintaining the high-speed shearing condition for 2h to prepare the barrier coating.
Preparing water vapor barrier coating paper:
coating the composite coating on the front surface of single-sided glossy paper by a coating machine at a coating speed of 70m/min and a fixed quantity of 28g/m 2 Thickness of 40 μm, coatingCloth amount 9g/m 2 And the thickness of the dry film of the coating is 6 mu m, drying and curing are carried out for 60min at the temperature of 100 ℃, and the barrier paper is obtained after drying and storing. The water vapor transmission of the barrier paper was measured as standard and the results are shown in table 1.
Comparative example 1
Preparing the coating:
dispersing 20g of nano aluminum sheets (solid content is 50%) with the particle size of 7 mu m in 13.33g of deionized water, dispersing the nano aluminum sheets into suspension under a high-speed shearing condition (400-800 rpm), adding 66.67g of ethylene-acrylic acid copolymer emulsion (solid content is 30%) and 1g of defoaming agent after 30min, and continuously maintaining the high-speed shearing condition for 2h to prepare the barrier coating.
Preparing coated paper:
coating the composite coating on the front surface of the single-sided glossy paper by a coating machine at a coating speed of 70m/min, wherein the quantitative amount of the single-sided glossy paper is 28g/m 2 Thickness of 40 μm and coating weight of 9g/m 2 And the thickness of the dry film of the coating is 6 mu m, drying and curing are carried out for 60min at the temperature of 100 ℃, and the barrier paper is obtained after drying and storing. The water vapor transmission of the barrier paper was measured according to the standard, and the results are shown in Table 1.
Comparative example 2
Preparing the coating:
dispersing 13.33g of nano zinc sheets (solid content is 75%) with the particle size of 9 mu m into 46.67g of deionized water, dispersing into suspension under a high-speed shearing condition (400-800 rpm), adding 40g of butylbenzene emulsion (solid content is 50%) and 1g of bactericide after 30min, and continuously maintaining the high-speed shearing condition for 2h to prepare the barrier coating.
Preparing coated paper:
coating the composite coating on the front surface of the white cardboard by a coating machine at a coating speed of 70m/min, wherein the coating speed is 236g/m 2 A thickness of 318 μm and a coating weight of 15g/m 2 And the thickness of the dry film of the coating is 11 mu m, drying and curing are carried out for 80min at the temperature of 110 ℃, and the barrier paper is obtained after drying and storing. The water vapor transmission of the barrier paper was measured according to the standard, and the results are shown in Table 1.
Comparative example 3
Preparing the coating:
2,2,6,6-tetramethylpiperidine-nitrogen-oxide (TEMPO) oxidized cellulose nanofibrils (length 5-10 μm, diameter 10-20 nm, crystallinity 40.8%) are added into deionized water to prepare a suspension with concentration of 5%, and the suspension is stirred by magnetic force until no obvious agglomeration exists, and is treated by ultrasonic for 1h at 90 Hz. 40g of butylbenzene emulsion (solid content is 50%), 8g of the nano-cellulose suspension and 1g of defoamer are mixed and kept for 2 hours under a high-speed shearing condition (400-800 rpm) to prepare the barrier coating.
Preparation of coated paper:
coating the composite coating on the front surface of the single-sided glossy paper by a coating machine at a coating speed of 70m/min, wherein the quantitative amount of the single-sided glossy paper is 28g/m 2 Thickness of 40 μm and coating weight of 9g/m 2 And the thickness of the dry film of the coating is 6 mu m, drying and curing are carried out for 60min at the temperature of 100 ℃, and the barrier paper is obtained after drying and storing. The water vapor transmission of the barrier paper was measured as standard and the results are shown in table 1.
Comparative example 4
Preparing the coating:
carboxymethylated cellulose nanofibrils (with the length of 3-10 mu m, the diameter of 10-15 nm and the crystallinity of 56.5%) are added into deionized water to prepare suspension with the concentration of 5%, and the suspension is stirred by magnetic force until no obvious agglomeration exists and is treated by ultrasonic for 1h at 90 Hz. Dispersing 5g of nano copper sheet (solid content is 55%) with the particle size of 5 mu m in 35g of deionized water, dispersing the nano copper sheet into suspension under a high-speed shearing condition (400-800 rpm), adding 30.77g of polyvinylidene chloride (PVDC) emulsion (solid content is 65%), 8g of the nano cellulose suspension and 1g of thickening agent after 30min, and continuously maintaining the high-speed shearing condition for 2h to prepare the barrier coating.
Preparing coated paper:
coating the composite coating on the front surface of kraft paper by a coating machine at a coating speed of 70m/min, wherein the kraft paper has a quantitative amount of 115g/m 2 Thickness of 151 μm and coating weight of 12g/m 2 And the thickness of the dry film of the coating is 9 mu m, drying and curing are carried out for 70min at 105 ℃, and the barrier paper is obtained after drying and storing. The water vapor transmission of the barrier paper was measured as standard and the results are shown in table 1.
TABLE 1
According to the embodiment and the comparative example, the barrier coating prepared by the nano metal sheet, the adhesive, the nano cellulose and the additive in a proper proportion can form an ultrahigh barrier coating when being applied to coated paper, and the water vapor transmission can reach less than or equal to 5g/m 2 24h. The addition of the nano metal sheet plays a crucial role in blocking the water vapor transmission amount of the coating. When no nano metal sheet is added into the comparison document 3, the water vapor transmission rate is as high as 3006.55g/m 2 24h, indicating that it has almost no water vapor barrier properties; the nano metal sheets are added in the comparison document 4, but the addition amount of the nano metal sheets is small, and perfect lap joint between the nano metal sheets cannot be completed, so that the water vapor barrier property is poor, and the water vapor transmission rate is as high as 82.68g/m 2 24h. The addition of the nano-cellulose can reduce the water vapor transmission of the coated paper, because a complex cellulose interweaving network structure is formed in the coating, a gas diffusion path is prolonged, so that the water vapor transmission is reduced, and a barrier effect is better played.
The features of the invention claimed and/or described in the specification may be combined, and are not limited to the combinations set forth in the claims by the recitations therein. The technical solutions obtained by combining the technical features in the claims and/or the specification also belong to the scope of the present invention.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.
Claims (10)
1. The water vapor barrier coating is characterized by comprising the following solid contents in percentage by mass:
20-45% of nano metal sheet;
45-75% of adhesive;
1-10% of nano cellulose;
0 to 5 percent of additive.
2. The water vapor barrier coating of claim 1, wherein the nano metal sheets are selected from at least one of nano aluminum sheets, nano zinc sheets, nano copper sheets and nano titanium sheets; wherein the average radial dimension of the nano metal sheet is 5-60 mu m, the length-diameter ratio is more than 50, and the thickness is less than 100nm.
3. The water vapor barrier coating of claim 1, wherein the binder is selected from at least one of ethylene-acrylic acid copolymer emulsion, styrene-butadiene emulsion, acrylic acid emulsion, polyvinylidene chloride emulsion, styrene-acrylic emulsion, cellulose derivative, and lignin binder.
4. The water vapor barrier coating of claim 1, wherein the nanocellulose is selected from at least one of unmodified cellulose nanofibrils, 2,2,6,6-tetramethylpiperidine-nitrogen-oxide oxidized cellulose nanofibrils, quaternary ammonium salt modified cellulose nanofibrils, and carboxymethylated cellulose nanofibrils; wherein the diameter of the nano-cellulose is 10-40 nm, the length is more than 1 mu m, and the crystallinity is 40-60%.
5. The preparation method of the water vapor barrier coating is characterized by comprising the following steps of:
1) Adding nano-cellulose into water under the condition of stirring, stirring until no agglomeration exists, and performing ultrasonic treatment to obtain a nano-cellulose suspension;
2) Preparing the nano metal sheet into a suspension under a high-speed shearing condition;
3) Adding an adhesive, a nano-cellulose suspension and an additive into the suspension obtained in the step 2) under a high-speed shearing condition, and keeping the high-speed shearing condition for 1-2 hours to obtain a water vapor barrier coating; wherein the solid content of the water vapor barrier coating comprises the following components in percentage by mass: 20 to 45 percent of nano metal sheet, 45 to 75 percent of adhesive, 1 to 10 percent of nano cellulose and 0 to 5 percent of additive.
6. The preparation method according to claim 5, wherein the solid content of the water vapor barrier coating is 20 to 50% by mass.
7. A method for preparing water vapor barrier coating paper, which is characterized in that the water vapor barrier coating of any one of claims 1 to 4 is coated on a paper base material and dried and cured.
8. The method for manufacturing according to claim 7, wherein the paper-based material is selected from any one of single-sided glossy paper, white cardboard, and kraft paper; the water vapor barrier coating is coated on the front surface of the paper base material; the coating weight of the water vapor barrier coating is 3-15 g/m 2 The dry film thickness of the coating is 3-14 μm.
9. A water vapor barrier coated paper, comprising:
a paper based material;
the water vapor barrier coating is coated on the front surface of the paper base material; wherein the solid content of the water vapor barrier coating comprises the following components in percentage by mass: 20 to 45 percent of nano metal sheet, 45 to 75 percent of adhesive, 1 to 10 percent of nano cellulose and 0 to 5 percent of additive.
10. The water vapor barrier coated paper according to claim 9, having a water vapor transmission rate of 5g/m or less 2 ·24h。
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