CN111648159B - Preparation method of mildew-proof glass partition paper - Google Patents
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- CN111648159B CN111648159B CN202010475799.5A CN202010475799A CN111648159B CN 111648159 B CN111648159 B CN 111648159B CN 202010475799 A CN202010475799 A CN 202010475799A CN 111648159 B CN111648159 B CN 111648159B
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Abstract
The invention relates to the technical field of papermaking, and provides a preparation method of mildew-proof glass partition paper aiming at the problem of poor mildew-proof effect of the existing glass partition paper. The method comprises the following steps: (1) preparing base paper: chemically soaking bleached softwood pulp and bleached hardwood pulp, and pulping; mixing the bleached chemical pulp, the filler and the cationic starch, filtering by using clear water, dehydrating the net part, soaking in the mildew-proof network polymer, squeezing and drying to obtain raw paper; (2) coating a hydrophobic layer: coating the surface of the base paper with a hydrophobic modified polymer, drying, and carrying out hot pressing to obtain a finished product. The glass partition paper has good hydrophobic and waterproof properties and high mildew-proof efficiency, when the mildew-proof agent in the paper is sealed in the network polymer, the crosslinking degree is improved to prevent the mildew-proof agent from being removed as much as possible, and when the water content in the paper rises, the mildew-proof agent begins to be gradually released, so that the waste caused by the premature release of the mildew-proof agent is avoided, and the glass partition paper is high in density, strength and surface smoothness.
Description
Technical Field
The invention relates to the technical field of papermaking, in particular to a preparation method of mildew-proof glass partition paper.
Background
The glass spacer paper is used as the spacer paper between various kinds of glass, the glass spacer paper is used for the back end packing interval of glass products, also can be used for the glass substrate cutting or the attenuate back, glass and glass spacer mat use, the glass substrate is got on A type frame and is prevented in the production process of being convenient for, it is high to require to have surface strength, dustless no impurity, do not fall the hair and fall the powder, play important protection and isolation in various kinds of glass transportation, prevent that glass from mildening and rot, protect glass, prevent friction or fish tail between the glass substrate. When the glass is transported and stored for a long time, the glass spacing paper can be mildewed due to factors such as environmental humidity change and the like, and then the glass substrate is corroded, so that the protected glass substrate is damaged. The current domestic produced interval paper has the defects of easy mildew after long-time storage, high production cost, unstable product quality and the like.
The invention discloses a manufacturing method of long-acting anti-corrosion glass spacing paper, which belongs to the papermaking technology, and is characterized in that the paper is manufactured by 40-60% of bleached sulfate softwood pulp and 60-40% of GP pulp, the pulping mode adopts free pulping, and the stiffness of the paper can be kept as much as possible by using light knife defibering as the main energy; meanwhile, aluminum potassium sulfate, cationic polyacrylamide and a wet strength agent are used as auxiliary agents and are applied with an optimized surface sizing proportion, and the cost is saved while the paper has a long-acting anti-mildew effect by effectively controlling the dosage of the mildew preventive and reasonably distributing the adding time of the mildew preventive. The method comprises the following specific steps: pulping, netting and making, pressing and drying, surface sizing, secondary drying, press polishing and paper rolling.
The defects that the mildew preventive is directly added into the coating, the mildew preventive is easy to be prematurely lost, and the persistence of the mildew preventive effect is not high.
Disclosure of Invention
The invention aims to overcome the problem of poor mildew-proof effect of the existing glass partition paper, and provides a preparation method of the mildew-proof glass partition paper.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of mildew-proof glass partition paper comprises the following steps:
(1) preparing base paper: chemically soaking 50-60% of bleached softwood pulp and 40-50% of bleached hardwood pulp, and pulping to 50-75 DEG SR; mixing 50-65 parts by weight of bleached chemical pulp, 5-10 parts by weight of filler and 5-10 parts by weight of cationic starch, filtering with clear water, dehydrating the net part, soaking in a mildew-proof penetrating network polymer, squeezing and drying to obtain base paper;
(2) coating a hydrophobic layer: coating the surface of base paper with a hydrophobic modified polymer, wherein the coating weight is 3-12g/m 2; drying, heat treating at 100-110 deg.c for 3-4 hr and hot pressing to obtain the product.
Moisture and temperature are two major factors promoting the mildew of the glass spacing paper, wherein the greatest influence is moisture, and when the moisture content in the glass spacing paper is higher, the mildew is most easily grown. The control method of the mold comprises the steps of reducing the moisture content in the paper as much as possible, and adding a mold inhibitor to inhibit the generation of the mold. Therefore, on one hand, the hydrophobic layer is coated on the surface of the base paper, so that a strong hydrophobic effect can be achieved, moisture is prevented from invading into the glass partition paper, the growth condition of mould is prevented from being damaged, and the probability of mould breeding is reduced; on the other hand, the chitosan-polyvinyl alcohol-hexa methacrylate mildew-proof polymer is introduced into the base paper to prevent the mildew from growing by dissolving the release mildew-proof agent with water when water enters the base paper of the glass partition paper. The invention realizes the inhibition of mould from multiple angles and has better mould-proof function.
Preferably, in the step (1), the clean water filtration is performed by circulating clean water filtration and a 5000-mesh precision cloth bag filter.
Adopt above-mentioned equipment to filter can effectively detach the tiny grains of sand in the clear water, promote the homogeneity of thoughtlessly starching the composition, effectively get rid of impurity and the granule of beating in thoughtlessly starching, reduce the granularity in the body paper, promote its homogeneity and surface smoothness nature.
Preferably, in the step (1), the mildew-proof through network polymer is chitosan-polyvinyl alcohol-hexa methacrylate mildew-proof polymer, and the preparation method comprises the following steps: dissolving chitosan cellulose in acetic acid solution with the mass fraction of 10-15%, adding a mildew preventive, adding polyvinyl alcohol, sealing a beaker, preventing the concentration of the solution from being influenced by water vapor evaporation, stirring and dissolving in a constant-temperature water bath at 70-80 ℃, cooling, adding 1, 5-glutaraldehyde solution, fully stirring, reacting at the constant temperature of 45-55 ℃ for 1-1.5h, adding hexa-methacrylate into the solution, slowly heating to 96-100 ℃, and reacting for 2-2.5 h.
Preferably, the weight ratio of the chitosan cellulose, the mildew preventive, the polyvinyl alcohol, the 1, 5-glutaraldehyde and the hexa-methacrylate is 1: 0.2-0.4: 6-8: 0.15-0.3: 2-3.
For the chitosan-polyvinyl alcohol-hexa methacrylate mildew-proof polymer, chitosan cellulose is a natural high molecular polymer, chitosan has good biocompatibility and degradability and wide source and has-NH 2 and-OH groups, polyvinyl alcohol is also a water-soluble polymer and has-OH groups, and the two polymers can be crosslinked by aldehydes to form a crosslinked polymer, but the polymer prepared by independently taking chitosan as a raw material has the problems of high brittleness, low strength and the like. The unique chain structure of chitosan in the solution can penetrate into the cell wall of leaf wood fiber, and an interpenetrating polymer network structure can be formed in the leaf mixed fiber. The wood fiber contains a large amount of hydroxyl, and can form intermolecular hydrogen bonds with amino and hydroxyl in the cross-linked polymer and react to form chemical bonds, so that interaction is generated, and meanwhile, the polymer can block pores on part of leaf wood fiber, so that the effect of improving the dimensional stability of the wood and bamboo is achieved.
The mildew preventive is coated in the interpenetrating polymer network structure, so that the mildew preventive can be bound, the continuous release of the mildew preventive, the waste of the mildew preventive and the empty structure in the base paper are prevented, and the compactness and the mechanical property of the base paper are further influenced. When the base paper has a certain water content, partial blocks in the chitosan-polyvinyl alcohol-hexa methacrylate polymer network structure can be hydrolyzed, so that the mildew preventive in the network is released, and the mildew preventive effect is achieved.
The hexa-methacrylate is introduced into the polymer to improve the oleophilic property of the polymer and reduce the hydrophilicity of the polymer.
Preferably, the mildew preventive comprises at least one of calcium propionate, sodium sorbate, sodium benzoate and dimethyl fumarate.
The organic acid mildew inhibitor is selected because of small corrosivity and safe use, when water permeates into paper, the mildew has growth conditions, and under the conditions that the water with specific content and the mildew penetrates through the network polymer layer and the pH value is low, the organic acid salts are promoted to be converted into corresponding organic acid to inhibit the growth of the mildew, so that the mildew-proof effect is achieved.
Preferably, in the step (1), the soaking time of the chemical pulp of the bleaching pulp is 2-4 h; the squeezing condition is pressure of 500 and 600kPa for 30-50 min.
Preferably, in the step (2), the preparation of the fluorine-containing coating liquid with the hydrophobically modified polymer of hydroxypropyl methylcellulose-titanium dioxide nanoparticles comprises the following steps:
(a) preparing a nano titanium dioxide sol solution: mixing and stirring deionized water, phosphoric acid and titanium dioxide nanoparticles to obtain a solution A; taking ethyl orthosilicate and absolute ethyl alcohol, mixing and stirring under an ice bath condition to obtain a solution B; pouring the solution B into the solution A under magnetic stirring, and reacting for 3-5h to obtain a nano titanium dioxide sol solution;
(b) preparing a hydroxypropyl methyl cellulose-titanium dioxide nanoparticle coating solution: taking a hydroxypropyl methyl cellulose solution with the mass fraction of 30-50%, adding the nano titanium dioxide sol solution, stirring for 15-20min, adding glycidyl methacrylate, heating to 40-50 ℃, and stirring for 30-40min to obtain a hydroxypropyl methyl cellulose-titanium dioxide nano particle mixed solution;
(c) and c, adding 10-15% of N-hydroxyethyl perfluorooctanoic amide and 5-10% of tetrabutyl titanate serving as a catalyst into the mixed solution in the step b, and heating to 140-150 ℃ for reaction for 2-2.5h to obtain a finished product.
Preferably, the mass ratio of the deionized water to the phosphoric acid to the titanium dioxide nanoparticles in the step (a) is 1-2: 1: 5-7; the volume ratio of the ethyl orthosilicate to the absolute ethyl alcohol is 4-6: 1.
preferably, the particle size range of the titanium dioxide in the nano titanium dioxide sol solution in the step (a) is less than or equal to 300 nm.
Preferably, the mass ratio of the hydroxypropyl methyl cellulose solution, the nano titanium dioxide sol solution and the glycidyl methacrylate in the step (b) is 6-8: 1-3: 1.
the surface of the hydroxypropyl methyl cellulose-titanium dioxide nano-particle fluorine-containing coating layer has stronger oleophobic property and waterproof structure. The hydroxypropyl methyl cellulose has a bark-like and ridge-like shape, the roughness of the surface of the fiber is greatly improved after titanium dioxide nano particle sol is introduced in situ, and the titanium dioxide nano particles have a nucleating effect in liquid, so that the titanium dioxide nano particles are dispersed unevenly in the liquid and are locally agglomerated in the hydroxypropyl methyl cellulose to form nodes; the hydroxypropyl methyl cellulose has coarse fibers, the fibers are staggered and closely arranged and are stacked layer by layer, and further the overall roughness of the composite membrane is improved. In addition, the addition of the hydroxypropyl methyl cellulose solution enables the nano titanium dioxide particles to be embedded and embedded inside the fibers to form nano spurs, the prepared titanium dioxide nano particles contain internal structure water, are combined with the hydroxypropyl methyl cellulose through hydrogen bonds, are embedded in the polymer hydroxypropyl methyl cellulose matrix, are attached and embedded inside the nano fiber membrane to form a stable protruding membrane structure, have good hydrophilic performance, namely oleophobic performance, and greatly reduce the wetting quality of liquid through the nano spurs. In addition, the surface energy of the macromolecules is reduced by adding a polymerized monomer N-hydroxyethyl perfluorooctanoic acid amide to modify the synthesized macromolecules, the water immersion is prevented, a double-hydrophobic effect is formed under the synergistic effect of the double-hydrophobic effect and the nano spurs, and the water repellency and antifouling capacity of the surface of the glass spacer paper is further improved.
The titanium dioxide also has a certain antibacterial and bactericidal effect, and can inhibit mould while forming water-proof stab convex surfaces.
Therefore, the invention has the following beneficial effects:
(1) the preparation method of the mildew-proof glass partition paper is provided, the glass partition paper has good hydrophobic and waterproof properties and high mildew-proof efficiency, and when the mildew-proof agent in the paper is sealed in the through network polymer, the crosslinking degree is improved to prevent the mildew-proof agent from being removed as much as possible;
(2) the mildew is prevented from breeding by coating the waterproof hydrophobic layer on the surface and releasing the mildew preventive in water at multiple angles, the mildew prevention efficiency is high, the bonding force between the added components and the wood fibers of the leaves is enhanced by introducing multiple celluloses, and the crosslinking force among all layers is enhanced;
(3) when the water content in the paper rises, the mildew preventive is gradually released, so that the waste caused by the premature release of the mildew preventive is avoided, the compactness, the strength and the surface smoothness are high, and the dimensional stability of the base paper is ensured.
Detailed Description
The invention is further described with reference to specific embodiments.
In the present invention, the raw materials and equipment used are commercially available or commonly used in the art, unless otherwise specified. The methods in the following examples are conventional in the art unless otherwise specified.
Example 1
A preparation method of mildew-proof glass partition paper comprises the following steps:
(1) preparing base paper: chemically soaking 55% of bleached softwood pulp and 45% of bleached broad leaf pulp for 3 hours, and pulping to 60-degree SR; mixing 58 parts by weight of bleached chemical pulp, 8 parts by weight of filler and 8 parts by weight of cationic starch, filtering with clear water, dehydrating a net part, soaking in a mildew-proof penetrating network polymer, squeezing for 40min at 550kPa, and drying to obtain base paper;
the clear water filtration is realized by adopting circulating clear water filtration and using a 5000-mesh precision cloth bag filter for filtration;
the mildew-proof through network polymer is chitosan-polyvinyl alcohol-hexa methacrylate mildew-proof polymer, and the preparation steps comprise: dissolving chitosan cellulose in an acetic acid solution with the mass fraction of 12%, adding a mildew preventive, namely sodium benzoate, adding polyvinyl alcohol, sealing a beaker to prevent the concentration of the solution from being influenced by evaporation of water vapor, stirring and dissolving in a 75 ℃ constant-temperature water bath, cooling, adding a 1, 5-glutaraldehyde solution, fully stirring, reacting at the constant temperature of 50 ℃ for 1.3h, adding hexa-methacrylate into the solution, slowly heating to 98 ℃, and reacting for 2.2 h; the addition mass ratio of the chitosan cellulose, the mildew preventive, the polyvinyl alcohol, the 1, 5-glutaraldehyde and the hexa-methacrylate is 1: 0.3: 7: 0.22: 2.5;
(2) coating a hydrophobic layer: coating the surface of base paper with a hydrophobic modified polymer, wherein the coating weight is 8g/m2(ii) a Drying, heat treating at 105 deg.C for 3.5h, and hot pressing to obtain the final product;
the preparation method of the hydrophobic modified polymer hydroxypropyl methyl cellulose-titanium dioxide nanoparticle fluorine-containing coating liquid comprises the following steps:
(a) preparing a nano titanium dioxide sol solution: mixing and stirring deionized water, phosphoric acid and titanium dioxide nanoparticles with the particle size range of less than or equal to 300nm to obtain a solution A; taking ethyl orthosilicate and absolute ethyl alcohol, mixing and stirring under an ice bath condition to obtain a solution B; pouring the solution B into the solution A under magnetic stirring, and reacting for 4h to obtain a nano titanium dioxide sol solution; the mass ratio of the deionized water to the phosphoric acid to the titanium dioxide nanoparticles is 1.5: 1: 6; the volume ratio of the ethyl orthosilicate to the absolute ethyl alcohol is 5: 1;
(b) preparing a hydroxypropyl methyl cellulose-titanium dioxide nanoparticle coating solution: taking a hydroxypropyl methyl cellulose solution with the mass fraction of 40%, adding the nano titanium dioxide sol solution, stirring for 18min, adding glycidyl methacrylate, heating to 45 ℃, and stirring for 35min to obtain a hydroxypropyl methyl cellulose-titanium dioxide nano particle mixed solution; the mass ratio of the hydroxypropyl methyl cellulose solution to the nano titanium dioxide sol solution to the glycidyl methacrylate is 7: 2: 1;
(c) and c, adding 12% of N-hydroxyethyl perfluorooctanoic acid amide and 8% of catalyst tetrabutyl titanate into the mixed solution in the step b, heating to 145 ℃, and reacting for 2.3 hours to obtain a finished product.
Example 2
The difference from the embodiment 1 is that the preparation method of the mildewproof glass spacing paper comprises the following steps:
(1) preparing base paper: chemically soaking 50% bleached softwood pulp and 50% bleached broad leaf pulp for 3h, and pulping to 60-degree SR; mixing 50 parts by weight of bleached chemical pulp, 10 parts by weight of filler and 5 parts by weight of cationic starch, filtering with clear water, dehydrating a net part, soaking in a mildew-proof penetrating network polymer, squeezing for 40min at 550kPa, and drying to obtain base paper;
the clear water filtration is realized by adopting circulating clear water filtration and using a 5000-mesh precision cloth bag filter for filtration;
the mildew-proof through network polymer is chitosan-polyvinyl alcohol-hexa methacrylate mildew-proof polymer, and the preparation steps comprise: dissolving chitosan cellulose in an acetic acid solution with the mass fraction of 12%, adding a mildew preventive sodium sorbate, adding polyvinyl alcohol, sealing a beaker, preventing the concentration of the solution from being influenced by water vapor evaporation, stirring and dissolving in a 75 ℃ constant-temperature water bath, cooling, adding a 1, 5-glutaraldehyde solution, fully stirring, reacting at a constant temperature of 50 ℃ for 1.3h, adding hexa-methacrylate into the solution, slowly heating to 98 ℃, and reacting for 2.2 h; the addition mass ratio of the chitosan cellulose, the mildew preventive, the polyvinyl alcohol, the 1, 5-glutaraldehyde and the hexa-methacrylate is 1: 0.2: 8: 0.15: 3;
(2) coating a hydrophobic layer: coating the surface of base paper with a hydrophobic modified polymer, wherein the coating weight is 8g/m2(ii) a Drying, heat treating at 105 deg.C for 3.5h, and hot pressing to obtain the final product;
the preparation method of the hydrophobic modified polymer hydroxypropyl methyl cellulose-titanium dioxide nanoparticle fluorine-containing coating liquid comprises the following steps:
(a) preparing a nano titanium dioxide sol solution: mixing and stirring deionized water, phosphoric acid and titanium dioxide nanoparticles with the particle size range of less than or equal to 300nm to obtain a solution A; taking ethyl orthosilicate and absolute ethyl alcohol, mixing and stirring under an ice bath condition to obtain a solution B; pouring the solution B into the solution A under magnetic stirring, and reacting for 4h to obtain a nano titanium dioxide sol solution; the mass ratio of the deionized water to the phosphoric acid to the titanium dioxide nanoparticles is 1: 1: 7; the volume ratio of the ethyl orthosilicate to the absolute ethyl alcohol is 6: 1;
(b) preparing a hydroxypropyl methyl cellulose-titanium dioxide nanoparticle coating solution: taking a hydroxypropyl methyl cellulose solution with the mass fraction of 40%, adding the nano titanium dioxide sol solution, stirring for 18min, adding glycidyl methacrylate, heating to 45 ℃, and stirring for 35min to obtain a hydroxypropyl methyl cellulose-titanium dioxide nano particle mixed solution; the mass ratio of the hydroxypropyl methyl cellulose solution to the nano titanium dioxide sol solution to the glycidyl methacrylate is 6: 1: 1;
(c) and c, adding 15% of N-hydroxyethyl perfluorooctanoic acid amide and 5-10% of catalyst tetrabutyl titanate into the mixed solution in the step b, and heating to 145 ℃ for reaction for 2.3 hours to obtain a finished product.
Example 3
The difference from the embodiment 1 is that the preparation method of the mildewproof glass spacing paper comprises the following steps:
(1) preparing base paper: chemically soaking 52% bleached softwood pulp and 48% bleached broad leaf pulp for 3h, and pulping to 60-degree SR; mixing 51 parts by weight of bleached chemical pulp, 9 parts by weight of filler and 6 parts by weight of cationic starch, filtering with clear water, dehydrating a net part, soaking in a mildew-proof penetrating network polymer, squeezing for 40min at 550kPa, and drying to obtain base paper;
the clear water filtration is realized by adopting circulating clear water filtration and using a 5000-mesh precision cloth bag filter for filtration;
the mildew-proof through network polymer is chitosan-polyvinyl alcohol-hexa methacrylate mildew-proof polymer, and the preparation steps comprise: dissolving chitosan cellulose in an acetic acid solution with the mass fraction of 12%, adding a mildew preventive calcium propionate, adding polyvinyl alcohol, sealing a beaker, preventing water vapor from evaporating to influence the concentration of the solution, stirring and dissolving in a 75 ℃ constant-temperature water bath, cooling, adding a 1, 5-glutaraldehyde solution, fully stirring, reacting at a constant temperature of 50 ℃ for 1.3h, adding hexa-methacrylate into the solution, slowly heating to 98 ℃, and reacting for 2.2 h; the addition mass ratio of the chitosan cellulose, the mildew preventive, the polyvinyl alcohol, the 1, 5-glutaraldehyde and the hexa-methacrylate is 1: 0.25: 7.5: 0.2: 2.8 of;
(2) coating a hydrophobic layer: coating the surface of base paper with a hydrophobic modified polymer, wherein the coating weight is 8g/m2(ii) a Drying, heat treating at 105 deg.C for 3.5h, and hot pressing to obtain the final product;
the preparation method of the hydrophobic modified polymer hydroxypropyl methyl cellulose-titanium dioxide nanoparticle fluorine-containing coating liquid comprises the following steps:
(a) preparing a nano titanium dioxide sol solution: mixing and stirring deionized water, phosphoric acid and titanium dioxide nanoparticles with the particle size range of less than or equal to 300nm to obtain a solution A; taking ethyl orthosilicate and absolute ethyl alcohol, mixing and stirring under an ice bath condition to obtain a solution B; pouring the solution B into the solution A under magnetic stirring, and reacting for 4h to obtain a nano titanium dioxide sol solution; the mass ratio of the deionized water to the phosphoric acid to the titanium dioxide nanoparticles is 1.2: 1: 6.5; the volume ratio of the ethyl orthosilicate to the absolute ethyl alcohol is 4.5: 1; (b) preparing a hydroxypropyl methyl cellulose-titanium dioxide nanoparticle coating solution: taking a hydroxypropyl methyl cellulose solution with the mass fraction of 40%, adding the nano titanium dioxide sol solution, stirring for 18min, adding glycidyl methacrylate, heating to 45 ℃, and stirring for 35min to obtain a hydroxypropyl methyl cellulose-titanium dioxide nano particle mixed solution; the mass ratio of the hydroxypropyl methyl cellulose solution to the nano titanium dioxide sol solution to the glycidyl methacrylate is 7.5: 1.5: 1;
(c) and c, adding 10-15% of N-hydroxyethyl perfluorooctanoic acid amide and 5-10% of catalyst tetrabutyl titanate into the mixed solution in the step b, and heating to 145 ℃ for reaction for 2.3 hours to obtain a finished product.
Example 4
The difference from the embodiment 1 is that the preparation method of the mildewproof glass spacing paper comprises the following steps:
(1) preparing base paper: chemically soaking 58% bleached softwood pulp and 42% bleached broad leaf pulp for 3h, and pulping to 60-degree SR; mixing 62 parts by weight of bleached chemical pulp, 6 parts by weight of filler and 8 parts by weight of cationic starch, filtering with clear water, dehydrating a net part, soaking in a mildew-proof penetrating network polymer, squeezing for 40min at 550kPa, and drying to obtain base paper;
the clear water filtration is realized by adopting circulating clear water filtration and using a 5000-mesh precision cloth bag filter for filtration;
the mildew-proof through network polymer is chitosan-polyvinyl alcohol-hexa methacrylate mildew-proof polymer, and the preparation steps comprise: dissolving chitosan cellulose in an acetic acid solution with the mass fraction of 12%, adding a mildew preventive dimethyl fumarate, adding polyvinyl alcohol, sealing a beaker to prevent the concentration of the solution from being influenced by water vapor evaporation, stirring and dissolving in a 75 ℃ constant-temperature water bath, cooling, adding a 1, 5-glutaraldehyde solution, fully stirring, reacting at the constant temperature of 50 ℃ for 1.3h, adding hexa-methacrylate into the solution, slowly heating to 98 ℃, and reacting for 2.2 h; the addition mass ratio of the chitosan cellulose, the mildew preventive, the polyvinyl alcohol, the 1, 5-glutaraldehyde and the hexa-methacrylate is 1: 0.35: 6.5: 0.28: 2.8 of;
(2) coating a hydrophobic layer: coating the surface of base paper with a hydrophobic modified polymer, wherein the coating weight is 8g/m2(ii) a Drying, heat treating at 105 deg.C for 3.5h, and hot pressing to obtain the final product;
the preparation method of the hydrophobic modified polymer hydroxypropyl methyl cellulose-titanium dioxide nanoparticle fluorine-containing coating liquid comprises the following steps:
(a) preparing a nano titanium dioxide sol solution: mixing and stirring deionized water, phosphoric acid and titanium dioxide nanoparticles with the particle size range of less than or equal to 300nm to obtain a solution A; taking ethyl orthosilicate and absolute ethyl alcohol, mixing and stirring under an ice bath condition to obtain a solution B; pouring the solution B into the solution A under magnetic stirring, and reacting for 4h to obtain a nano titanium dioxide sol solution; the mass ratio of the deionized water to the phosphoric acid to the titanium dioxide nanoparticles is 1.8: 1: 6.8; the volume ratio of the ethyl orthosilicate to the absolute ethyl alcohol is 5.2: 1;
(b) preparing a hydroxypropyl methyl cellulose-titanium dioxide nanoparticle coating solution: taking a hydroxypropyl methyl cellulose solution with the mass fraction of 40%, adding the nano titanium dioxide sol solution, stirring for 18min, adding glycidyl methacrylate, heating to 45 ℃, and stirring for 35min to obtain a hydroxypropyl methyl cellulose-titanium dioxide nano particle mixed solution; the mass ratio of the hydroxypropyl methyl cellulose solution to the nano titanium dioxide sol solution to the glycidyl methacrylate is 6.2: 1.2: 1;
(c) and c, adding 14% of N-hydroxyethyl perfluorooctanoic acid amide and 6% of catalyst tetrabutyl titanate into the mixed solution in the step b, heating to 145 ℃, and reacting for 2.3 hours to obtain a finished product.
Example 5
The difference from the embodiment 1 is that the preparation method of the mildewproof glass spacing paper comprises the following steps:
(1) preparing base paper: chemically soaking 60% bleached softwood pulp and 40% bleached broad leaf pulp for 3h, and pulping to 60-degree SR; mixing 65 parts by weight of bleached chemical pulp, 8 parts by weight of filler and 5 parts by weight of cationic starch, filtering with clear water, dehydrating a net part, soaking in a mildew-proof penetrating network polymer, squeezing for 40min at 550kPa, and drying to obtain base paper;
the clear water filtration is realized by adopting circulating clear water filtration and using a 5000-mesh precision cloth bag filter for filtration;
the mildew-proof through network polymer is chitosan-polyvinyl alcohol-hexa methacrylate mildew-proof polymer, and the preparation steps comprise: dissolving chitosan cellulose in an acetic acid solution with the mass fraction of 12%, adding a mildew preventive dimethyl fumarate, adding polyvinyl alcohol, sealing a beaker to prevent the concentration of the solution from being influenced by water vapor evaporation, stirring and dissolving in a 75 ℃ constant-temperature water bath, cooling, adding a 1, 5-glutaraldehyde solution, fully stirring, reacting at the constant temperature of 50 ℃ for 1.3h, adding hexa-methacrylate into the solution, slowly heating to 98 ℃, and reacting for 2.2 h; the addition mass ratio of the chitosan cellulose, the mildew preventive, the polyvinyl alcohol, the 1, 5-glutaraldehyde and the hexa-methacrylate is 1: 0.4: 6: 0.3: 2;
(2) coating a hydrophobic layer: coating the surface of base paper with a hydrophobic modified polymer, wherein the coating weight is 8g/m2(ii) a Drying, heat treating at 105 deg.C for 3.5h, and hot pressing to obtain the final product;
the preparation method of the hydrophobic modified polymer hydroxypropyl methyl cellulose-titanium dioxide nanoparticle fluorine-containing coating liquid comprises the following steps:
(a) preparing a nano titanium dioxide sol solution: mixing and stirring deionized water, phosphoric acid and titanium dioxide nanoparticles with the particle size range of less than or equal to 300nm to obtain a solution A; taking ethyl orthosilicate and absolute ethyl alcohol, mixing and stirring under an ice bath condition to obtain a solution B; pouring the solution B into the solution A under magnetic stirring, and reacting for 4h to obtain a nano titanium dioxide sol solution; the mass ratio of the deionized water to the phosphoric acid to the titanium dioxide nanoparticles is 2: 1: 5; the volume ratio of the ethyl orthosilicate to the absolute ethyl alcohol is 6: 1;
(b) preparing a hydroxypropyl methyl cellulose-titanium dioxide nanoparticle coating solution: taking a hydroxypropyl methyl cellulose solution with the mass fraction of 40%, adding the nano titanium dioxide sol solution, stirring for 18min, adding glycidyl methacrylate, heating to 45 ℃, and stirring for 35min to obtain a hydroxypropyl methyl cellulose-titanium dioxide nano particle mixed solution; the mass ratio of the hydroxypropyl methyl cellulose solution to the nano titanium dioxide sol solution to the glycidyl methacrylate is 8: 3: 1;
(c) and c, adding 15% of N-hydroxyethyl perfluorooctanoic acid amide and 10% of catalyst tetrabutyl titanate into the mixed solution in the step b, heating to 145 ℃, and reacting for 2.3 hours to obtain a finished product.
Comparative example 1 (different from example 1 in that no mildewproof agent was added to the base paper of the glass separation paper.)
A preparation method of mildew-proof glass partition paper comprises the following steps:
(1) preparing base paper: chemically soaking 55% of bleached softwood pulp and 45% of bleached broad leaf pulp for 3 hours, and pulping to 60-degree SR; mixing 58 parts by weight of bleached chemical pulp, 8 parts by weight of filler and 8 parts by weight of cationic starch, filtering by using clear water, dehydrating a net part, soaking in a through-network polymer, squeezing for 40min at 550kPa, and drying to obtain base paper;
the clear water filtration is realized by adopting circulating clear water filtration and using a 5000-mesh precision cloth bag filter for filtration;
the penetrating network polymer is chitosan-polyvinyl alcohol-hexa methacrylate polymer, and the preparation steps comprise: dissolving chitosan cellulose in an acetic acid solution with the mass fraction of 12%, adding polyvinyl alcohol, sealing a beaker, preventing the concentration of the solution from being influenced by the evaporation of water vapor, stirring and dissolving in a 75 ℃ constant-temperature water bath, cooling, adding a 1, 5-glutaraldehyde solution, fully stirring, reacting at a constant temperature of 50 ℃ for 1.3h, adding hexa-methacrylate into the solution, slowly heating to 98 ℃, and reacting for 2.2 h; the adding mass ratio of the chitosan cellulose, the polyvinyl alcohol, the 1, 5-glutaraldehyde and the hexa-methacrylate is 1: 7: 0.22: 2.5;
(2) coating a hydrophobic layer: coating the surface of base paper with a hydrophobic modified polymer, wherein the coating weight is 8g/m2(ii) a Drying, heat treating at 105 deg.C for 3.5h, and hot pressing to obtain the final product;
the preparation method of the hydrophobic modified polymer hydroxypropyl methyl cellulose-titanium dioxide nanoparticle fluorine-containing coating liquid comprises the following steps:
(a) preparing a nano titanium dioxide sol solution: mixing and stirring deionized water, phosphoric acid and titanium dioxide nanoparticles with the particle size range of less than or equal to 300nm to obtain a solution A; taking ethyl orthosilicate and absolute ethyl alcohol, mixing and stirring under an ice bath condition to obtain a solution B; pouring the solution B into the solution A under magnetic stirring, and reacting for 4h to obtain a nano titanium dioxide sol solution; the mass ratio of the deionized water to the phosphoric acid to the titanium dioxide nanoparticles is 1.5: 1: 6; the volume ratio of the ethyl orthosilicate to the absolute ethyl alcohol is 5: 1;
(b) preparing a hydroxypropyl methyl cellulose-titanium dioxide nanoparticle coating solution: taking a hydroxypropyl methyl cellulose solution with the mass fraction of 40%, adding the nano titanium dioxide sol solution, stirring for 18min, adding glycidyl methacrylate, heating to 45 ℃, and stirring for 35min to obtain a hydroxypropyl methyl cellulose-titanium dioxide nano particle mixed solution; the mass ratio of the hydroxypropyl methyl cellulose solution to the nano titanium dioxide sol solution to the glycidyl methacrylate is 7: 2: 1;
(c) and c, adding 12% of N-hydroxyethyl perfluorooctanoic acid amide and 8% of catalyst tetrabutyl titanate into the mixed solution in the step b, heating to 145 ℃, and reacting for 2.3 hours to obtain a finished product.
Comparative example 2 (different from example 1 in that chitosan-polyvinyl alcohol-hexa methacrylate was not introduced into the base paper of the glass barrier paper)
A preparation method of mildew-proof glass partition paper comprises the following steps:
(1) preparing base paper: chemically soaking 55% of bleached softwood pulp and 45% of bleached broad leaf pulp for 3 hours, and pulping to 60-degree SR; mixing 58 parts by weight of bleached chemical pulp, 8 parts by weight of filler and 8 parts by weight of cationic starch, filtering with clear water, dehydrating a net part, soaking in a mildew preventive sodium benzoate, squeezing for 40min at 550kPa, and drying to obtain base paper;
the clear water filtration is realized by adopting circulating clear water filtration and using a 5000-mesh precision cloth bag filter for filtration;
(2) coating a hydrophobic layer: coating the surface of base paper with a hydrophobic modified polymer, wherein the coating weight is 8g/m2(ii) a Drying, heat treating at 105 deg.C for 3.5h, and hot pressing to obtain the final product;
the preparation method of the hydrophobic modified polymer hydroxypropyl methyl cellulose-titanium dioxide nanoparticle fluorine-containing coating liquid comprises the following steps:
(a) preparing a nano titanium dioxide sol solution: mixing and stirring deionized water, phosphoric acid and titanium dioxide nanoparticles with the particle size range of less than or equal to 300nm to obtain a solution A; taking ethyl orthosilicate and absolute ethyl alcohol, mixing and stirring under an ice bath condition to obtain a solution B; pouring the solution B into the solution A under magnetic stirring, and reacting for 4h to obtain a nano titanium dioxide sol solution; the mass ratio of the deionized water to the phosphoric acid to the titanium dioxide nanoparticles is 1.5: 1: 6; the volume ratio of the ethyl orthosilicate to the absolute ethyl alcohol is 5: 1;
(b) preparing a hydroxypropyl methyl cellulose-titanium dioxide nanoparticle coating solution: taking a hydroxypropyl methyl cellulose solution with the mass fraction of 40%, adding the nano titanium dioxide sol solution, stirring for 18min, adding glycidyl methacrylate, heating to 45 ℃, and stirring for 35min to obtain a hydroxypropyl methyl cellulose-titanium dioxide nano particle mixed solution; the mass ratio of the hydroxypropyl methyl cellulose solution to the nano titanium dioxide sol solution to the glycidyl methacrylate is 7: 2: 1;
(c) and c, adding 12% of N-hydroxyethyl perfluorooctanoic acid amide and 8% of catalyst tetrabutyl titanate into the mixed solution in the step b, heating to 145 ℃, and reacting for 2.3 hours to obtain a finished product.
Comparative example 3 (different from example 1 in that the hydroxypropylmethylcellulose-titanium dioxide nanoparticle fluorine-containing coating liquid was replaced with a hydroxypropylmethylcellulose fluorine-containing coating liquid)
A preparation method of mildew-proof glass partition paper comprises the following steps:
(1) preparing base paper: chemically soaking 55% of bleached softwood pulp and 45% of bleached broad leaf pulp for 3 hours, and pulping to 60-degree SR; mixing 58 parts by weight of bleached chemical pulp, 8 parts by weight of filler and 8 parts by weight of cationic starch, filtering with clear water, dehydrating a net part, soaking in a mildew-proof penetrating network polymer, squeezing for 40min at 550kPa, and drying to obtain base paper;
the clear water filtration is realized by adopting circulating clear water filtration and using a 5000-mesh precision cloth bag filter for filtration;
the mildew-proof through network polymer is chitosan-polyvinyl alcohol-hexa methacrylate mildew-proof polymer, and the preparation steps comprise: dissolving chitosan cellulose in an acetic acid solution with the mass fraction of 12%, adding a mildew preventive dimethyl fumarate, adding polyvinyl alcohol, sealing a beaker to prevent the concentration of the solution from being influenced by water vapor evaporation, stirring and dissolving in a 75 ℃ constant-temperature water bath, cooling, adding a 1, 5-glutaraldehyde solution, fully stirring, reacting at the constant temperature of 50 ℃ for 1.3h, adding hexa-methacrylate into the solution, slowly heating to 98 ℃, and reacting for 2.2 h; the addition mass ratio of the chitosan cellulose, the mildew preventive, the polyvinyl alcohol, the 1, 5-glutaraldehyde and the hexa-methacrylate is 1: 0.3: 7: 0.22: 2.5;
(2) coating a hydrophobic layer: coating the surface of base paper with a hydrophobic modified polymer, wherein the coating weight is 8g/m2(ii) a Drying, heat treating at 105 deg.C for 3.5h, and hot pressing to obtain the final product;
the preparation method of the hydrophobic modified polymer hydroxypropyl methyl cellulose-titanium dioxide nanoparticle fluorine-containing coating liquid comprises the following steps: preparing a hydroxypropyl methyl cellulose-titanium dioxide nanoparticle coating solution: taking hydroxypropyl methyl cellulose solution with the mass fraction of 40%, stirring for 18min, adding N-hydroxyethyl perfluorooctanoic amide accounting for 12% of the mass ratio and tetrabutyl titanate serving as a catalyst accounting for 8%, heating to 145 ℃, and reacting for 2.3h to obtain the finished product.
Comparative example 4 (different from example 1 in that the surface is not coated with a hydrophobic layer)
A preparation method of mildew-proof glass partition paper comprises the following steps:
(1) preparing base paper: chemically soaking 55% of bleached softwood pulp and 45% of bleached broad leaf pulp for 3 hours, and pulping to 60-degree SR; mixing 58 parts by weight of bleached chemical pulp, 8 parts by weight of filler and 8 parts by weight of cationic starch, filtering with clear water, dehydrating a net part, soaking in a mildew-proof penetrating network polymer, squeezing for 40min at 550kPa, and drying to obtain base paper;
the clear water filtration is realized by adopting circulating clear water filtration and using a 5000-mesh precision cloth bag filter for filtration;
the mildew-proof through network polymer is chitosan-polyvinyl alcohol-hexa methacrylate mildew-proof polymer, and the preparation steps comprise: dissolving chitosan cellulose in an acetic acid solution with the mass fraction of 12%, adding a mildew preventive dimethyl fumarate, adding polyvinyl alcohol, sealing a beaker to prevent the concentration of the solution from being influenced by water vapor evaporation, stirring and dissolving in a 75 ℃ constant-temperature water bath, cooling, adding a 1, 5-glutaraldehyde solution, fully stirring, reacting at the constant temperature of 50 ℃ for 1.3h, adding hexa-methacrylate into the solution, slowly heating to 98 ℃, and reacting for 2.2 h; the addition mass ratio of the chitosan cellulose, the mildew preventive, the polyvinyl alcohol, the 1, 5-glutaraldehyde and the hexa-methacrylate is 1: 0.3: 7: 0.22: 2.5;
the detection method comprises the following steps: cutting the mildew-proof glass partition paper into a circular sheet with the diameter of 2 cm, coating a soil bean culture medium on the mildew-proof coating of the mildew-proof coated paper, inoculating mildew on the potato culture medium, culturing for 48 hours in an environment with the temperature of 55% at 25 ℃, and observing.
The detection methods of other parameters are conventional test detection methods in the field.
TABLE 1 various performance indexes of the mildewproof glass spacer paper
Note: grade 0 indicates no mold growth observed under microscope; grade 1 indicates that mold growth is visible to the naked eye, but the growth area is less than 1%; grade 2 means that the mold growth coverage is less than 10%; grade 3 indicates a mold growth coverage of greater than 20%.
And (4) conclusion: examples 1 to 5 show that the mildewproof glass partition paper with excellent performance prepared by the method of the invention introduces a chitosan-polyvinyl alcohol-hexa methacrylate mildewproof polymer into base paper to prevent the mildewproof agent from being released by water dissolution to inhibit the growth of the mildewproof when water is soaked into the base paper of the glass partition paper; in addition, the hydrophobic layer is coated on the surface of the base paper, so that a strong hydrophobic effect can be achieved, moisture is prevented from invading into the glass partition paper, the growth condition of mould is damaged, and the breeding probability of mould is reduced.
The difference between the comparative example 1 and the example 1 is that the raw paper of the glass partition paper is not added with the mildew preventive; the organic acid mildew inhibitor is selected because the organic acid mildew inhibitor is low in corrosivity and safe to use, when water permeates into paper, the mildew has growth conditions, the organic acid salts are promoted to be converted into corresponding organic acid under the conditions that the water with specific content and the mildew penetrates through the network polymer layer and the pH value is low, the cell structure of the mildew is damaged, the growth of the mildew is further inhibited, and therefore the mildew-proof effect is achieved.
The difference between the comparative example 2 and the example 1 is that the penetrating network polymer which is not introduced into the base paper of the glass spacing paper is chitosan-polyvinyl alcohol-hexa methacrylate; can realize the formation of an interpenetrating polymer network structure in the leaf mixed fiber. The wood fiber contains a large amount of hydroxyl, and can form intermolecular hydrogen bonds with amino and hydroxyl in the cross-linked polymer and react to form chemical bonds, so that interaction is generated, meanwhile, the polymer can block pores on part of leaf wood fiber, the effect of improving the dimensional stability of the wood and bamboo is achieved, and the mildew inhibitor can be bound by coating the mildew inhibitor in an interpenetrating polymer network structure; the chitosan-polyvinyl alcohol-hexa methacrylate polymer is not added, so that the mechanical property of the whole base paper is poor, the continuous release of the mildew preventive, the waste of the mildew preventive and the hollowing of the internal structure of the base paper can be caused, the compactness and the mechanical property of the base paper are further influenced, and the mildew-proof and bacteriostatic ability is poor.
Comparative example 3 is different from example 1 in that hydroxypropylmethylcellulose-titanium dioxide nanoparticle fluorine-containing coating liquid was replaced with hydroxypropylmethylcellulose fluorine-containing coating liquid; the hydroxypropyl methyl cellulose has a bark-like and ridge-like shape, the roughness of the surface of the fiber is greatly improved after titanium dioxide nano particle sol is introduced in situ, and the titanium dioxide nano particles have a nucleating effect in liquid, so that the titanium dioxide nano particles are dispersed unevenly in the liquid and are locally agglomerated in the hydroxypropyl methyl cellulose to form nodes; the chitosan cellulose membrane has coarse fibers, the fibers are staggered and closely arranged and are stacked layer by layer, and further the overall roughness of the composite membrane is improved. In addition, the addition of the chitosan cellulose sol solution enables the nano titanium dioxide particles to be embedded and embedded in the fibers to form nano spurs, the wetting angle of the liquid is greatly improved by the nano spurs, the obvious amphiphobic effect is achieved, and the nano spurs cannot be formed on the surface of the second coating layer without the addition of the titanium dioxide nanoparticles, so that the amphiphobic effect of the mildew-proof glass partition paper is poor; the antibacterial and bactericidal performance of the glass partition paper can be reduced without adding titanium dioxide, so that the mildew-proof and mildew-proof capability of the glass partition paper is poor.
Comparative example 4 is different from example 1 in that the surface is not coated with a hydrophobic layer; the glass partition paper does not have good waterproof performance in a high-humidity environment, moisture can easily invade into paper to trigger the release of a mildew preventive, when the moisture content in the paper is too high, the growth of mildew can be caused to be tenacious, the waterproof and bacteriostatic effects in the final detection result are reduced, and all performance indexes of the glass partition paper are reduced.
The embodiments described above are merely preferred embodiments of the present invention, which is not intended to be limiting in any way, and other variations and modifications are possible without departing from the scope of the invention as set forth in the claims below.
The raw materials and equipment used in the invention are common raw materials and equipment in the field if not specified; the methods used in the present invention are conventional in the art unless otherwise specified.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, alterations and equivalents of the above embodiments according to the technical spirit of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (8)
1. The preparation method of the mildew-proof glass partition paper is characterized by comprising the following steps of:
(1) preparing base paper: chemically soaking 50-60% of bleached softwood pulp and 40-50% of bleached hardwood pulp, and pulping to 50-75 DEG SR; mixing 50-65 parts by weight of bleached chemical pulp, 5-10 parts by weight of filler and 5-10 parts by weight of cationic starch, filtering with clear water, dehydrating the net part, soaking in a mildew-proof penetrating network polymer, squeezing and drying to obtain base paper;
(2) coating a hydrophobic layer: coating the surface of base paper with hydrophobic modified polymer, wherein the coating weight is 3-12g/m2(ii) a Drying, heat treating at 100-110 deg.c for 3-4 hr and hot pressing to obtain the product;
in the step (1), the mildew-proof through network polymer is chitosan-polyvinyl alcohol-hexa methacrylate mildew-proof polymer, and the preparation steps comprise: dissolving chitosan cellulose in acetic acid solution with the mass fraction of 10-15%, adding a mildew preventive, adding polyvinyl alcohol, sealing a beaker, preventing the concentration of the solution from being influenced by water vapor evaporation, stirring and dissolving in a constant-temperature water bath at 70-80 ℃, cooling, adding 1, 5-glutaraldehyde solution, fully stirring, reacting at the constant temperature of 45-55 ℃ for 1-1.5h, adding hexa-methacrylate into the solution, slowly heating to 96-100 ℃, and reacting for 2-2.5 h;
the hydrophobic modified polymer is hydroxypropyl methyl cellulose-titanium dioxide nanoparticle fluorine-containing coating liquid, and the preparation steps comprise:
(a) preparing a nano titanium dioxide sol solution: mixing and stirring deionized water, phosphoric acid and titanium dioxide nanoparticles to obtain a solution A; taking ethyl orthosilicate and absolute ethyl alcohol, mixing and stirring under an ice bath condition to obtain a solution B; pouring the solution B into the solution A under magnetic stirring, and reacting for 3-5h to obtain a nano titanium dioxide sol solution;
(b) preparing a hydroxypropyl methyl cellulose-titanium dioxide nanoparticle coating solution: taking a hydroxypropyl methyl cellulose solution with the mass fraction of 30-50%, adding the nano titanium dioxide sol solution, stirring for 15-20min, adding glycidyl methacrylate, heating to 40-50 ℃, and stirring for 30-40min to obtain a hydroxypropyl methyl cellulose-titanium dioxide nano particle mixed solution;
(c) and c, adding 10-15% of N-hydroxyethyl perfluorooctanoic amide and 5-10% of tetrabutyl titanate serving as a catalyst into the mixed solution in the step b, and heating to 140-150 ℃ for reaction for 2-2.5h to obtain a finished product.
2. The method for preparing the mildewproof glass spacing paper according to the claim 1, wherein in the step (1), the clean water is filtered by circulating clean water and a 5000-mesh precision cloth bag filter.
3. The preparation method of the mildewproof glass partition paper according to claim 1, wherein the chitosan cellulose, the mildewproof agent, the polyvinyl alcohol, the 1, 5-glutaraldehyde and the hexa-methacrylate are added in a mass ratio of 1: (0.2-0.4): (6-8): (0.15-0.3): (2-3).
4. The method for preparing mildewproof glass spacing paper according to claim 1, wherein the mildewcide comprises at least one of calcium propionate, sodium sorbate, sodium benzoate and dimethyl fumarate.
5. The method for preparing mildewproof glass spacing paper according to claim 1, wherein in the step (1), the chemical pulp of the bleaching pulp is soaked for 2-4 h; the squeezing condition is pressure of 500 and 600kPa for 30-50 min.
6. The preparation method of the mildewproof glass spacing paper according to claim 1, wherein the mass ratio of the deionized water to the phosphoric acid to the titanium dioxide nano particles in the step (a) is (1-2): 1: (5-7); the volume ratio of the ethyl orthosilicate to the absolute ethyl alcohol is (4-6): 1.
7. the method for preparing mildewproof glass spacing paper according to claim 1, wherein the particle size range of the titanium dioxide in the nano titanium dioxide sol solution in the step (a) is less than or equal to 300 nm.
8. The method for preparing the mildewproof glass spacing paper according to claim 1, wherein the mass ratio of the hydroxypropyl methyl cellulose solution, the nano titanium dioxide sol solution and the glycidyl methacrylate in the step (b) is (6-8): (1-3): 1.
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