CN114163562A - Paper moisture-proof agent and preparation method thereof - Google Patents
Paper moisture-proof agent and preparation method thereof Download PDFInfo
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- CN114163562A CN114163562A CN202111600200.7A CN202111600200A CN114163562A CN 114163562 A CN114163562 A CN 114163562A CN 202111600200 A CN202111600200 A CN 202111600200A CN 114163562 A CN114163562 A CN 114163562A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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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
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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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
- 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
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- Polymerisation Methods In General (AREA)
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Abstract
The invention provides a paper moisture-proof agent and a preparation method thereof, belonging to the technical field of high polymer materials, and comprising a modified water-soluble acrylate emulsion and a preparation method thereof, wherein the preparation method specifically comprises the following steps: preparing a pre-emulsion; stirring and dissolving a compound emulsifier, propylene glycol alginate, L-carnitine tartrate and a buffer, and dropwise adding an acrylate monomer, GMA and an initiator to prepare a seed emulsion; carrying out polymerization reaction; acrylate monomers include MMA, BA, BMA. The preparation method of the modified water-soluble acrylate emulsion provided by the invention has the advantages of low production cost, good moisture permeability resistance and water resistance of the product, and convenience in transportation and storage.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a paper moisture-proof agent and a preparation method thereof.
Background
The paper or the paperboard is a three-dimensional reticular structure material formed by interweaving numerous fibers, the surface of the plant fiber is provided with a large number of hydroxyl groups and has natural hydrophilicity, the cell cavities of the fibers have a microtube structure and form a three-dimensional reticular structure with the fibers to play a capillary action together, so the paper or the paperboard without any treatment has strong liquid absorption, liquid drops quickly generate diffusion and permeation phenomena on the paper surface, and the paper or the paperboard is not suitable for writing and printing; meanwhile, the requirement of prohibiting plastic molding is higher and higher at present, and different performances such as water resistance, oil resistance, moisture permeability resistance and the like are endowed on paper, so that plastic packaging paper products can be effectively replaced, and plastic wastes are reduced.
Compared with the traditional solvent-based coating, the water-soluble coating has the advantages of low price, safe use, resource and energy conservation, environmental pollution and public nuisance reduction, and the like, thereby becoming the main direction for developing the coating industry at present. The water-soluble acrylic resin coating has the advantages of good leveling property, high gloss, good film forming property, good film compactness and the like, can obviously improve the safety and reliability in the construction and curing process, retains the advantages of the solvent-type acrylic resin coating in the aspects of mechanical property, protective property, decorative property and the like, and becomes a pollution-free coating with the fastest development and the most varieties in the water-soluble coating.
Disclosure of Invention
The invention aims to provide a preparation method of a modified water-soluble acrylate emulsion, which has the advantages of low cost, high monomer conversion rate, high emulsion stability, good moisture permeability resistance and water resistance after film forming and capability of effectively blocking water vapor.
The technical scheme adopted by the invention for realizing the purpose is as follows:
the preparation method of the modified water-soluble acrylate emulsion comprises the following specific steps:
A. preparation of pre-emulsion: adding a compound emulsifier into deionized water, heating and stirring, dissolving, dropwise adding an acrylate monomer and Glycidyl Methacrylate (GMA), and stirring to obtain a pre-emulsion;
B. preparing a seed emulsion: adding the compound emulsifier, propylene glycol alginate, L-carnitine tartrate and buffer into a container filled with deionized water, stirring for dissolving, and introducing N2Removing air in the container, raising the temperature to 35-40 ℃, dropwise adding an acrylate monomer and glycidyl methacrylate, preserving the temperature for 10-30min, raising the temperature to 60-70 ℃, dropwise adding an initiator solution S1, raising the temperature to 70-75 ℃, and reacting for 50-80min to obtain a seed emulsion;
C. polymerization reaction: synchronously dropwise adding the pre-emulsion and the initiator solution S2 into the seed emulsion at 70-75 ℃, uniformly and stably dropwise adding within 3-4h, then synchronously dropwise adding Acrylic Acid (AA) and a neutralizing agent, keeping the temperature for reacting for 50-80min after completing dropwise adding within 30min, supplementing the initiator solution S3, continuously reacting for 50-80min, and filtering through a copper net of 80-100 meshes to obtain a finished product.
The deionized water in the step A accounts for 35-45% of the total deionized water; the acrylate monomers comprise Methyl Methacrylate (MMA), Butyl Acrylate (BA), and Behenyl Methacrylate (BMA); the compound emulsifier comprises ES-400 (special alcohol polyether), SDS (sodium dodecyl sulfate); the total deionized water is the sum of the deionized water in the step A and the deionized water in the step B. The water-based acrylate coating has the advantages of no toxicity, no odor, energy conservation, no environmental pollution, convenient processing and construction and the like, and eliminates the dangers of flammability, explosiveness and the like of the coating in the production, transportation and use processes. The common water-based acrylate has the defects of water resistance, chemical corrosion resistance, mechanical property and the like, and the application of the common water-based acrylate in certain special fields with high performance and high requirements is influenced. Therefore, it is necessary to modify the acrylic resin to obtain high-performance water-based acrylic resin, and the application range and field of the acrylic resin are enlarged. The preparation method adopts the technical scheme of taking acrylic acid and glycidyl methacrylate as functional monomers, can introduce epoxy functional groups on the acrylate polymer, and the epoxy functional groups are taken as sites for crosslinking and react with other groups to generate a three-dimensional network crosslinking structure, thereby increasing the crosslinking density of the system and improving the performances of the emulsion and the membrane. Furthermore, the addition amount of the propylene glycol alginate is 0.08-0.25wt% of the deionized water, and the addition amount of the L-carnitine tartrate is 0.05-0.12wt% of the deionized water. By optimizing the preparation method again, the use amount of the emulsifier can be reduced, so that the emulsifier remained in the latex film can be reduced, the water absorption rate is reduced, the water resistance is improved, and the purposes of reducing the cost and improving the product performance are achieved. The propylene glycol alginate and the L-carnitine tartrate are added in the preparation process of the seed emulsion of the water-based acrylate emulsion, so that the seed emulsion still has smaller emulsion particle size while using less emulsifier, and has higher conversion rate and low gel rate, and the prepared water-based acrylate emulsion has high stability and is convenient to transport and store.
In the invention, the total amount of the acrylate monomer represents the sum of the addition amounts of the acrylate monomer in the step A and the acrylate monomer in the step B, the total amount of GMA represents the sum of the addition amounts of the GMA in the step A and the GMA in the step B, and the total amount of the compound emulsifier represents the sum of the addition amounts of the compound emulsifier in the step A and the step B.
In some embodiments, the neutralizing agent is one or more of triethanolamine, triethylamine, and diethanolamine.
In some embodiments, the buffer is any one of sodium carbonate, sodium bicarbonate, sodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, ammonium carbonate, ammonium bicarbonate, ammonium phosphate, and ammonium dihydrogen phosphate.
In some embodiments, the initiator solution S1: initiator solution S2: the initiator solution S3 is 2-3:5-6: 1-2. Further, the above initiator solution is 5 to 10wt% KPS (potassium persulfate) aqueous solution.
In some embodiments, the mass ratio of MMA, BA and BMA is 8-10:10-15: 1-3.
In some embodiments, the MMA is added in an amount of 28 to 35wt% of the total deionized water.
In some embodiments, the total amount of GMA described above is 2 to 8wt% of the total amount of acrylate monomers.
In some embodiments, the above AA is added in an amount of 30 to 70wt% of the total amount of GMA.
In some embodiments, the total amount of the above formulated emulsifiers is 2 to 5wt% of the total deionized water.
In some embodiments, the compound emulsifier in step a is 60-70% of the total amount of compound emulsifier.
In some embodiments, the acrylate monomer in step a above comprises 70-80% of the total amount of acrylate monomer.
Provides a modified water-soluble acrylate emulsion which is prepared by adopting the preparation method.
Provides the application of the preparation method of the modified water-soluble acrylate emulsion in preparing the moisture-proof paper.
Provides a moisture-proof agent which comprises the modified water-soluble acrylate emulsion. The paper moisture-proof agent provided by the invention can effectively block water vapor permeation when being coated on paper, and can be used as packaging paper for preventing water vapor to replace plastic packaging, such as nuts, dog food, cement bags and the like which need to block water vapor and prevent moisture.
A method for imparting moisture barrier properties to a desired paper comprising: the moisture-proof agent is applied to paper and then dried.
In some embodiments, the desired paper includes, but is not limited to, cultural paper, food paper, wallpaper, kraft paper.
A method for imparting moisture vapor barrier and composite properties to a desired paper comprising: the moisture-proof agent is coated on paper, and then a layer of paper is compounded before drying, and then drying is carried out.
Provides the application of the moisture-proof agent in the preparation of the sandwich paper of the cement paper bag.
Because the propylene glycol alginate and the L-carnitine tartrate are added in the process of preparing the seed emulsion of the epoxy modified water-based acrylate emulsion, the invention has the following beneficial effects: 1) the emulsion has smaller particle size while using less emulsifier, higher conversion rate and low gel rate, and the prepared water-based acrylate emulsion has high stability and is convenient to transport and store; 2) by optimizing the preparation method again, the use amount of the emulsifier can be reduced, so that the emulsifier remained in the latex film can be reduced, the water absorption rate is reduced, the water resistance is improved, and the purposes of reducing the cost and improving the product performance are achieved.
Therefore, the invention is a preparation method of the modified water-soluble acrylate emulsion which has the advantages of low production cost, good moisture permeability resistance and water resistance of the product and convenient transportation and storage.
Drawings
FIG. 1 is an infrared spectrum of a modified water-based acrylate latex film in example 1 of the present invention;
FIG. 2 is a graph showing the results of particle size measurement of the emulsion in test example 1 of the present invention;
FIG. 3 is a result of measurement of monomer conversion in test example 1 of the present invention;
FIG. 4 is a result of measurement of gel fraction in test example 1 of the present invention;
FIG. 5 is a graph showing the measurement results of the viscosity of the emulsion in test example 2 of the present invention;
FIG. 6 is a result of measuring a crosslinking rate in test example 2 of the present invention;
FIG. 7 shows water absorption of adhesive films of examples 1 to 6 in test example 2 of the present invention;
FIG. 8 shows the results of measuring the absorption rates of the adhesive films of examples 1 and 7 to 13 in test example 2 of the present invention with respect to water and a 10v/v% ethanol solution.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further clarified with the following specific embodiments, but the following embodiments are only the preferred embodiments of the invention, and not all embodiments. Based on the embodiments in the implementation, other embodiments obtained by those skilled in the art without any creative efforts belong to the protection scope of the present invention.
A preparation method of modified water-soluble acrylate emulsion comprises the following specific steps:
A. preparation of pre-emulsion: adding a compound emulsifier into deionized water, heating and stirring, dissolving, dropwise adding an acrylate monomer, and stirring with GMA to obtain a pre-emulsion;
B. preparing a seed emulsion: adding the compound emulsifier, propylene glycol alginate, L-carnitine tartrate and buffer into a container filled with deionized water, stirring for dissolving, and introducing N2Removing air in the container, raising the temperature to 35-40 ℃, dropwise adding an acrylate monomer and GMA, preserving the temperature for 10-30min, raising the temperature to 60-70 ℃, dropwise adding an initiator solution S1, raising the temperature to 70-75 ℃, and reacting for 50-80min to obtain a seed emulsion;
C. polymerization reaction: synchronously dropwise adding the pre-emulsion and the initiator solution S2 into the seed emulsion at 70-75 ℃, finishing dropwise adding at a constant speed and stably within 3-4h, then synchronously dropwise adding AA and a neutralizing agent, finishing dropwise adding within 30min, preserving heat for reacting for 50-80min, supplementing the initiator solution S3, continuing to react for 50-80min, and filtering through a copper net of 80-100 meshes to obtain a finished product.
The deionized water in the step A accounts for 35-45% of the total deionized water; the acrylate monomer comprises MMA, BA and BMA; the compound emulsifier comprises ES-400 and SDS; the total deionized water is the sum of the deionized water in the step A and the deionized water in the step B. The water-based acrylate coating has the advantages of no toxicity, no odor, energy conservation, no environmental pollution, convenient processing and construction and the like, and eliminates the dangers of flammability, explosiveness and the like of the coating in the production, transportation and use processes. The common water-based acrylate has the defects of water resistance, chemical corrosion resistance, mechanical property and the like, and the application of the common water-based acrylate in certain special fields with high performance and high requirements is influenced. Therefore, it is necessary to modify the acrylic resin to obtain high-performance water-based acrylic resin, and the application range and field of the acrylic resin are enlarged. The preparation method adopts the technical scheme of taking acrylic acid and glycidyl methacrylate as functional monomers, can introduce epoxy functional groups on the acrylate polymer, and the epoxy functional groups are taken as sites for crosslinking and react with other groups to generate a three-dimensional network crosslinking structure, thereby increasing the crosslinking density of the system and improving the performances of the emulsion and the membrane. Furthermore, the addition amount of the propylene glycol alginate is 0.08-0.25wt% of the total deionized water, and the addition amount of the L-carnitine tartrate is 0.05-0.12wt% of the total deionized water. By optimizing the preparation method again, the use amount of the emulsifier can be reduced, so that the emulsifier remained in the latex film can be reduced, the water absorption rate is reduced, the water resistance is improved, and the purposes of reducing the cost and improving the product performance are achieved. The propylene glycol alginate and the L-carnitine tartrate are added in the preparation process of the water-based acrylate seed emulsion, so that the water-based acrylate seed emulsion still has smaller emulsion particle size while using less emulsifier, and has higher conversion rate and low gel rate, and the prepared water-based acrylate seed emulsion has high stability and is convenient to transport and store.
In some embodiments, the neutralizing agent is one or more of triethanolamine, triethylamine, and diethanolamine. Further, the neutralizing agent is triethylamine.
In some embodiments, the buffer is any one of sodium carbonate, sodium bicarbonate, sodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, ammonium carbonate, ammonium bicarbonate, ammonium phosphate, and ammonium dihydrogen phosphate. Further, the buffer is sodium bicarbonate. Further, the amount of the buffer added is 0.1 to 0.5wt% of the total deionized water.
In some embodiments, the initiator solution S1: initiator solution S2: the initiator solution S3 is 2-3:5-6: 1-2. Further, the initiator solution is a 5-10wt% KPS aqueous solution. Further, the total amount of addition of the above KPS is 0.5-1.0wt% of the total amount of the acrylate monomers in steps A and B.
In some embodiments, the mass ratio of MMA, BA and BMA is 8-10:10-15: 1-3.
In some embodiments, the total amount of MMA in steps A and B above is 28 to 35wt% of the total deionized water.
In some embodiments, the total amount of GMA described above is 2 to 8wt% of the total amount of acrylate monomers.
In some embodiments, the above AA is added in an amount of 30 to 70wt% of the total amount of GMA. Further, the amount of the above-mentioned neutralizing agent added is 115-135wt% of AA.
In some embodiments, the total amount of the above formulated emulsifiers is 2 to 5wt% of the total deionized water.
In some embodiments, maltotetraose and sodium stearyl fumarate are added before the addition of AA in step a above. Further, the addition amount of the sodium stearyl fumarate is 0.3-0.6wt% of the total deionized water, and the addition amount of the maltotetraose is 20-35wt% of the sodium stearyl fumarate. The addition of a certain proportion of maltotetraose and sodium stearyl fumarate in the preparation process of the pre-emulsion can reduce the viscosity of a system, is favorable for the diffusion of a polymer chain in the film forming process, further improves the crosslinking density, has higher gel content of a glue film, can effectively reduce the absorption of moisture and chemicals, thereby having better water resistance and chemical resistance and expanding the application range.
In some embodiments, the mass fraction of SDS in the above formulated emulsifier is 35 to 50 wt%.
In some embodiments, the compound emulsifier in step a is 60-70% of the total amount of compound emulsifier.
In some embodiments, the acrylate monomer in step a above comprises 70-80% of the total amount of acrylate monomer.
The modified water-soluble acrylate emulsion is prepared by the preparation method.
The application of the preparation method of the modified water-soluble acrylate emulsion in preparing the moisture-proof paper.
A moisture penetration-proof agent comprises the modified water-soluble acrylate emulsion.
A method of imparting moisture resistance to a desired paper comprising: the moisture-proof agent is applied to paper and then dried.
In some embodiments, the desired paper includes, but is not limited to, cultural paper, food paper, wallpaper, kraft paper.
A method of imparting moisture barrier properties to a desired paper comprising: the moisture-proof agent is coated on paper, and then a layer of paper is compounded before drying, and then drying is carried out.
An application of a moisture-proof agent in preparing sandwich paper of a cement paper bag.
The present invention and the conventional techniques in the embodiments are known to those skilled in the art and will not be described in detail herein.
It should be understood that the foregoing description is to be considered illustrative or exemplary and not restrictive, and that in particular the invention covers other embodiments having any combination of features from the different embodiments described above and below, without the scope of the invention being limited to the specific examples below.
Reagents and vendors used in the following examples:
ES-400, available from Junxin chemical technology, Inc., Guangzhou; SDS, available from WUJIANGTIANCHEN chemical Co., Ltd, glycidyl methacrylate, available from Jinan and Xin chemical Co., Ltd; methyl methacrylate, behenyl methacrylate, purchased from renda chemical ltd, yokko, zhang; butyl acrylate, purchased from exchange chemical trade, ltd, zhang, port bonded area; acrylic acid, purchased from exchange chemical trade limited, zhangjia, bonded area; maltotetraose, available from Dougeno Rui Biotech, Inc.; sodium stearyl fumarate, available from Jinquan food science and technology, Inc.; propylene glycol alginate, L-carnitine tartrate, available from Frey Biotech, Suzhou; sodium bicarbonate, available from flourocene chemical co ltd, suzhou; potassium persulfate, purchased from the shin-repairing fine chemical research institute of Tianjin; triethylamine, purchased from jinan mingmi chemicals ltd.
Example 1:
1. a paper moisture-proof agent is a modified water-soluble acrylate emulsion, and comprises the following raw materials:
45g of methyl methacrylate, 67.5g of butyl acrylate, 11g of behenyl methacrylate, 8g of glycidyl methacrylate, ES-4003.6 g, 2.4g of SDS, 0.23g of propylene glycol alginate, 0.12g of L-carnitine tartrate, 0.8g of potassium persulfate, 4g of acrylic acid, 5g of triethylamine, 0.2g of sodium bicarbonate and 150g of deionized water.
2. A preparation method of modified water-soluble acrylate emulsion comprises the following specific steps:
2.1 preparation of Pre-emulsion: after adding 1.56g SDS and 2.34g ES-400 into 60g deionized water, stirring and dissolving, 32.4g MMA, 48.6g BA, 8g BMA and 4.8g GMA were added dropwise, and vigorously stirred at 800rpm for 30min to obtain a pre-emulsion.
2.2 preparation of seed emulsion: 90g of deionized water, 0.84g of SDS, 1.26g of ES-400, 0.23g of propylene glycol alginate, 0.12g L-carnitine tartrate and 0.2g of sodium bicarbonate were added to a solution containing a mechanical stirrer, a constant pressure dropping funnel, N2Adding into a three-neck flask with a tube, stirring for dissolving, and adding N2Removing air in a container, slowly heating to 40 ℃, dropwise adding 12.6g of MMA, 18.9g of BA, 3g of BMA and 3.2g of GMA, preserving heat for 20min, heating to 65 ℃, dropwise adding 2g of 10wt% KPS aqueous solution, heating to 75 ℃, and reacting for 70min to obtain seed emulsion; the rest of the process was identical to example 1.
2.3 polymerization reaction: synchronously dropwise adding the pre-emulsion and 5g of 10wt% KPS aqueous solution into the seed emulsion at 70 ℃, uniformly and stably dropwise adding within 3h, then synchronously dropwise adding 4g of acrylic acid and 5g of triethylamine, keeping the temperature for reaction for 70min after 30min of dropwise adding, supplementing 1g of 10wt% KPS aqueous solution, continuing the reaction for 60min, and filtering through a 80-mesh copper net to obtain a finished product.
The modified aqueous acrylate emulsion obtained in example 1 was spread evenly on a glass slide, dried in a drying oven at 80 ℃, and the film was removed from the glass slide and a small piece was taken for infrared conversion spectroscopy (FT-IR) analysis. The infrared spectrogram of the modified water-based acrylate latex film is shown in figure 1. As can be seen from FIG. 1, 2953cm-1And 2871cm-1is-CH3and-CH2C-H of (2), and 1726cm-1Peak of telescopic vibration at C = O, 1449cm-1is-CH2Peak of bending vibration of 1385cm-1Is at the bending vibration peak of C-H, 1237cm-1And 1144cm-1Is the symmetric stretching vibration peak of C-O-C in the copolymer, 841cm-1A stretching vibration absorption peak of 1500-1700cm with C = O bond-1The stretching vibration without C = C in the range indicates that all monomers participate in the polymerization reaction, and the characteristic absorption peak of the epoxy group appears, indicating that the epoxy group has a crosslinking reaction.
The modified water-based acrylate emulsion prepared by the invention is subjected to multi-angle test: the process comprises the following steps: respectively coating the product on base paper, drying at 130 deg.C for 30s, stabilizing at 23 deg.C and 50% humidity for 30min, and testing. The MVTR test method comprises the following steps: GB1037-88 Plastic film and sheet Water vapor Permeability test method (cup method). The comparison test of the kraft base paper used as a coating object and the market competitive products is shown in table 1. The moisture resistance of the coating of different base papers was tested using the modified aqueous acrylate emulsion prepared in example 1, and the effect of the different base papers on moisture resistance is shown in table 2. The moisture-proof effect of the modified water-based acrylate emulsion prepared in example 1 on kraft base paper with varying coating weight is shown in table 3, and the moisture-proof effect of the uncoated cultural paper with varying coating weight is shown in table 4, by using the moisture-proof test of varying coating weight on different base paper.
TABLE 1 comparison test with commercial contests
Sizing degree: stockigt sizing; MVTR: 40 ℃ X90% RH X24 hr
TABLE 2 Effect of different base papers on moisture resistance
Sizing degree: stockigt sizing; MVTR: 40 ℃ X90% RH X24 hr
TABLE 3 moisture protection effect on Kraft base paper by varying coating weight
TABLE 4 moisture protection effect on uncoated cultural paper with varying coating weight
Example 2:
1. a modified water-soluble acrylate emulsion comprises the following raw materials:
45g of methyl methacrylate, 67.5g of butyl acrylate, 11g of behenyl methacrylate, 8g of glycidyl methacrylate, ES-4003.6 g, 2.4g of SDS, 0.36g of propylene glycol alginate, 0.16g of L-carnitine tartrate, 0.8g of potassium persulfate, 4g of acrylic acid, 5g of triethylamine, 0.2g of sodium bicarbonate and 150g of deionized water.
2. A preparation method of modified water-soluble acrylate emulsion comprises the following specific steps:
2.2 preparation of seed emulsion: 90g of deionized water, 0.84g of SDS, 1.26g of ES-400, 0.36g of propylene glycol alginate, 0.16g L-carnitine tartrate and 0.2g of sodium bicarbonate were added to a solution containing a mechanical stirrer, a constant pressure dropping funnel, N2Adding into a three-neck flask with a tube, stirring for dissolving, and adding N2Removing air in a container, slowly heating to 40 ℃, dropwise adding 12.6g of MMA, 18.9g of BA, 3g of BMA and 3.2g of GMA, preserving heat for 20min, heating to 65 ℃, dropwise adding 2g of 10wt% KPS aqueous solution, heating to 75 ℃, and reacting for 70min to obtain seed emulsion; the rest of the process was identical to example 1.
Example 3:
1. a modified water-soluble acrylate emulsion comprises the following raw materials:
45g of methyl methacrylate, 67.5g of butyl acrylate, 11g of behenyl methacrylate, 8g of glycidyl methacrylate, ES-4003.6 g, 2.4g of SDS, 0.14g of propylene glycol alginate, 0.11g of L-carnitine tartrate, 0.8g of potassium persulfate, 4g of acrylic acid, 5g of triethylamine, 0.2g of sodium bicarbonate and 150g of deionized water.
2. A preparation method of modified water-soluble acrylate emulsion comprises the following specific steps:
2.2 preparation of seed emulsion: 90g of deionized water, 0.84g of SDS, 1.26g of ES-400, 0.14g of propylene glycol alginate, 0.11g L-carnitine tartrate and 0.2g of sodium bicarbonate were added to a solution containing a mechanical stirrer, a constant pressure dropping funnel, N2Adding into a three-neck flask with a tube, stirring for dissolving, and adding N2Removing air in a container, slowly heating to 40 ℃, dropwise adding 12.6g of MMA, 18.9g of BA, 3g of BMA and 3.2g of GMA, preserving heat for 20min, heating to 65 ℃, dropwise adding 2g of 10wt% KPS aqueous solution, heating to 75 ℃, and reacting for 70min to obtain seed emulsion; the rest of the process was identical to example 1.
Example 4:
1. a modified water-soluble acrylate emulsion comprises the following raw materials:
45g of methyl methacrylate, 67.5g of butyl acrylate, 11g of behenyl methacrylate, 8g of glycidyl methacrylate, ES-4003.6 g, 2.4g of SDS, 0.23g of propylene glycol alginate, 0.8g of potassium persulfate, 4g of acrylic acid, 5g of triethylamine, 0.2g of sodium bicarbonate and 150g of deionized water.
2. A preparation method of modified water-soluble acrylate emulsion comprises the following specific steps:
2.2 preparation of seed emulsion: 90g of deionized water, 0.84g of SDS, 1.26g of ES-400, 0.23g of propylene glycol alginate and 0.2g of sodium bicarbonate were added to a flask equipped with a mechanical stirrer, a dropping funnel at constant pressure, and N2Adding into a three-neck flask with a tube, stirring for dissolving, and adding N2Removing air in a container, slowly heating to 40 ℃, dropwise adding 12.6g of MMA, 18.9g of BA, 3g of BMA and 3.2g of GMA, preserving heat for 20min, heating to 65 ℃, dropwise adding 2g of 10wt% KPS aqueous solution, heating to 75 ℃, and reacting for 70min to obtain seed emulsion; the rest of the process was identical to example 1.
Example 5:
1. a modified water-soluble acrylate emulsion comprises the following raw materials:
45g of methyl methacrylate, 67.5g of butyl acrylate, 11g of behenyl methacrylate, 8g of glycidyl methacrylate, ES-4003.6 g, 2.4g of SDS, 0.12g of L-carnitine tartrate, 0.8g of potassium persulfate, 4g of acrylic acid, 5g of triethylamine, 0.2g of sodium bicarbonate and 150g of deionized water.
2. A preparation method of modified water-soluble acrylate emulsion comprises the following specific steps:
2.2 preparation of seed emulsion: 90g of deionized water, 0.84g of SDS, 1.26g of ES-400, 0.12g of 0.12g L-carnitine tartrate and 0.2g of sodium bicarbonate were added to a flask equipped with a mechanical stirrer, a dropping funnel at constant pressure, and N2Adding into a three-neck flask with a tube, stirring for dissolving, and adding N2Removing air in a container, slowly heating to 40 ℃, dropwise adding 12.6g of MMA, 18.9g of BA, 3g of BMA and 3.2g of GMA, preserving heat for 20min, heating to 65 ℃, dropwise adding 2g of 10wt% KPS aqueous solution, heating to 75 ℃, and reacting for 70min to obtain seed emulsion; the rest of the process was identical to example 1.
Example 6:
1. a modified water-soluble acrylate emulsion comprises the following raw materials:
45g of methyl methacrylate, 67.5g of butyl acrylate, 11g of behenyl methacrylate, 8g of glycidyl methacrylate, ES-4003.6 g, 2.4g of SDS, 0.8g of potassium persulfate, 4g of acrylic acid, 5g of triethylamine, 0.2g of sodium bicarbonate and 150g of deionized water.
2. A preparation method of modified water-soluble acrylate emulsion comprises the following specific steps:
2.2 preparation of seed emulsion: 90g of deionized water, 0.84g of SDS, 1.26g of ES-400 and 0.2g of sodium bicarbonate were added to a flask equipped with a mechanical stirrer, a dropping funnel at constant pressure, and N2Adding into a three-neck flask with a tube, stirring for dissolving, and adding N2Removing air in a container, slowly heating to 40 ℃, dropwise adding 12.6g of MMA, 18.9g of BA, 3g of BMA and 3.2g of GMA, preserving heat for 20min, heating to 65 ℃, dropwise adding 2g of 10wt% KPS aqueous solution, heating to 75 ℃, and reacting for 70min to obtain seed emulsion; the rest of the process was identical to example 1.
Example 7:
1. a modified water-soluble acrylate emulsion comprises the following raw materials:
45g of methyl methacrylate, 67.5g of butyl acrylate, 11g of behenyl methacrylate, 8g of glycidyl methacrylate, ES-4003.6 g, 2.4g of SDS, 0.14g of propylene glycol alginate, 0.11g of L-carnitine tartrate, 0.8g of potassium persulfate, 4g of acrylic acid, 5g of triethylamine, 0.18g of maltotetraose, 0.6g of sodium stearyl fumarate, 0.2g of sodium bicarbonate and 150g of deionized water.
2. A preparation method of modified water-soluble acrylate emulsion comprises the following specific steps:
2.1 preparation of Pre-emulsion: after adding 1.56g of SDS, 2.34g of ES-400, 0.18g of maltotetraose and 0.6g of sodium stearyl fumarate into 60g of deionized water and stirring to dissolve, 32.4g of MMA, 48.6g of BA, 8g of BMA and 4.8g of GMA were added dropwise and stirred vigorously at 800rpm for 30 minutes to prepare a pre-emulsion. The rest of the process was identical to example 1.
Example 8:
1. a modified water-soluble acrylate emulsion comprises the following raw materials:
45g of methyl methacrylate, 67.5g of butyl acrylate, 11g of behenyl methacrylate, 8g of glycidyl methacrylate, ES-4003.6 g, 2.4g of SDS, 0.14g of propylene glycol alginate, 0.11g of L-carnitine tartrate, 0.8g of potassium persulfate, 4g of acrylic acid, 5g of triethylamine, 0.13g of maltotetraose, 0.6g of sodium stearyl fumarate, 0.2g of sodium bicarbonate and 150g of deionized water.
2. A preparation method of modified water-soluble acrylate emulsion comprises the following specific steps:
2.1 preparation of Pre-emulsion: after adding 1.56g of SDS, 2.34g of ES-400, 0.13g of maltotetraose and 0.6g of sodium stearyl fumarate into 60g of deionized water and stirring to dissolve, 32.4g of MMA, 48.6g of BA, 8g of BMA and 4.8g of GMA were added dropwise and stirred vigorously at 800rpm for 30 minutes to prepare a pre-emulsion. The rest of the process was identical to example 1.
Example 9:
1. a modified water-soluble acrylate emulsion comprises the following raw materials:
45g of methyl methacrylate, 67.5g of butyl acrylate, 11g of behenyl methacrylate, 8g of glycidyl methacrylate, ES-4003.6 g, 2.4g of SDS, 0.14g of propylene glycol alginate, 0.11g of L-carnitine tartrate, 0.8g of potassium persulfate, 4g of acrylic acid, 5g of triethylamine, 0.21g of maltotetraose, 0.6g of sodium stearyl fumarate, 0.2g of sodium bicarbonate and 150g of deionized water.
2. A preparation method of modified water-soluble acrylate emulsion comprises the following specific steps:
2.1 preparation of Pre-emulsion: after adding 1.56g of SDS, 2.34g of ES-400, 0.21g of maltotetraose and 0.6g of sodium stearyl fumarate into 60g of deionized water and stirring to dissolve, 32.4g of MMA, 48.6g of BA, 8g of BMA and 4.8g of GMA were added dropwise and stirred vigorously at 800rpm for 30 minutes to prepare a pre-emulsion. The rest of the process was identical to example 1.
Example 10:
1. a modified water-soluble acrylate emulsion comprises the following raw materials:
45g of methyl methacrylate, 67.5g of butyl acrylate, 11g of behenyl methacrylate, 8g of glycidyl methacrylate, ES-4003.6 g, 2.4g of SDS, 0.14g of propylene glycol alginate, 0.11g of L-carnitine tartrate, 0.8g of potassium persulfate, 4g of acrylic acid, 5g of triethylamine, 0.06g of maltotetraose, 0.6g of sodium stearyl fumarate, 0.2g of sodium bicarbonate and 150g of deionized water.
2. A preparation method of modified water-soluble acrylate emulsion comprises the following specific steps:
2.1 preparation of Pre-emulsion: after adding 1.56g of SDS, 2.34g of ES-400, 0.06g of maltotetraose and 0.6g of sodium stearyl fumarate into 60g of deionized water and stirring to dissolve, 32.4g of MMA, 48.6g of BA, 8g of BMA and 4.8g of GMA were added dropwise and stirred vigorously at 800rpm for 30 minutes to prepare a pre-emulsion. The rest of the process was identical to example 1.
Example 11:
1. a modified water-soluble acrylate emulsion comprises the following raw materials:
45g of methyl methacrylate, 67.5g of butyl acrylate, 11g of behenyl methacrylate, 8g of glycidyl methacrylate, ES-4003.6 g, 2.4g of SDS, 0.14g of propylene glycol alginate, 0.11g of L-carnitine tartrate, 0.8g of potassium persulfate, 4g of acrylic acid, 5g of triethylamine, 0.3g of maltotetraose, 0.6g of sodium stearyl fumarate, 0.2g of sodium bicarbonate and 150g of deionized water.
2. A preparation method of modified water-soluble acrylate emulsion comprises the following specific steps:
2.1 preparation of Pre-emulsion: after adding 1.56g of SDS, 2.34g of ES-400, 0.3g of maltotetraose and 0.6g of sodium stearyl fumarate into 60g of deionized water and stirring to dissolve, 32.4g of MMA, 48.6g of BA, 8g of BMA and 4.8g of GMA were added dropwise and stirred vigorously at 800rpm for 30 minutes to prepare a pre-emulsion. The rest of the process was identical to example 1.
Example 12:
1. a modified water-soluble acrylate emulsion comprises the following raw materials:
45g of methyl methacrylate, 67.5g of butyl acrylate, 11g of behenyl methacrylate, 8g of glycidyl methacrylate, ES-4003.6 g, 2.4g of SDS, 0.14g of propylene glycol alginate, 0.11g of L-carnitine tartrate, 0.8g of potassium persulfate, 4g of acrylic acid, 5g of triethylamine, 0.6g of sodium stearyl fumarate, 0.2g of sodium bicarbonate and 150g of deionized water.
2. A preparation method of modified water-soluble acrylate emulsion comprises the following specific steps:
2.1 preparation of Pre-emulsion: after adding 1.56g of SDS, 2.34g of ES-400 and 0.6g of sodium stearyl fumarate into 60g of deionized water, stirring and dissolving, 32.4g of MMA, 48.6g of BA, 8g of BMA and 4.8g of GMA were added dropwise, and vigorously stirred at 800rpm for 30 minutes to prepare a pre-emulsion. The rest of the process was identical to example 1.
Example 13:
1. a modified water-soluble acrylate emulsion comprises the following raw materials:
45g of methyl methacrylate, 67.5g of butyl acrylate, 11g of behenyl methacrylate, 8g of glycidyl methacrylate, ES-4003.6 g, 2.4g of SDS, 0.14g of propylene glycol alginate, 0.11g of L-carnitine tartrate, 0.8g of potassium persulfate, 4g of acrylic acid, 5g of triethylamine, 0.18g of maltotetraose, 0.2g of sodium bicarbonate and 150g of deionized water.
2. A preparation method of modified water-soluble acrylate emulsion comprises the following specific steps:
2.1 preparation of Pre-emulsion: after adding 1.56g SDS, 2.34g ES-400, 0.18g maltotetraose into 60g deionized water, stirring and dissolving, 32.4g MMA, 48.6g BA, 8g BMA, 4.8g GMA were added dropwise, and vigorously stirred at 800rpm for 30min to prepare a pre-emulsion. The rest of the process was identical to example 1.
Test example 1:
1.1 emulsion particle size: the particle size of the emulsion was determined at room temperature using a Berttesize 2000 laser particle size distribution instrument. The samples were diluted with deionized water and ultrasonically dispersed before measurement, and each sample was tested 3 times and averaged. The results of the particle size measurement of the emulsion are shown in FIG. 2.
1.2 determination of monomer conversion: 20g of the filtered emulsion is weighed, dried to constant weight at 100 ℃ and weighed. The monomer conversion X was calculated as follows:
X（%）=
wherein, W1Is the mass of the emulsion sample, W2Mass of dried sample, W3W is the total amount of raw materials added4Is the mass of other non-volatile components in the raw material, W5Represents the total mass of the monomers. The results of the monomer conversion measurements are shown in FIG. 3.
1.3 determination of gel fraction: collecting the gel of the stirrer, the thermometer and the bottle wall and the filtered substance of the 100-mesh wire net, washing with deionized water, drying at 130 ℃ to constant weight, and weighing. The gel fraction G was calculated as follows:
G（%）=（W0/Wn）×100%
wherein, W0For gel quality, WnIs the total mass of the added monomers. The results of the gel fraction measurement are shown in FIG. 4.
1.4 testing of the mechanical stability of the emulsion: measuring 5mL of emulsion sample in a centrifuge tube, centrifuging the sample in the centrifuge tube at the rotating speed of 4000r/min for 30min, and taking out the sample to see whether a precipitate is separated out from the centrifuge tube, wherein if the precipitate is more, the poorer the mechanical stability of the emulsion is. Conversely, the better the mechanical stability of the emulsion.
1.5 testing of emulsion chemical stability: in the sample measuring tube, 16mL of the emulsion sample was added, and 4mL of 0.5wt% CaCl was added to the sample2The solution is shaken up and kept stand for 2 days without layering and gel, which indicates the chemical stability of the emulsionIs excellent. Conversely, the less chemically stable the emulsion. The results of the tests for the mechanical and chemical stability of the emulsions are shown in Table 5.
TABLE 5 mechanical and chemical stability of the emulsions
| Mechanical stability | Chemical stability | |
| Example 1 | By passing | By passing |
| Example 2 | By passing | By passing |
| Example 3 | By passing | By passing |
| Example 4 | By passing | By passing |
| Example 5 | Do not pass through | Do not pass through |
| Example 6 | Do not pass through | Do not pass through |
Test example 2:
2.1 emulsion viscosity measurement: the viscosity of the emulsion was determined by a paint-4 cup viscometer, according to GB/T1723 & 1993 paint viscosity determination. The results of the emulsion viscosity measurements are shown in FIG. 5.
2.2 respectively and evenly spreading the modified water-based acrylate emulsion prepared in the embodiment on a glass sheet, placing the glass sheet at 80 ℃ and drying the glass sheet to form a glue film with even thickness, and then testing the glue film.
2.2.1 calculation of the crosslinking ratio: weighing mass WxThe gel film of (1) is extracted by a Soxhlet extractor for 48h using THF as a solvent to remove linear molecules not participating in crosslinking, then dried to constant weight, and the mass W of the residual gel film is weighedy. The cross-linking rate Q is calculated as follows:
Q（%）=（Wy/Wx）×100%。
the measurement results of the crosslinking rate are shown in FIG. 6.
2.2.2 Water absorption measurement of adhesive film: the film was cut into squares (about 2 cm. times.2 cm), and weighed (m)0) Soaking in deionized water at room temperature for 24hr, removing water from the surface of the adhesive film with absorbent paper, and weighing (m)1) The measurement was performed 3 times, and the average value was obtained. Water absorption A was calculated by the following formula1：
A1（%）=[(m1-m0)/m0]×100%。
2.2.3 determination of the chemical resistance of the adhesive film: cutting the adhesive film into 2cm × 2cm squares, weighing (m)2) Soaking in 10v/v% ethanol solution at 25 deg.C for 24hr, removing water from the surface of the jelly membrane with absorbent paper, and weighing (m)3). The assay was performed 3 times in parallel and the mean value was taken. The absorbance A of a 10v/v% ethanol solution was calculated according to the following formula2：
A2（%）=[(m3-m2)/m2]×100%。
The water absorption of the adhesive films of examples 1 to 6 is shown in FIG. 7. The results of measuring the absorption rates of the adhesive films of examples 1 and 7 to 13 with respect to water and 10v/v% ethanol solution are shown in FIG. 8.
As can be seen from fig. 2, 3 and 4, compared with examples 4, 5 and 6, the emulsion of examples 1, 2 and 3 has significantly higher particle size and monomer conversion rate and significantly lower gel rate, as can be seen from table 5, the emulsion of examples 1, 2 and 3 has better stability, and as can be seen from fig. 7, the water absorption rate of the adhesive film of examples 1, 2 and 3 is significantly lower, which illustrates that the addition of alginic acid propylene glycol alginate and L-carnitine tartrate in the preparation process of the aqueous acrylate seed emulsion can reduce the particle size of the emulsion, optimize the water resistance of the adhesive film, improve the conversion rate and reduce the gel rate, and the stability of the prepared aqueous acrylate emulsion is high.
As can be seen from fig. 5, 6 and 8, compared with examples 1, 10, 11, 12 and 13, the emulsions of examples 7, 8 and 9 have lower viscosity, higher crosslinking degree of the adhesive films and lower absorptivity to water and 10v/v% ethanol solution, which indicates that adding a certain proportion of maltotetraose and sodium stearyl fumarate in the pre-emulsion preparation process can reduce the system viscosity, improve the crosslinking density and optimize the water resistance and chemical resistance of the adhesive films.
Conventional techniques in the above embodiments are known to those skilled in the art, and therefore, will not be described in detail herein.
The above embodiments are merely illustrative, and not restrictive, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the invention. Therefore, all equivalent technical solutions also belong to the scope of the present invention, and the protection scope of the present invention should be defined by the claims.
Claims (10)
1. A preparation method of modified water-soluble acrylate emulsion is characterized by comprising the following specific steps:
A. preparation of pre-emulsion: adding the compound emulsifier into deionized water, heating and stirring, dissolving, dropwise adding an acrylate monomer and GMA, and stirring to obtain a pre-emulsion;
B. preparing a seed emulsion: adding the compound emulsifier, propylene glycol alginate, L-carnitine tartrate and buffer into a container filled with deionized water, stirring for dissolving, and introducing N2Removing air in the container, raising the temperature to 35-40 ℃, dropwise adding an acrylate monomer and GMA, preserving the temperature for 10-30min, raising the temperature to 60-70 ℃, dropwise adding an initiator solution S1, raising the temperature to 70-75 ℃, and reacting for 50-80min to obtain a seed emulsion;
C. polymerization reaction: synchronously dropwise adding the pre-emulsion and the initiator solution S2 into the seed emulsion at 70-75 ℃, stably dropwise adding at a constant speed within 3-4h, then synchronously dropwise adding AA and a neutralizing agent, after dropwise adding within 30min, keeping the temperature for reaction for 50-80min, supplementing the initiator solution S3, continuing the reaction for 50-80min, and filtering through a copper net of 80-100 meshes to obtain a finished product;
the deionized water in the step A accounts for 35-45% of the total deionized water; the acrylate monomer comprises MMA, BA and BMA; the compound emulsifier comprises ES-400 and SDS; the total deionized water is the sum of the deionized water in the step A and the deionized water in the step B.
2. The method of claim 1, wherein: the initiator solution S1: initiator solution S2: the initiator solution S3 is 2-3:5-6: 1-2.
3. The method of claim 1, wherein: the mass ratio of MMA, BA and BMA in the acrylate monomer is 8-10:10-15: 1-3.
4. The method of claim 1, wherein: the total amount of GMA in steps A and B is 2-8wt% of the total amount of acrylate monomers in steps A and B.
5. Use of a modified water-soluble acrylate emulsion as claimed in any one of claims 1 to 4 in the preparation of moisture barrier paper.
6. A modified water-soluble acrylate emulsion is characterized in that: the preparation is carried out by the preparation method described in any one of claims 1 to 4.
7. A moisture barrier comprising the modified water-soluble acrylate emulsion of claim 6.
8. A method of imparting moisture barrier properties to a desired paper comprising: the moisture barrier agent according to claim 7, which is applied to paper and then dried.
9. A method for imparting moisture vapor barrier and composite properties to a desired paper comprising: the moisture barrier agent according to claim 7, which is applied to paper, laminated with a paper layer before drying, and dried.
10. Use of the moisture barrier agent of claim 7 in the preparation of a core paper for a cement paper bag.
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