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CN115897284B - Production method of waterproof wear-resistant corrugated board - Google Patents

Production method of waterproof wear-resistant corrugated board Download PDF

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Publication number
CN115897284B
CN115897284B CN202211630185.5A CN202211630185A CN115897284B CN 115897284 B CN115897284 B CN 115897284B CN 202211630185 A CN202211630185 A CN 202211630185A CN 115897284 B CN115897284 B CN 115897284B
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waterproof
corrugated board
isocyanate
monomer
parts
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CN115897284A (en
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孙学成
李凯
吕荣菊
姚永富
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Hangzhou Yongjing Technology Co ltd
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Hangzhou Yongjing Technology Co ltd
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Abstract

The application discloses waterproof wear-resisting corrugated board and production method thereof, this corrugated board surface is formed with waterproof resin layer through the coating stoving, waterproof resin includes the raw materials of following parts by weight: aqueous acrylic emulsion: 40-60 parts; chlorinated paraffin: 5-10 parts; dispersing agent: 1-2 parts; isocyanate modified filler: 5-12 parts; isocyanate groups are grafted on the surface of the isocyanate modified filler. The corrugated board is waterproof, wear-resistant and easy to store, and can be used for manufacturing corrugated boxes with more repeated utilization times.

Description

Production method of waterproof wear-resistant corrugated board
Technical Field
The application relates to the field of corrugated boards, in particular to a production method of waterproof and wear-resistant corrugated boards.
Background
The corrugated case is the most widely applied commodity packaging material on the market due to the advantages of light weight, recoverability, degradability, low price, abundant raw materials, mature process and the like. Corrugated board is the upstream raw material of corrugated boxes, and is usually formed by compounding at least one layer of corrugated surface paper and a corrugated medium, and has certain mechanical strength.
Most of the corrugated cartons on the market at present are disposable articles, and the corrugated cartons lack reusable performance, such as waterproofness and wear resistance, when being designed and manufactured, so that the corrugated cartons are difficult to store and recycle, and a large amount of resources are wasted.
Disclosure of Invention
The application provides a production method of waterproof wear-resistant corrugated board, which has excellent waterproof property and wear resistance, so that the corrugated board manufactured by the method is more beneficial to long-term preservation and recycling.
In a first aspect, the present application provides a waterproof and abrasion-resistant corrugated board, the surface of which is coated and dried to form a waterproof resin layer, wherein the waterproof resin comprises the following raw materials in parts by weight:
aqueous acrylic emulsion: 40-60 parts;
chlorinated paraffin: 5-10 parts;
dispersing agent: 1-2 parts;
isocyanate modified filler: 5-12 parts;
isocyanate groups are grafted on the surface of the isocyanate modified filler.
By adopting the technical scheme, the aqueous acrylic emulsion has good waterproof performance after being dried, and the corrugated board can be endowed with excellent waterproof effect by being matched with chlorinated paraffin. The addition of the inorganic filler can endow the corrugated case with excellent wear-resistant effect, but in order to reduce the powder falling probability of the corrugated case, the wear-resistant effect with longer effect is obtained. According to the method, the filler is subjected to surface modification, and isocyanate groups are introduced into the surface of the filler, so that the filler can react and crosslink with carboxylic acid groups or hydroxyl groups in the aqueous acrylic emulsion to form firm chemical connection, the probability of filler falling is effectively reduced, and the long-acting wear resistance of the filler is ensured. In addition, the crosslinking reaction of the isocyanate modified filler and the aqueous acrylic emulsion can effectively enhance the compactness of the resin layer and improve the waterproof performance of the resin layer.
Preferably, the isocyanate modified filler has a D50 particle size of 10 to 500. Mu.m, more preferably 100 to 200. Mu.m.
Typically, but not by way of limitation, the dispersant employs a nonionic surfactant.
Typically, but not by way of limitation, the carbodiimide hydrochloride is 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride.
Preferably, the polymerized monomers of the aqueous acrylic emulsion are as follows:
soft monomer: 10-20 parts;
hard monomer: 10-20 parts;
hydroxyl-containing monomers: 2-5 parts;
the hydroxyl-containing monomer is selected from one or a combination of a plurality of N-methylolacrylamide, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
The adoption of the soft and hard monomer ratio is beneficial to obtaining the acrylic resin coating with good hardness and toughness. By adding the hydroxyl-containing monomer, the carboxyl content and density of emulsion particles can be effectively improved, the reaction crosslinking of the emulsion particles and isocyanate modified filler is promoted, and the filler falling-off phenomenon is effectively reduced.
Preferably, the soft monomer is selected from one or a combination of several of acrylic acid, ethyl acrylate and butyl acrylate; the hard monomer is selected from one or a combination of more of styrene, acrylonitrile, methyl acrylate, methyl methacrylate and vinylidene chloride.
Preferably, the soft monomer is a combination of acrylic acid and other monomers, and the acrylic acid accounts for 50-70 wt% of the soft monomer.
Preferably, the acrylic emulsion is prepared according to the following method:
pre-emulsification: mixing and dispersing soft monomer, hard monomer and 40-60 wt% hydroxyl-containing monomer into emulsifier water solution to obtain pre-emulsified monomer; dissolving an initiator in water to obtain an initiator solution;
and (3) primary polymerization: adding a pre-emulsified monomer and an initiator solution with the weight percent of 90-95% into a sodium bicarbonate buffer solution with the temperature of 76-88 ℃ for stirring reaction;
and (3) secondary polymerization: adding the rest hydroxyl-containing monomer and initiator solution, continuing stirring and reacting, and finishing the reaction when the solid content reaches 45-50%, thus obtaining the aqueous acrylic emulsion.
The application adopts a secondary polymerization process, and more hydroxyl groups can be introduced on the surface of emulsion particles by adding 40-60 wt% of hydroxyl-containing monomers in the later polymerization stage, so that the reactivity of the aqueous acrylic emulsion and isocyanate modified filler is improved, the probability of powder falling and abrasion resistance reduction is obviously reduced, and the waterproof performance of a resin layer is enhanced.
Preferably, the emulsifier accounts for 2-5 wt% of the amount of the polymerized monomer, and the initiator accounts for 1-3 wt% of the amount of the polymerized monomer.
Preferably, the isocyanate modified filler consists of the following components in mass ratio of 100: 3-5 of filler and modifier, wherein the modifier is prepared by blending the filler and the modifier in a molar ratio of 2-3: 1 and a phenylsilane coupling agent.
Preferably, the raw materials of the modifier further comprise dimethyl dimethoxy silane, and the mol ratio of the isocyanate silane coupling agent to the dimethyl dimethoxy silane is 2-3: 1.
preferably, the isocyanatosilane coupling agent is selected from one or a combination of more of 3-isocyanatopropyl trimethoxysilane, 3-isocyanatopropyl triethoxysilane, 3-isocyanatopropyl methyl dimethoxysilane and 3-isocyanatopropyl methyl diethoxysilane.
Preferably, the phenylsilane coupling agent is selected from one or more of phenyltrimethoxysilane, phenyltriethoxysilane, diphenyltrimethoxysilane and diphenyldiethoxysilane.
The oligomer prepared by hydrolysis and condensation of the isocyanate silane coupling agent and the phenyl silane coupling agent has higher crosslinking activity with the aqueous acrylic emulsion, can effectively improve the crosslinking density and strength of the waterproof resin layer, further improve the waterproofness and wear resistance of the waterproof resin layer and reduce the powder falling probability. Meanwhile, the silicon hydroxyl groups contained in the modified filler can enable the modified filler to be crosslinked through silicon hydroxyl condensation, so that the performance is improved.
However, too high a crosslinking density also results in too high rigidity of the waterproof resin film layer, increased brittleness, and reduced abrasion resistance. Therefore, the application adds a proper amount of phenyl silane coupling agent to participate in hydrolytic polymerization, and can effectively prevent the local crosslinking density of the waterproof resin film layer from being too high due to the strong steric hindrance effect of phenyl, so that the toughness and the wear resistance of the waterproof resin film layer are ensured.
Further, the dimethyl dimethoxy silane has a chain extension function in the hydrolysis polymerization process, and the molecular chain of the obtained polymer (modifier) is prolonged, so that the toughness of the polymer is improved, the rigidity and toughness of the waterproof resin film layer are balanced, and the wear resistance of the waterproof resin film is improved.
Preferably, the filler is selected from one or a combination of more of calcium carbonate, silica micropowder, titanium dioxide and white carbon black.
In a second aspect, the present application provides a method for producing waterproof and wear-resistant corrugated board, which comprises uniformly mixing an aqueous acrylic emulsion, a dispersant, chlorinated paraffin and an isocyanate modified filler to prepare a waterproof resin, coating the waterproof resin on the surface of the corrugated board according to the amount of 10-20 g/square meter, and drying at 105-120 ℃.
In summary, the application has the following beneficial effects:
1. the waterproof resin prepared by coating the water-based acrylic emulsion, the isocyanate modified filler and the chlorinated paraffin together on the corrugated board can remarkably improve the waterproof performance and the wear resistance of the corrugated board.
2. The hydroxyl-containing monomer is adopted and matched with the secondary polymerization process, so that the crosslinking bonding of the aqueous acrylic emulsion and the isocyanate modified filler can be obviously promoted, and the waterproof performance and the wear resistance of the resin layer are improved.
3. The filler modifier is prepared by hydrolyzing and polymerizing an isocyanate silane coupling agent, a phenyl silane coupling agent and dimethyl dimethoxy silane together, so that the crosslinking density of the isocyanate modified filler and acrylic emulsion can be effectively controlled, the rigidity and toughness of a waterproof resin layer are balanced, and the wear resistance and the waterproof performance of the waterproof resin layer are ensured.
Detailed Description
Preparation example of aqueous acrylic emulsion
Preparation example 1-1, an aqueous acrylic emulsion, was prepared as follows:
pre-emulsification: adding 3 kg of deionized water into a reaction kettle, adding 60gOP-10 g of sodium dodecyl sulfate and 30g of sodium dodecyl sulfate, and uniformly stirring; 1 kg of acrylic acid, 1 kg of ethyl acrylate, 1.5 kg of styrene and 0.2 kg of hydroxyethyl methacrylate are added, and the mixture is stirred and mixed uniformly to obtain a pre-emulsified monomer; 80g of sodium persulfate was dissolved in 0.8 kg of water to obtain an initiator solution;
and (3) primary polymerization: to 1 kg of sodium bicarbonate buffer (10 wt%) at a temperature of 82℃were added the pre-emulsified monomer and 95wt% of the initiator solution, and the reaction was stirred for 5h;
and (3) secondary polymerization: 0.2 kg of hydroxyethyl methacrylate and an initiator solution are added, the reaction is continued to be stirred, and the reaction is finished when the solid content of a sampled sample reaches 45-50%, so that the aqueous acrylic emulsion is prepared.
Preparation examples 1-2, an aqueous acrylic emulsion, were prepared as follows:
pre-emulsification: adding 1.5 kg of deionized water into a reaction kettle, adding 50-gOP-10 g of sodium dodecyl sulfate and uniformly stirring; then 0.7 kg of acrylic acid, 0.3 kg of ethyl acrylate, 1.2 kg of styrene and 0.12 kg of hydroxyethyl methacrylate are added, and the mixture is stirred and mixed uniformly to obtain a pre-emulsified monomer; 25g of sodium persulfate was dissolved in 0.2 kg of water to obtain an initiator solution;
and (3) primary polymerization: to 1 kg of sodium bicarbonate buffer (10 wt%) at a temperature of 78℃were added the pre-emulsified monomer and 90wt% of the initiator solution, and the reaction was stirred for 4h;
and (3) secondary polymerization: adding 0.08 kg of hydroxyethyl methacrylate and the rest of initiator solution, continuously stirring and reacting, and finishing the reaction when the solid content of the sampled sample reaches 45-50%, thus obtaining the aqueous acrylic emulsion.
Preparation examples 1-3, an aqueous acrylic emulsion, were prepared as follows:
pre-emulsification: adding 3 kg of deionized water into a reaction kettle, adding 80-gOP-10 g of sodium dodecyl sulfate and 45g of sodium dodecyl sulfate, and uniformly stirring; 1.2 kg of acrylic acid, 0.8 kg of ethyl acrylate, 1.5 kg of styrene, 0.5 kg of methyl methacrylate and 0.3 kg of hydroxyethyl methacrylate are added, and the mixture is stirred and mixed uniformly to obtain a pre-emulsified monomer; 100g of sodium persulfate is dissolved in 1 kg of water to obtain an initiator solution;
and (3) primary polymerization: to 1 kg of sodium bicarbonate buffer (10 wt%) at 86℃were added pre-emulsified monomer and 90wt% initiator solution, and the reaction was stirred for 5h;
and (3) secondary polymerization: 0.2 kg of hydroxyethyl methacrylate and the rest of initiator solution are added, the stirring reaction is continued, and the reaction is finished when the solid content of a sampled sample reaches 45-50%, so that the aqueous acrylic emulsion is prepared.
Preparation examples 1 to 4, an aqueous acrylic emulsion, differ from preparation example 1 in that a hydroxyl group-containing monomer (hydroxyethyl methacrylate) was added at one time in a pre-emulsification step, and the specific preparation steps were as follows:
pre-emulsification: adding 3 kg of deionized water into a reaction kettle, adding 60gOP-10 g of sodium dodecyl sulfate and 30g of sodium dodecyl sulfate, and uniformly stirring; 1 kg of acrylic acid, 1 kg of ethyl acrylate, 1.5 kg of styrene and 0.4 kg of hydroxyethyl methacrylate are added, and the mixture is stirred and mixed uniformly to obtain a pre-emulsified monomer; 80g of sodium persulfate was dissolved in 0.8 kg of water to obtain an initiator solution;
polymerization: in 1 kg of sodium bicarbonate buffer solution (10 wt%) at 82 deg.C, adding pre-emulsified monomer and 95wt% initiator solution, stirring and making reaction, when the solid content of sampled sample is up to 45-50%, the reaction is completed so as to obtain the invented aqueous acrylic emulsion.
Preparation examples 1 to 5, an aqueous acrylic emulsion, differed from preparation example 1 in that the hydroxyl group-containing monomer (hydroxyethyl methacrylate) in each step was replaced with an equal amount of acrylic acid.
Preparation of isocyanate modified Filler
Preparation example 2-1, isocyanate modified filler, was prepared as follows:
and (3) preparation of a modifier: 675g of 3-isocyanatopropyl trimethoxysilane (3 mol), 198g of phenyl trimethoxysilane (1 mol) and 120g of dimethyl dimethoxy silane are added into 200g of methanol solution (1 mol), stirred and dissolved, and hydrochloric acid is added to adjust the pH value to 3-4; stirring and heating to 55 ℃, then dripping 150g of mixed solution of alcohol and 50g of water, and hydrolyzing for 1.5h to obtain a hydrolysate. Heating the hydrolysate to 110 ℃, polymerizing for 4 hours, distilling under reduced pressure after the reaction is finished to collect methanol, cooling to room temperature, and obtaining the modifier.
Blending modification: 25g of modifier is dissolved in 500g of methanol solution, 400g of calcium carbonate (D50 with the particle size of 100 mu m) and 200g of silica micropowder (D50 with the particle size of 100 mu m) are added, stirred and mixed, and methanol is recovered by reduced pressure distillation after 1h, so that isocyanate modified filler is obtained.
Preparation example 2-2, isocyanate modified filler, was prepared as follows:
and (3) preparation of a modifier: 450g of 3-isocyanatopropyl trimethoxysilane (2 mol), 198g of phenyl trimethoxysilane (1 mol) and 120g of dimethyl dimethoxy silane are added into 150g of methanol solution (1 mol), stirred and dissolved, and hydrochloric acid is added to adjust the pH value to 3-4; stirring and heating to 60 ℃, then dripping 100g of mixed solution of alcohol and 30g of water, and hydrolyzing for 1h to obtain a hydrolysate. Heating the hydrolysate to 110 ℃, polymerizing for 3 hours, distilling under reduced pressure after the reaction is finished to collect methanol, cooling to room temperature, and obtaining the modifier.
Blending modification: 15g of modifier is taken and dissolved in 500g of methanol solution, 500g of calcium carbonate (D50 with the particle size of 100 mu m) is added, and the mixture is stirred and mixed, and methanol is recovered by reduced pressure distillation after 1h, so as to obtain the isocyanate modified filler.
Preparation examples 2-3, isocyanate modified fillers, were prepared as follows:
and (3) preparation of a modifier: 500g of 3-isocyanatopropyl trimethoxysilane (2 mol), 198g of phenyl trimethoxysilane (1 mol) and 120g of dimethyl dimethoxy silane are added into 200g of methanol solution (1 mol), stirred and dissolved, and hydrochloric acid is added to adjust the pH value to 3-4; stirring and heating to 50 ℃, then dropwise adding 120g of mixed solution of alcohol and 30g of water, and hydrolyzing for 1.5h to obtain a hydrolysate. Heating the hydrolysate to 120 ℃, polymerizing for 3 hours, distilling under reduced pressure after the reaction is finished to collect methanol, cooling to room temperature, and obtaining the modifier.
Blending modification: 25g of the modifier is dissolved in 500g of methanol solution, 500g of calcium carbonate (D50 with the particle size of 100 mu m) is added, and the mixture is stirred and mixed, and methanol is recovered by reduced pressure distillation after 1h, so that isocyanate modified filler is obtained.
Preparation examples 2-4, isocyanate modified fillers, differ from preparation examples 2-1 in that in the modifier preparation step, an equivalent amount of phenyltrimethoxysilane was used instead of dimethyldimethoxysilane.
Preparation examples 2-5, isocyanate modified fillers, differ from preparation examples 2-1 in that in the modifier preparation step, an equivalent amount of dimethyl dimethoxy silane was used instead of phenyl trimethoxy silane.
Preparation examples 2-6, isocyanate modified fillers, differ from preparation example 2-1 in that in the modifier preparation step, an equivalent amount of 3-isocyanatopropyl trimethoxysilane was used instead of dimethyl dimethoxy silane and phenyl trimethoxysilane.
Examples
Example 1, a waterproof and wear-resistant corrugated board, was made according to the following procedure:
and (3) preparing resin: 5.3 kg of the aqueous acrylic emulsion obtained in preparation example 1-1, 0.1 kg of AEO-9, 0.75 kg of chlorinated paraffin-42 and 0.8 kg of the isocyanate-modified filler obtained in preparation example 2-1 were uniformly mixed to prepare a water-repellent resin.
And (3) surface glue: and uniformly coating waterproof resin on the surface of the corrugated board according to the coating weight of 15 g/square meter, and drying and curing at 110 ℃ to obtain the waterproof board.
Example 2, a waterproof and abrasion-resistant corrugated board, was made according to the following procedure:
and (3) preparing resin: 4 kg of the aqueous acrylic emulsion obtained in preparation examples 1-2, 0.2 kg of AEO-9, 1 kg of chlorinated paraffin-42 and 0.3 kg of the isocyanate modified filler obtained in preparation examples 2-2 were uniformly mixed to prepare a waterproof resin.
And (3) surface glue: and uniformly coating waterproof resin on the surface of the corrugated board according to the coating weight of 20 g/square meter, and drying and curing at 110 ℃ to obtain the waterproof board.
Example 3, a waterproof and abrasion-resistant corrugated board, was made according to the following procedure:
and (3) preparing resin: 6 kg of the aqueous acrylic emulsion obtained in preparation examples 1 to 31, 0.15 kg of AEO-9, 0.5 kg of chlorinated paraffin-42 and 1 kg of the isocyanate modified filler obtained in preparation examples 2 to 3 were uniformly mixed to prepare a waterproof resin.
And (3) surface glue: uniformly coating waterproof resin on the surface of the corrugated board according to the coating weight of 15+/-2 g/square meter, and drying and curing at 110 ℃ to obtain the waterproof board.
Example 4, a waterproof abrasion-resistant corrugated board, was different from example 1 in that in the resin preparation step, the aqueous acrylic emulsion obtained in preparation example 1-1 was replaced with the aqueous acrylic emulsion obtained in preparation example 1-4 in the same amount.
Example 5, a waterproof abrasion-resistant corrugated board, was different from example 1 in that the aqueous acrylic emulsion obtained in preparation example 1-1 was replaced with the aqueous acrylic emulsion obtained in preparation example 1-5 in the same amount in the resin preparation step.
Example 6, a waterproof abrasion-resistant corrugated board, was different from example 1 in that in the resin preparation step, the aqueous acrylic emulsion obtained in preparation example 2-4 was used in place of the aqueous acrylic emulsion obtained in preparation example 1-1 in the same amount.
Example 7, a waterproof abrasion-resistant corrugated board, was different from example 1 in that the aqueous acrylic emulsion obtained in preparation example 1-1 was replaced with the aqueous acrylic emulsion obtained in preparation example 2-5 in the same amount in the resin preparation step.
Example 8, a waterproof abrasion-resistant corrugated board, was different from example 1 in that in the resin preparation step, the aqueous acrylic emulsion obtained in preparation example 2-6 was used in place of the aqueous acrylic emulsion obtained in preparation example 1-1 in the same amount.
Comparative example
Comparative example 1, a waterproof and abrasion-resistant corrugated board, was different from example 1 in that chlorinated paraffin was not added in the resin preparation step.
Comparative example 2, a waterproof and abrasion-resistant corrugated board, was different from example 1 in that in the resin preparation step, the isocyanate-modified filler obtained in preparation example 2-1 was replaced with a composition of an equivalent amount of unmodified filler and the modifier obtained in preparation example 2-1; the specific operation is as follows:
5.3 kg of the aqueous acrylic emulsion obtained in preparation example 1-1, 0.1 kg of AEO-9, 0.75 kg of chlorinated paraffin-42 and 0.8 kg of calcium carbonate (D50 particle size 100 μm), 0.4 kg of fine silica powder (D50 particle size 100 μm) and 25g of a modifier were uniformly mixed to prepare a water-repellent resin.
And (3) surface glue: and uniformly coating waterproof resin on the surface of the corrugated board according to the coating weight of 15 g/square meter, and drying and curing at 110 ℃ to obtain the waterproof board.
Performance test
1. Waterproof property measurement experiment
(1) A250 mm X250 mm test piece was taken in the middle of each of the four sides of the carton, the water content of any two of the test pieces was measured as specified in GB462-2003, and an average value was calculated, which represents the water content (H) 1 )。
(2) The inner surfaces (which are not subjected to moisture-proof external surface) of the other two test pieces are relatively overlapped, the peripheries of the test pieces are fixed together by a material-based pressure-sensitive adhesive tape in a sealed manner, the test pieces are hung in a temperature-adjusting and humidity-adjusting box with the temperature of 50 ℃ and the temperature of 2 ℃ and the relative humidity of 90+/-5 percent for 48 hours, then the test pieces are taken out, water vapor on the surfaces of the test pieces is sucked by filter paper, the test pieces are hung under the conditions that the temperature of 23+/-2 ℃ is the relative humidity of 50+/-5 percent for 10 minutes, the two test pieces are separated, the water content of the test pieces is measured according to the specification of GB462, and the average value is calculated. The average value represents the moisture content (H) 2 )。
(3) Moisture-proof H T Characterization: h T ＝H 2 -H 1
2. Wear resistance test
(1) Sample preparation and experimental steps: from the corrugated cardboards of the above examples and comparative examples, 3 round test pieces having a diameter of 5cm were cut. Then the sample to be tested is put into a constant temperature and humidity laboratory, the temperature is 20 ℃, the relative humidity is 65%, and the humidity is regulated for 48 hours. And after the corrugated paper box sample is taken out, testing the corrugated paper box sample by using a fabric flat grinder according to a circular track method of GB/T21196.2-200. In the experiment, the amount of the pressurizing material was 395g
(2) Evaluation criteria: during the test, the number of times of friction when the friction surface of the sample was broken (a hole appears on the appearance of the surface layer of the sample) was observed and recorded as the number of times of abrasion resistance, and the test results are shown in Table 1.
TABLE 1 Experimental results
Analysis of experimental results:
(1) It can be seen from the combination of examples 1 to 8 and comparative examples 1 to 2 and the combination of table 1 that the abrasion resistance and water resistance of the aqueous acrylic emulsion can be remarkably improved by adopting the aqueous acrylic emulsion and chlorinated paraffin wax and isocyanate modified filler to be combined together.
(2) As can be seen from the combination of example 1 and examples 4 to 5 and the combination of table 1, the present application can effectively promote the improvement of the waterproof performance and the waterproof performance of corrugated boards by adopting the hydroxyl group-containing monomer and combining with the stepwise and multiple polymerization process. The reason for this may be that the stepwise multiple polymerization process may allow the surface of the aqueous acrylic emulsion particles to contain more hydroxyl groups, which may increase the crosslink density of the aqueous acrylic emulsion and the isocyanate modified filler. On one hand, the connection fastness of the filler can be improved through chemical bonding, the phenomenon of falling powder under the action of external force is reduced, and the wear resistance is improved; on the other hand, the compactness of waterproof resin layer can be improved, and then the waterproof performance of corrugated container board is strengthened.
(3) As can be seen from the combination of example 1 and examples 6 to 8 and table 1, the present application is advantageous in improving the abrasion resistance of corrugated board by using the isocyanate-based silane coupling agent, the phenylsilane coupling agent and the dimethyldimethoxysilane. The reason for this is probably that the modifier is a hydrolysis polymerization product of the above three raw materials, and the isocyanate group in the molecular chain thereof provides a crosslinking curing group for the modifier to react with the aqueous acrylic emulsion, thereby ensuring the reactivity. The introduction of phenyl can control the crosslinking density of the modifier and the aqueous acrylic emulsion, and prevent the decrease of the strength performance and the wear resistance caused by the increase of the rigidity and the brittleness due to the decrease of the toughness of the resin layer caused by the overhigh local crosslinking density. In addition, the filler surface modifier can be crosslinked and bonded through hydroxyl groups, and the dimethyl dimethoxy silane is added to play a role in chain extension, so that the elasticity of the waterproof resin layer is improved, and the wear resistance of the waterproof resin layer is ensured.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.

Claims (7)

1. The waterproof wear-resistant corrugated board is characterized in that a waterproof resin layer is formed on the surface of the corrugated board through coating and drying, and the waterproof resin comprises the following raw materials in parts by weight:
aqueous acrylic emulsion: 40-60 parts;
chlorinated paraffin: 5-10 parts;
dispersing agent: 1-2 parts;
isocyanate modified filler: 5-12 parts;
isocyanate groups are grafted on the surface of the isocyanate modified filler;
the isocyanate modified filler comprises the following components in percentage by mass: 3-5 of filler and modifier, wherein the modifier is prepared by blending the filler and the modifier in a molar ratio of 2-3: 1 and a phenylsilane coupling agent;
the polymerized monomers of the aqueous acrylic emulsion are as follows:
soft monomer: 10-20 parts;
hard monomer: 10-20 parts;
hydroxyl-containing monomers: 2-5 parts;
the hydroxyl-containing monomer is selected from one or a combination of a plurality of N-methylolacrylamide, hydroxyethyl methacrylate and hydroxypropyl methacrylate;
the aqueous acrylic emulsion is prepared by the following steps:
pre-emulsification: mixing and dispersing soft monomer, hard monomer and hydroxyl monomer accounting for 40-60 wt% of the total weight of the hydroxyl monomer into an emulsifier aqueous solution to obtain a pre-emulsified monomer; dissolving an initiator in water to obtain an initiator solution;
and (3) primary polymerization: adding a pre-emulsified monomer and an initiator solution with the weight percent of 90-95% into a sodium bicarbonate buffer solution with the temperature of 76-88 ℃ for stirring reaction;
and (3) secondary polymerization: adding the rest hydroxyl-containing monomer and initiator solution, continuing stirring and reacting, and finishing the reaction when the solid content reaches 45-50%, thus obtaining the aqueous acrylic emulsion.
2. The waterproof and wear-resistant corrugated board according to claim 1, wherein the soft monomer is one or a combination of several of acrylic acid, ethyl acrylate and butyl acrylate; the hard monomer is selected from one or a combination of more of styrene, acrylonitrile, methyl acrylate, methyl methacrylate and vinylidene chloride.
3. The waterproof and wear-resistant corrugated board according to claim 1, wherein the raw materials of the modifier further comprise dimethyl dimethoxy silane, and the molar ratio of the isocyanate silane coupling agent to the dimethyl dimethoxy silane is 2-3: 1.
4. the waterproof and wear-resistant corrugated board according to claim 1, wherein the isocyanate-based silane coupling agent is selected from one or more of 3-isocyanate-based propyl trimethoxysilane, 3-isocyanate-based propyl triethoxysilane, 3-isocyanate-based propyl methyl dimethoxy silane and 3-isocyanate-based propyl methyl diethoxy silane.
5. The waterproof wear-resistant corrugated board according to claim 1, wherein the phenylsilane coupling agent is selected from one or more of phenyltrimethoxysilane, phenyltriethoxysilane, diphenyltrimethoxysilane and diphenyldiethoxysilane.
6. The waterproof and wear-resistant corrugated board according to claim 1, wherein the filler is one or a combination of several of calcium carbonate, silica micropowder, titanium dioxide and white carbon black.
7. The method for producing waterproof and wear-resistant corrugated board according to any one of claims 1 to 6, wherein the waterproof resin is prepared by uniformly mixing aqueous acrylic emulsion, a dispersing agent, chlorinated paraffin and isocyanate modified filler, coating the waterproof resin on the surface of the corrugated board according to the amount of 10 to 20 g/square meter, and drying at 105 to 120 ℃.
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CN103665269A (en) * 2013-11-12 2014-03-26 江南大学 Preparation method of amphiphilic acrylate copolymer surface grafting modified nano silicon dioxide
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CN104631207A (en) * 2015-01-08 2015-05-20 湖南华望科技股份有限公司 Waterproof coating for water-based paperboards and preparation method thereof
CN104861844A (en) * 2015-05-07 2015-08-26 姜捷 Waterproof anticorrosion two-component water-borne polyurethane coating and preparation method thereof
WO2017020513A1 (en) * 2015-07-31 2017-02-09 华南理工大学 Hydroxyl polyacrylate emulsion and preparation method and application thereof
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* Cited by examiner, † Cited by third party
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KR100249431B1 (en) * 1997-12-30 2000-03-15 김승욱 Chemical composition using for water proof liner paper of paper vessel
CN103998008A (en) * 2011-12-15 2014-08-20 登特斯普伊德特雷有限公司 Composite filler particles and process for the preparation thereof
CN103665269A (en) * 2013-11-12 2014-03-26 江南大学 Preparation method of amphiphilic acrylate copolymer surface grafting modified nano silicon dioxide
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CN104861844A (en) * 2015-05-07 2015-08-26 姜捷 Waterproof anticorrosion two-component water-borne polyurethane coating and preparation method thereof
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