CN114108371B - UV-cured paper surface sizing agent and preparation and application thereof - Google Patents

UV-cured paper surface sizing agent and preparation and application thereof Download PDF

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CN114108371B
CN114108371B CN202111502414.0A CN202111502414A CN114108371B CN 114108371 B CN114108371 B CN 114108371B CN 202111502414 A CN202111502414 A CN 202111502414A CN 114108371 B CN114108371 B CN 114108371B
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paper
surface sizing
sizing agent
curing
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CN114108371A (en
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姚慧玲
李田田
王明陆
郑万强
邢训坤
唐明成
王红乐
崔世栋
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Shandong Ruibolong Chemical Science & Technology Co ltd
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    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H21/00Non-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
    • D21H21/14Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16Sizing or water-repelling agents
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00Manufacture or treatment of nanostructures
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/46Polymerisation initiated by wave energy or particle radiation
    • C08F2/48Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10Esters
    • C08F222/1006Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/106Esters of polycondensation macromers
    • C08F222/1061Esters of polycondensation macromers of alcohol terminated polyesters or polycarbonates, e.g. polyester (meth)acrylates
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H19/00Coated paper; Coating material
    • D21H19/36Coatings with pigments
    • D21H19/38Coatings with pigments characterised by the pigments
    • D21H19/40Coatings with pigments characterised by the pigments siliceous, e.g. clays
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H19/00Coated paper; Coating material
    • D21H19/36Coatings with pigments
    • D21H19/44Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H19/00Coated paper; Coating material
    • D21H19/36Coatings with pigments
    • D21H19/44Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/46Non-macromolecular organic compounds
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H19/00Coated paper; Coating material
    • D21H19/36Coatings with pigments
    • D21H19/44Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/62Macromolecular organic compounds or oligomers thereof obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H21/00Non-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
    • D21H21/50Non-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 form
    • D21H21/52Additives of definite length or shape
    • D21H21/54Additives of definite length or shape being spherical, e.g. microcapsules, beads

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  • Manufacturing & Machinery (AREA)
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Abstract

The invention relates to a UV-cured paper surface sizing agent and preparation and application thereof, belonging to the technical field of paper surface sizing agents. The acryloyl morpholine, the organic functional dendritic nano silicon dioxide and the polyester acrylate prepolymer are used as main components, the polar acryloyl morpholine is used for replacing the traditional styrene and acrylic acid, the polar acryloyl morpholine can be combined with fiber hydrogen bonds in paper, and the high-temperature resistant, saline-alkali resistant, shearing resistant, high curing speed and other excellent characteristics are achieved. The addition of the nano silicon dioxide endows the surface sizing agent with excellent water resistance, mechanical property and heat resistance, and improves the ultraviolet absorptivity. After UV curing, the polyester acrylate prepolymer is polymerized and crosslinked to form a high-molecular net structure, so that the bonding force among fibers is enhanced, the compactness of a coating film is improved, and the smoothness and the wet strength of the surface of paper can be improved. By adopting UV curing, an emulsifier is not needed, so that the problems of reduction of physical and mechanical properties and chemical properties of paper, water absorption and swelling in water and the like caused by the residual emulsifier can be avoided.

Description

UV-cured paper surface sizing agent and preparation and application thereof
Technical Field
The invention relates to a UV curing paper surface sizing agent and a preparation and application method thereof, in particular to a UV curing paper surface sizing agent containing acryloyl morpholine and a preparation and application method thereof, belonging to the technical field of paper surface sizing agents.
Background
Surface sizing is an important way for treating the surface of paper to improve the application performance of the paper, and the application of the surface sizing agent is more and more extensive with the continuous improvement of the technical level of the paper-making production process and the upgrading and upgrading of paper-making equipment. The surface sizing has the advantages of low sizing cost, capability of reducing the strength reduction of paper caused by sizing agents in pulp, paper machine dirt, net water white water load and the like, and can obviously improve the surface properties of the paper, such as surface strength, water resistance and the like. The surface sizing agent becomes an effective method for changing the performance of paper and producing paper with high added value, and is also an effective method for solving the problem of paper product quality, and is increasingly concerned and applied by paper-making workers. For example, chinese patent CN108690159a discloses a polymer surface sizing agent, which is prepared by dispersing styrene monomer and acrylate monomer as main monomers in an emulsifier and polymerizing under the action of an initiator. Chinese patent CN106283869A discloses an organic/inorganic composite surface sizing agent, silica sol is prepared by reacting simple substance silicon powder and water under the catalysis of sodium hydroxide, and the mass of oligomeric chitosan and silica sol is 2:3-1:9. The organic/inorganic composite surface sizing agent improves the water resistance and the surface strength of the surface sizing agent by preparing nano silica sol and compounding oligomeric chitosan, but the silica sol in the system is easy to be condensed to form gel, and the shrinkage and the fracture can occur in the paper making and drying process, thereby affecting the performance index of the paper.
In the prior art, the surface sizing agent is mostly prepared by adopting an emulsion polymerization process, the polymer surface sizing agent can better meet the special requirements of high-performance paper, however, the residual emulsifier in a polymerization product can influence the water resistance and chemical corrosion resistance of an adhesive film, pinholes can easily appear in the adhesive film, the physical mechanical property and the chemical property are reduced, in addition, the emulsifier molecules in the adhesive film can easily migrate to the surface, a non-chemical bonding emulsifier layer is formed on the surface of the film, and the emulsifier layer can absorb water and swell when meeting water, has complex components and higher cost. When inorganic nano materials such as nano silicon dioxide and the like are compounded with organic polymers for use, the surface strength and the water resistance of paper and the printing performance of the paper can be effectively improved, and the cost is reduced. However, the nano particles have the characteristics of large specific surface energy, strong polarity and the like, and are easy to agglomerate and promote sedimentation in the preparation and treatment processes, so that the nano silicon dioxide has poor dispersion stability in organic molecules, cannot achieve a good composite effect, and influences the service performance.
In order to overcome the defects of the paper surface sizing agent in the prior art that the physical and mechanical properties and the chemical properties of paper are reduced and water absorption swelling is caused by the residual emulsifier, the paper surface sizing agent capable of improving the dispersibility of nano silicon dioxide and organic polymer in composite use and improving the product performance, and the preparation and application methods thereof are in urgent need of development.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a UV curing paper surface sizing agent and a preparation method and application thereof, wherein organic functional dendritic nano-silica is used as an inorganic composite material, and a UV curing process is adopted, so that the influence of the use residue of an emulsifier in a polymerization product on the performance of the surface sizing agent is avoided, and the UV curing paper surface sizing agent has the advantages of improving the smoothness of the paper surface, the paper printing adaptability, the paper surface strength, the bursting strength, the folding strength, the wet strength and the like.
The technical scheme adopted by the invention for solving the technical problems is as follows: the UV-curing paper surface sizing agent is prepared from the following components in parts by weight:
Figure BDA0003402267070000021
the organic functionalized dendritic nano-silica is dendritic porous nano-silica with the particle size of 100-200 nm, and the preparation method comprises the following steps:
a. preparing dendritic nano silicon dioxide:
adding 30.2-45.5 g of ethyl orthosilicate and 60-80 ml of absolute ethyl alcohol into the reactor A, keeping the temperature to 30-40 ℃, and fully stirring to form a solution. Adding 70.5-80.8 g of deionized water, 0.2-1.3 g of dodecyl benzyl trimethyl ammonium bromide and 0.5-2.6g of urea into the reactor B, fully stirring, and mixing with the solution in the reactor A to form reaction mother liquor. Carrying out hydrothermal synthesis on the mother liquor in a homogeneous reactor, heating to 120-125 ℃, reacting for 4-5 h at a stirring speed of 60r/min, and obtaining the stable white emulsion.
And centrifugally separating the obtained white emulsion, washing the white emulsion for 3 times by using acetone and deionized water respectively, and drying the white emulsion at the temperature of 70 ℃ to obtain white powder. And placing the white powder in a muffle furnace, heating to 500 ℃, calcining for 6-7 h, and removing the template agent dodecyl benzyl trimethyl ammonium bromide to obtain the dendritic nano silicon dioxide.
b. Organically functionalizing the dendritic nano silicon dioxide:
dispersing 10.5-20.5 g of dendritic nano-silica in an organic solvent, and performing ultrasonic dispersion for 20min to obtain a uniformly dispersed suspension. Adding the suspension into a three-neck flask, slowly dripping 70.2-80.5 g of N, N-dimethylpropionamide, 70.2-80.5 g of toluene-2,4-diisocyanate and 5.5-10.6 g of dibutylene dilaurate at the temperature of 70-80 ℃, reacting for 2-3 h, cooling to 45-55 ℃, adding 2.5-5 g of hydroquinone, and dripping a mixture of 70-80 g of hydroxyethyl acrylate and 70-80gN, N-dimethylpropionamide. After reacting for 2-3 h, drying the product in a vacuum oven at the drying temperature of 30-40 ℃, and fully grinding to obtain the organic functionalized silicon dioxide with active double bonds on the surface, namely the organic functionalized dendritic nano-silicon dioxide.
Preferably, the organic solvent in step b is N, N-dimethylpropionamide.
The polyester acrylate prepolymer is an acrylic acid-terminated terpolymer of adipic acid, diethylene glycol and maleic anhydride, and is prepared from the following components in parts by weight:
Figure BDA0003402267070000031
preferably, the catalyst is p-toluenesulfonic acid.
Preferably, the polymerization inhibitor is hydroquinone.
The polyester acrylate prepolymer is prepared by the following steps:
adding 60-70 parts of toluene, 30-40 parts of adipic acid, 80-90 parts of diethylene glycol and 30-40 parts of maleic anhydride into a four-neck flask, adding 0.2-0.4 part of catalyst p-toluenesulfonic acid, heating under the protection of nitrogen, stirring at a stirring speed of 120r/min while heating to fully dissolve the components, heating to 125-135 ℃, refluxing for 2-3 hours, and distributing water, wherein the reaction equation is as follows:
Figure BDA0003402267070000032
when the reaction temperature is reduced to 100-105 ℃, adding 25-30 parts of acrylic acid and 0.01-0.02 part of polymerization inhibitor hydroquinone, keeping the stirring speed at 120r/min, continuously heating, refluxing when the temperature is increased to 135-145 ℃, distributing water after refluxing for 2-3 h until no water is distilled off, cooling and discharging. Washing the product with water to remove the catalyst p-toluenesulfonic acid, and removing toluene and unreacted acrylic acid by reduced pressure distillation to obtain the polyester acrylate prepolymer, wherein the reaction equation is as follows:
Figure BDA0003402267070000041
wherein n is more than or equal to 4 and less than or equal to 8.
The characterization shows that the viscosity of the polyester acrylate prepolymer at 25 ℃ is 10000-13000 mPa & s.
A UV curing paper surface sizing agent is prepared by the following steps:
(1) Preparing the organic functional dendritic nano silicon dioxide.
(2) Preparing a polyester acrylate prepolymer.
(3) Preparing a UV curing paper surface sizing agent:
under the condition of room temperature, firstly adding 20-40 parts of reactive diluent, 20-30 parts of acryloyl morpholine and 50-80 parts of polyester acrylate prepolymer, starting stirring, controlling the rotating speed at 100-200 r/min, heating to 75-85 ℃, stirring for 20min, adding 10-15 parts of organic functionalized dendritic nano-silica, continuing stirring for 30-40 min, cooling to 48-52 ℃, adding 1-4 parts of photoinitiator, and stirring for 30-40 min to obtain the UV cured paper surface sizing agent.
Preferably, the reactive diluent is a combination of tripropylene glycol diacrylate and ethoxylated trimethylolpropane triacrylate. The mass ratio of the tripropylene glycol diacrylate to the ethoxylated trimethylolpropane triacrylate is 1:1-3.
Preferably, the photoinitiator is: 2-phenylbenzyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide and one or more of 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone in any proportion.
The UV-curing paper surface sizing agent is applied to surface sizing of paper, and comprises the following steps:
and (3) adopting an ST-1-260 type coating machine to glue the surface sizing agent of the UV-cured paper on the surface of the paper, and then adopting an ultraviolet curing machine with the power of 3kW to irradiate for UV curing.
Preferably, the coating amount of the coating machine on the surface of the paper is 0.8-1.4 g/m 2
The invention has the advantages of
(1) Compared with the paper surface sizing agent in the prior art, the UV curing paper surface sizing agent has the advantages that no emulsifier is needed in the UV curing, the physical and mechanical properties and chemical properties of paper are reduced due to the residual emulsifier, and the problems that a non-chemically bonded emulsifier layer is formed on the surface of a film, and the film absorbs water and swells when meeting water are solved.
(2) The polar acryloyl morpholine component is adopted to replace the traditional styrene and acrylic acid components, and the acryloyl morpholine has higher polarity and can be combined with fiber hydrogen bonds in paper. The side chain is a heterocyclic structure containing nitrogen elements and oxygen elements, has good adhesive force, has the rigidity of a six-membered ring and certain flexibility, has excellent characteristics of high temperature resistance, saline and alkaline resistance, shear resistance, high curing speed and the like as a UV curing monomer, and can ensure that paper can quickly absorb ink after being applied with glue, the tensile strength is high and no curling occurs.
(3) After UV curing, the polyester acrylate prepolymer free radical polymerization crosslinking forms a high-molecular net structure, the fibers are fixed in the polyester acrylate net through the hydrogen bond combination of hydrophilic groups in the acryloyl morpholine and the fibers, the bonding force among the fibers is enhanced, the free movement of single fibers is restrained, the fiber arrangement form is more regular, and the surface wrinkles of the paper are reduced and are smoother. In addition, according to a photocuring mechanism, a cross-linked net structure can be formed after curing, so that the compactness of a coating film is increased, the smoothness of the surface of the paper can be improved, and the wet strength of the paper can be improved.
(4) Dendritic nano silicon dioxide prepared by adding dodecyl benzyl trimethyl ammonium bromide as a template agent: firstly, the addition of the nano silicon dioxide endows the surface sizing agent with excellent water resistance, mechanical property, heat resistance and extremely strong ultraviolet absorption characteristic. Secondly, the dendritic nano-silica has a three-dimensional radial dendritic superstructure, a large number of active functional groups exist on the surface, and a large number of photochemical active carbon-carbon double bonds are introduced on the surface of the dendritic nano-silica through organic modification, so that the UV curing rate is improved. Thirdly, under the action of the photoinitiator, chemical bonds combined with the organic polymer are increased, firm binding force is generated, the affinity and the internal stability between the nano silicon dioxide and the organic polymer are improved, and a good composite effect is achieved. Fourthly, the dendritic nano silicon dioxide has a three-dimensional center radial porous structure, so that the density of the dendritic nano silicon dioxide is reduced, and the weight of the surface sizing agent is reduced.
(5) By adding maleic anhydride into the polyester acrylate prepolymer, the density of C = = C double bonds in the prepolymer structure is increased, so that the photocuring speed is improved. In addition, the introduction of ether bond in diglycol in the polyester acrylate prepolymer improves the adhesion with paper.
Detailed Description
In order to better understand the invention, the following examples further illustrate the content of the invention, but the content of the invention is not limited to the following examples, and the examples should not be construed as limiting the scope of the invention.
Example 1
The UV curing paper surface sizing agent is prepared from the following components in parts by weight:
Figure BDA0003402267070000051
the preparation steps of the UV curing paper surface sizing agent are as follows:
(1) Preparing organic functional dendritic nano-silica:
a. preparing dendritic nano silicon dioxide: 30.2g of ethyl orthosilicate and 60ml of absolute ethanol are added into a reactor A, the temperature is kept constant to 30 ℃, and the mixture is fully stirred to form a solution. Adding 70.5-80.8 g of deionized water, 0.2-1.3 g of dodecyl benzyl trimethyl ammonium bromide and 0.5-2.6g of urea into the reactor B, fully stirring, and mixing with the solution in the reactor A to form reaction mother liquor. Carrying out hydrothermal synthesis on the mother liquor in a homogeneous reactor, heating to 120-125 ℃, reacting for 4 hours at a stirring speed of 60r/min, and obtaining the stable white emulsion.
The obtained white emulsion is centrifugally separated, washed by acetone and deionized water for 3 times respectively, and dried at the temperature of 70 ℃ to obtain white powder. And placing the white powder in a muffle furnace, heating to 500 ℃, calcining for 6h, and removing the template agent to obtain the dendritic nano silicon dioxide.
b. Organically functionalizing the dendritic nano silicon dioxide: dispersing 10.5g of dendritic nano-silica in an organic solvent, and performing ultrasonic dispersion for 20min to obtain a uniformly dispersed suspension. Adding the suspension into a reaction vessel, slowly dripping 70.2gN, N-dimethylpropionamide, 70.2g of toluene-2,4-diisocyanate and 5.5g of dibutylene dilaurate at the temperature of 70 ℃, reacting for 2h, cooling to 45 ℃, adding 2.5g of hydroquinone, and dripping a mixture of 70g of hydroxyethyl acrylate and 70gN, N-dimethylpropionamide. After reacting for 2h, drying the product in a vacuum oven at the drying temperature of 30 ℃, and fully grinding to obtain the organic functionalized silicon dioxide with active double bonds on the surface. The characterization shows that the grain diameter of the organic functional dendritic nano silicon dioxide is 100-200 nm.
(2) Preparation of polyester acrylate prepolymer:
the polyester acrylate prepolymer is prepared from the following components in parts by weight:
Figure BDA0003402267070000061
the preparation method comprises the following steps:
adding 60 parts of toluene, 30 parts of adipic acid, 80 parts of diethylene glycol and 30 parts of maleic anhydride into a four-neck flask, adding 0.2 part of catalyst p-toluenesulfonic acid, heating under the protection of nitrogen at a stirring speed of 120r/min while stirring to fully dissolve the components, heating to 125-135 ℃, refluxing for 2 hours, and distributing water.
When the reaction temperature is reduced to 100 ℃, adding 25 parts of acrylic acid and 0.01 part of polymerization inhibitor hydroquinone, keeping the stirring speed at 120r/min, continuing heating, heating to 135 ℃, refluxing for 2h, then distributing water until no water is distilled off, cooling and discharging. And washing the product with water to remove the catalyst p-toluenesulfonic acid, and removing toluene and unreacted acrylic acid by reduced pressure distillation to obtain the polyester acrylate prepolymer. The characterization shows that the viscosity of the polyester acrylate prepolymer at 25 ℃ is 10000-11000 mPa & s.
(3) Preparing a UV curing paper surface sizing agent:
under the condition of room temperature, firstly adding 10 parts of tripropylene glycol diacrylate, 10 parts of ethoxylated trimethylolpropane triacrylate, 20 parts of acryloyl morpholine and 50 parts of prepolymer, starting stirring, controlling the rotating speed at 60r/min, heating to 75 ℃, stirring for 20min, adding 10 parts of organic functional dendritic nano-silica, continuing stirring for 30min, cooling to 48-52 ℃, adding 0.5 part of 2-benzyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone and 0.5 part of 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone photoinitiator, and stirring for 30min to obtain the UV curing paper surface sizing agent.
Example 2
The UV-curing paper surface sizing agent is prepared from the following components in parts by weight:
Figure BDA0003402267070000071
the preparation method of the UV curing paper surface sizing agent comprises the following steps:
(1) Preparing organic functional dendritic nano-silica:
a. preparing dendritic nano silicon dioxide: 38.6g of tetraethoxysilane and 700ml of absolute ethanol are added to the reactor A, the temperature is kept constant at 35 ℃, and the mixture is fully stirred to form a solution. 75.8g of deionized water, 0.8g of dodecylbenzyltrimethylammonium bromide and 1.8g of urea are added into a reactor B, and the mixture is mixed with the solution after being fully stirred to form a reaction mother solution. Carrying out hydrothermal synthesis on the mother liquor in a homogeneous reactor, heating to 120-125 ℃, reacting for 4.5h, and stirring at the speed of 60r/min to obtain stable white emulsion.
And centrifugally separating the obtained white emulsion, washing the white emulsion for 3 times by using acetone and deionized water respectively, and drying the white emulsion at the temperature of 70 ℃ to obtain white powder. And then placing the white powder in a muffle furnace, heating to 500 ℃, calcining for 6.5h, and removing the template agent to obtain the dendritic nano silicon dioxide.
b. Organically functionalizing the dendritic nano silicon dioxide: dispersing 18.6g of dendritic nano-silica in an organic solvent, and performing ultrasonic dispersion for 20min to obtain a uniformly dispersed suspension. Adding the suspension into a reaction vessel, slowly and dropwise adding 76.5g of N, N-dimethylpropionamide, 75.6g of toluene-2,4-diisocyanate and 8.5g of dibutylene dilaurate at 75 ℃, reacting for 2.5h, cooling to 50 ℃, adding 4.5g of hydroquinone, and dropwise adding a mixture of 75g of hydroxyethyl acrylate and 75g of N, N-dimethylpropionamide. After 2.5h of reaction, the product is dried in a vacuum oven, the drying temperature is 35 ℃, and the organic functionalized silicon dioxide with active double bonds on the surface is obtained after full grinding. The characterization shows that the grain diameter of the organic functional dendritic nano silicon dioxide is 100-200 nm.
(2) Preparation of polyester acrylate prepolymer:
the polyester acrylate prepolymer is prepared from the following components in parts by weight:
Figure BDA0003402267070000081
the preparation method comprises the following steps:
adding 65 parts of toluene, 35 parts of adipic acid, 85 parts of diethylene glycol and 35 parts of maleic anhydride into a four-neck flask, adding 0.3 part of catalyst p-toluenesulfonic acid, heating under the protection of nitrogen at a stirring speed of 120r/min while stirring to fully dissolve the components, heating to 130 ℃, refluxing for 2.5 hours, and distributing water.
When the reaction temperature is reduced to 100 ℃, adding 27 parts of acrylic acid and 0.015 part of polymerization inhibitor hydroquinone, keeping the stirring speed at 120r/min, continuously heating, refluxing when the temperature is increased to 130 ℃, distributing water after refluxing for 2.5 hours until no water is distilled off, cooling and discharging. And washing the product with water to remove the catalyst p-toluenesulfonic acid, and removing toluene and unreacted acrylic acid by reduced pressure distillation to obtain the polyester acrylate prepolymer. The characterization shows that the viscosity of the polyester acrylate prepolymer at 25 ℃ is 11000-12000 mPa.s.
(3) Preparing a UV curing paper surface sizing agent:
under the condition of room temperature, firstly adding 10 parts of tripropylene glycol diacrylate, 15 parts of ethoxylated trimethylolpropane triacrylate, 25 parts of acryloyl morpholine and 60 parts of prepolymer, starting stirring, controlling the rotating speed at 160r/min, heating to 80 ℃, stirring for 20min, adding 12 parts of organic functionalized dendritic nano-silica, continuing stirring for 35min, cooling to 48-52 ℃, adding 1 part of 2-benzyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone, 1 part of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide and 1 part of phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide photoinitiator, and stirring for 35min to obtain the UV-cured paper surface sizing agent.
Example 3
The UV-curing paper surface sizing agent is prepared from the following components in parts by weight:
Figure BDA0003402267070000082
the preparation method of the UV curing paper surface sizing agent comprises the following steps:
(1) Preparing organic functional dendritic nano-silica:
a. preparing dendritic nano silicon dioxide: 45.5g of tetraethoxysilane and 80ml of absolute ethanol are added to the reactor A, the temperature is kept constant to 40 ℃, and the mixture is fully stirred to form a solution. 80.8g of deionized water, 1.3g of dodecylbenzyltrimethylammonium bromide and 2.6g of urea are added into the reactor B, fully stirred and mixed with the solution in the reactor A to form reaction mother liquor. Carrying out hydrothermal synthesis on the mother liquor in a homogeneous reactor, heating to 120-125 ℃, reacting for 5 hours at a stirring speed of 60r/min, and obtaining the stable white emulsion.
And centrifugally separating the obtained white emulsion, washing the white emulsion for 3 times by using acetone and deionized water respectively, and drying the white emulsion at the temperature of 70 ℃ to obtain white powder. And placing the white powder in a muffle furnace, heating to 500 ℃, calcining for 7h, and removing the template agent to obtain the dendritic nano silicon dioxide.
b. Organically functionalizing the dendritic nano silicon dioxide: dispersing 20.5g of dendritic nano-silica in an organic solvent, and performing ultrasonic dispersion for 20min to obtain a uniformly dispersed suspension. Adding the suspension into a reaction vessel, slowly dripping 80.5g of N, N-dimethylpropionamide, 80.5g of toluene-2,4-diisocyanate and 10.6g of dibutylene dilaurate at the temperature of 80 ℃, reacting for 3h, cooling to 55 ℃, adding 5g of hydroquinone, and dripping a mixture of 80g of hydroxyethyl acrylate and 80g of N, N-dimethylpropionamide. After reacting for 3h, drying the product in a vacuum oven at 40 ℃, and fully grinding to obtain the organic functionalized silicon dioxide with active double bonds on the surface. The characterization shows that the grain diameter of the organic functional dendritic nano silicon dioxide is 100-200 nm.
(2) Preparation of polyester acrylate prepolymer:
the polyester acrylate prepolymer is prepared from the following components in parts by weight:
Figure BDA0003402267070000091
the preparation method comprises the following steps:
adding 70 parts of toluene, 40 parts of adipic acid, 90 parts of diethylene glycol and 40 parts of maleic anhydride into a four-neck flask, adding 0.4 part of catalyst p-toluenesulfonic acid, heating under the protection of nitrogen at a stirring speed of 120r/min while stirring to fully dissolve the components, heating to 135 ℃, refluxing for 3 hours, and distributing water.
When the reaction temperature is reduced to 100 ℃, adding 30 parts of acrylic acid and 0.02 part of polymerization inhibitor hydroquinone, keeping the stirring speed at 120r/min, continuously heating, refluxing when the temperature is increased to 135 ℃, distributing water after refluxing for 3h until no water is distilled off, cooling and discharging. And washing the product with water to remove the catalyst p-toluenesulfonic acid, and removing toluene and unreacted acrylic acid by reduced pressure distillation to obtain the polyester acrylate prepolymer. The viscosity of the polyester acrylate prepolymer at 25 ℃ is 12000-13000 mPa & s through characterization.
(3) Preparing a UV curing paper surface sizing agent:
under the condition of room temperature, firstly adding 10 parts of tripropylene glycol diacrylate, 30 parts of an ethoxylated trimethylolpropane triacrylate active diluent, 30 parts of acryloyl morpholine and 80 parts of prepolymer, starting stirring, controlling the rotating speed at 300r/min, heating to 85 ℃, stirring for 20min, adding 15 parts of organic functional dendritic nano-silica, continuing stirring for 40min, cooling to 48-52 ℃, adding 1 part of 2-benzyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone, 1 part of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 1 part of phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide and 1 part of 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone photoinitiator, and stirring for 40min to obtain the UV-cured paper surface sizing agent.
And (3) comparison test:
comparative example 1
The preparation process of the UV curing paper surface sizing agent is as follows, and the rest is the same as the example 1.
Under the condition of room temperature, firstly adding 10 parts of tripropylene glycol diacrylate, 10 parts of ethoxylated trimethylolpropane triacrylate, 20 parts of acryloyl morpholine and 50 parts of prepolymer, starting stirring, controlling the rotating speed at 60r/min, heating to 75 ℃, stirring for 20min, adding 10 parts of organic functionalized dendritic nano-silica, continuing stirring for 30min, cooling to 48-52 ℃, adding 2 parts of potassium persulfate initiator, and stirring for 30min to obtain the surface sizing agent.
Comparative example 2
The same procedure as in example 1 was followed except that only the organofunctionalized dendritic nanosilica was replaced with the dendritic nanosilica which had not been organofunctionalized.
Comparative example 3
The same procedure as in example 1 was followed except that only the organic functionalized dendritic nanosilica was replaced with the commercially available silica cabot white carbon black CAB-O-SIL TS-530 fumed silica.
Comparative example 4
The procedure of example 1 was otherwise the same as in the preparation of the UV-curable paper surface sizing agent except that acryloyl morpholine alone was not used.
Comparative example 5
The procedure of example 1 was repeated except that the photoinitiator was replaced with 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinobenzylphenyl) butanone as a single component.
Detection, characterization and comparison:
the UV-curing paper surface sizing agents prepared in the examples 1-3 and the comparative examples 1-5 are respectively used for sizing the surface of the paper by using an ST-1-260 type coating machine, UV curing is carried out by irradiating an ultraviolet curing machine with the power of 3kW, and the paper is subjected to detection of tensile strength, coBB value, surface strength and smoothness, wherein the detection items are as follows:
(1) CoBB value
The CoBB value refers to the surface absorbency of paper and board, also known as the surface absorbent weight of the paper, with a higher weight generally indicating a higher absorbency of the paper. The test method comprises the following steps: cutting the paper to be tested into 10cm 2 And (4) pouring 100ml of water into the paper, pouring the water after 45 seconds of absorption, and completely absorbing the water on the surface of the paper by using water-absorbing paper, wherein the weight difference of the paper before and after comparison.
(2) Tensile strength
The tensile strength of paper is usually the maximum tensile force that can be borne when a paper sample with a certain width is subjected to stress fracture, the tensile strength represents the toughness and the tensile force of the paper, and also represents the bonding force between fibers and the strength of the fibers, and the tensile strength performance test of the paper is one of the performances which must be tested in paper production enterprises and use industries. The detection method comprises the following steps: 10 test pieces each having a width of 15mm and a length of 250mm were cut out in the longitudinal and transverse directions of the paper by a sample cutter. The tensile strength test is carried out by using a tensile strength tester, and the test length is adjusted to 180mm +/-1 mm at the position of a chuck of the tester device. Adjusting the stretching speed to be 20mm/min +/-5 mm/min; the sample is held in the test jaw and the tensile tester is started to pull the sample at a rate of 20mm/min + -5 mm/min until the sample breaks. The maximum tensile force applied was recorded. The sample broke within 10mm of the grip distance during the test and all readings should be discarded. The calculation formula is as follows:
Figure BDA0003402267070000111
t- -tensile index, N.m/g;
G P absolute tensile strength, N/m;
w- -quantitative, g/m 2
(3) Paper bursting strength
During testing, according to the pressure transmission principle, the paper pattern is gradually raised under the action of pressure until the paper pattern is finally broken, and the maximum pressure borne by the paper pattern in the process is the bursting strength of the test sample. Burst is the burst strength of paper, representing the overall strength, uniformity and toughness of the paper. The detection method comprises the following steps: a standard sample of 100 square centimeters to be tested is cut, and an NP-1 electronic paper bursting strength tester is used for displaying a stable input layer numerical value and a quantitative value. Install the sample on anchor clamps, press "automatic" key, the last clamping ring of instrument pushes down slowly, and pressure reaches certain degree, stops to push down. The hydraulic piston starts to move, pressure is applied to the center of the sample through the adhesive film and gradually increases until the sample is broken, the upper pressing ring and the piston return to the initial position, and the display window displays the burst strength and the test times. The calculation formula is as follows:
Figure BDA0003402267070000112
b- -burst index, KPa.m 2 /g;
p- -absolute burst, KPa.
(4) Wet strength of paper
Paper strength is highly susceptible to moisture and paper saturated with water typically loses 95% or more of its tensile strength, with the remainder of the strength often referred to as wet strength. The detection method comprises the following steps: cutting a test sample according to GB/T450, cutting the paper to be tested into a test sample of 15mm multiplied by 100mm on a paper cutter, respectively soaking paper strips in deionized water for 10min under a dry condition, absorbing excessive moisture on the surface by using filter paper, and quickly measuring by using a ZL-300A type paper and paperboard tensile testing machine, wherein the speed of the testing machine is 40rpm. The calculation formula is as follows:
Figure BDA0003402267070000121
w- -Wet Strength, KPa;
d- -Dry Strength, KPa.
(5) Folding strength of paper
Folding endurance is one of the basic mechanical properties of paper and is used to indicate the ability of paper to resist folding back and forth. The folding strength of a paper sheet is measured as the number of times of folding, expressed in number of times, in which the paper sheet is stretched with a certain force and then folded back and forth to break the paper sheet, and the unit is the double fold. The detection method comprises the following steps: 10 test specimens 15mm by 100mm are cut out according to GB/T450, measured using a Shoebert refractometer, and the specimens are placed in a chuck, clamped parallel between the two chucks of the tester, and the spring cartridge is pulled apart until the pin locks the spring cartridge, applying tension to the specimens. And (4) returning the counter to zero, starting the instrument to enable the sample to start to be folded until the sample is broken, automatically stopping counting by the instrument, and recording the reading.
(6) Paper smoothness inspection
The smoothness of the paper is the time required for a certain amount of air to escape from the atmosphere between the sample side and the annular plate side under a specific contact condition and a certain pressure difference. The measurement was carried out by placing paper and cardboard on a glass plate, applying a specific pressure to generate a semi-vacuum, thereby sucking air and passing the air through the contact surface, and measuring the time required for the degree of vacuum to vary within a prescribed range. The detection method comprises the following steps: sampling according to the GB/T450 specification. On the extracted large sheets, enough samples for each of the front and back sides to be tested 10 times are cut out uniformly along the cross-web 15mm from the edge, the area of the sample is at least 60mm x 60mm, and the samples are ensured to be free of folds, wrinkles, visible cracks or other paper defects. For testing, the test sample was placed with its measuring side against a glass plate, and then a rubber pad and top platen were placed on the test sample, applying a pressure of (100. + -. 2) kPa and creating a vacuum of 50.66kPa in a large vacuum vessel. The time, expressed in seconds, required for the vacuum to drop from 50.66kPa to 48.00kPa was measured and recorded. Such as over 300s. The small volume is used instead and the test is retested with additional samples. If the time is less than 15s, the time required to reduce the vacuum from 50.66kPa to 29.33kPa is measured with additional samples. The time from the loading of the sample to the start of the timing should be about 60s.
Figure BDA0003402267070000122
Δ P — smoothness difference between two sides,%;
P big (a) -a greater smoothness measurement, S;
P small A less smooth measurement, S.
The specific experimental results are shown in the following table:
Figure BDA0003402267070000131
the comparison results show that: the paper surface sizing agent prepared by the UV curing process can restrict free movement of single fiber, so that surface wrinkles of paper are reduced, a cross-linked network structure can be formed after curing, compactness of a coating film is increased, smoothness of the paper surface is improved, and wet strength of the paper is improved. Without the UV curing process, the paper smoothness decreased significantly, the water absorption value CoBB increased, and the wet strength decreased, see comparative example 1.
After the organic functionalized dendritic nano-silica is replaced by the dendritic nano-silica which is not subjected to organic functionalization, the nano-silica which is not subjected to organic functionalization is extremely easy to agglomerate, and double bonds are not formed on the surface of the nano-silica, so that the nano-silica cannot participate in the photocuring reaction of the system, the UV curing time of the system is prolonged, the smoothness of the paper is reduced, and the mechanical properties (tensile index, burst index and folding strength) and the water resistance (CoBB rising and wet strength reducing) of the paper are reduced, as shown in a comparative example 2.
Compared with the commercially available nano-silica, the dendritic nano-silica prepared by the method has the advantages that a large number of carbon-carbon double bonds with photochemical activity are introduced into the surface of the dendritic nano-silica, so that the UV curing rate can be obviously improved, the internal stability with organic polymers can be enhanced, the dispersity is improved, the smoothness of paper is improved, and the mechanical properties (tensile index, burst index and folding strength) and the water resistance (CoBB reduction and wet strength increase) of the paper are improved, as shown in a comparative example 3.
The side chain of the acryloyl morpholine is a six-membered ring structure containing nitrogen and oxygen, when the acryloyl morpholine is applied to a UV curing paper surface sizing agent, a copolymer of the acryloyl morpholine has good adhesion, not only has rigidity, but also has certain flexibility, when the acryloyl morpholine is not used, the UV curing time is prolonged, the paper smoothness is reduced, and the mechanical properties (tensile index, bursting index and folding endurance) of the paper are reduced, as shown in a comparative example 4.
When only a single component photoinitiator, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinebenzyl) butanone, was used, the UV curing time was prolonged, the smoothness was reduced, the CoBB was increased, and the wet strength was reduced, as shown in comparative example 5.

Claims (5)

1. The UV-curing paper surface sizing agent is characterized by being prepared from the following components in parts by weight:
10-15 parts of organic functionalized dendritic nano silicon dioxide;
50-80 parts of polyester acrylate prepolymer;
20-30 parts of acryloyl morpholine;
20-40 parts of an active diluent;
1-4 parts of a photoinitiator;
wherein the organic functional dendritic nano-silica is dendritic porous nano-silica with the particle size of 100 to 200nm;
wherein the polyester acrylate prepolymer is acrylic acid-terminated terpolymer of adipic acid, diethylene glycol and maleic anhydride, and the structural formula of the terpolymer is as follows:
Figure 610684DEST_PATH_IMAGE001
wherein n is more than or equal to 4 and less than or equal to 8;
the polyester acrylate prepolymer is prepared from the following components in parts by weight:
30-40 parts of adipic acid;
80 to 90 parts of diethylene glycol;
30-40 parts of maleic anhydride;
60 to 70 parts of toluene;
25 to 30 parts of acrylic acid;
0.2 to 0.4 portion of catalyst;
0.01 to 0.02 portion of polymerization inhibitor;
the UV-curing paper surface sizing agent is prepared by the following steps:
1) Preparing organic functional dendritic nano silicon dioxide;
2) Preparing a polyester acrylate prepolymer;
3) Preparing a UV curing paper surface sizing agent: under the condition of room temperature, firstly adding 20-40 parts of active diluent, 20-30 parts of acryloyl morpholine and 50-80 parts of polyester acrylate prepolymer, starting stirring, controlling the rotating speed at 100-200 r/min, heating to 75-85 ℃, stirring for 20min, adding 10-15 parts of organic functional dendritic nano-silica, continuing stirring for 30-40 min, cooling to 48-52 ℃, adding 1-4 parts of photoinitiator, and stirring for 30-40 min to obtain a UV (ultraviolet) curing paper surface sizing agent;
the preparation method of the organic functionalized dendritic nano-silica comprises the following steps:
a. preparing dendritic nano silicon dioxide: adding 30.2-45.5 g of tetraethoxysilane and 60-80ml of absolute ethyl alcohol into the reactor A, keeping the temperature to 30-40 ℃, and fully stirring to form a solution; adding 70.5 to 80.8g of deionized water, 0.2 to 1.3g of template dodecyl benzyl trimethyl ammonium bromide and 0.5 to 2.6g of urea into a reactor B, fully stirring, and mixing with the solution in the reactor A to form reaction mother liquor; carrying out hydrothermal synthesis on the mother liquor in a homogeneous reactor, heating to 120-125 ℃, reacting for 4-5h, and stirring at 60r/min to obtain a stable white emulsion;
centrifugally separating the obtained white emulsion, washing the white emulsion for 3 times by using acetone and deionized water respectively, and drying the white emulsion at the temperature of 70 ℃ to obtain white powder; placing the white powder in a muffle furnace, heating to 500 ℃, calcining for 6 to 7h, and removing a template agent of dodecyl benzyl trimethyl ammonium bromide to obtain dendritic nano silicon dioxide;
b. organically functionalizing the dendritic nano silicon dioxide: dispersing 10.5-20.5 g of the dendritic nano silicon dioxide prepared in the step a in N, N-dimethylpropionamide, and performing ultrasonic dispersion for 20min to obtain a uniformly dispersed suspension; adding the suspension into a three-neck flask, slowly dripping 70.2-80.5 g of N, N-dimethylpropionamide, 70.2-80.5 g of toluene-2,4-diisocyanate and 5.5-10.6 g of dibutyltin dilaurate at the temperature of 70-80 ℃, reacting for 2-3 h, cooling to 45-55 ℃, adding 2.5-5 g of hydroquinone, and dripping a mixture of 70-80g of hydroxyethyl acrylate and 70-80g of N, N-dimethylpropionamide; after reacting for 2 to 3 hours, drying the product in a vacuum box at the drying temperature of 30 to 40 ℃, and fully grinding to obtain the organic functionalized dendritic nano-silica with the surface provided with the active double bonds;
the preparation method of the polyester acrylate prepolymer comprises the following steps:
adding 60 to 70 parts of toluene, 30 to 40 parts of adipic acid, 80 to 90 parts of diethylene glycol and 30 to 40 parts of maleic anhydride into a four-neck flask, adding 0.2 to 0.4 part of catalyst p-toluenesulfonic acid, heating under the protection of nitrogen, stirring at a stirring speed of 120r/min while heating to fully dissolve the components, heating to 125 to 135 ℃, refluxing for 2 to 3 hours, and distributing water, wherein the reaction equation is as follows:
Figure 159477DEST_PATH_IMAGE002
when the reaction temperature is reduced to 100 to 105 ℃, adding 25 to 30 parts of acrylic acid and 0.01 to 0.02 part of polymerization inhibitor hydroquinone, keeping the stirring speed at 120r/min, continuously heating, refluxing when the temperature is increased to 135 to 145 ℃, distributing water after refluxing for 2 to 3 hours until no water is distilled off, and cooling and discharging; washing the product with water to remove the catalyst p-toluenesulfonic acid, and removing toluene and unreacted acrylic acid by reduced pressure distillation to obtain the polyester acrylate prepolymer, wherein the reaction equation is as follows:
Figure 155508DEST_PATH_IMAGE003
2. a UV-curable paper surface sizing agent according to claim 1, characterized in that: the reactive diluent is a composition of tripropylene glycol diacrylate and ethoxylated trimethylolpropane triacrylate, and the mass ratio of the tripropylene glycol diacrylate to the ethoxylated trimethylolpropane triacrylate is 1 to 3.
3. A UV-curable paper surface sizing agent according to claim 1, wherein: the photoinitiator is as follows: 2-phenylbenzyl-2-dimethylamine-1- (4-morpholine benzyl phenyl) butanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, phenyl bis (2,4,6-trimethylbenzoyl) phosphine oxide, and one or more of 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone in any proportion.
4. The use of a UV-curable paper surface sizing agent according to claim 1 for surface sizing paper, wherein: and (3) applying glue on the surface of the paper by using a UV curing paper surface sizing agent by using a coating machine, and irradiating by using an ultraviolet curing machine to perform UV curing.
5. The use of a UV-curable paper surface sizing agent according to claim 4, wherein: the coating area of the coating machine on the surface of the paper is 0.8-1.4 g/m 2
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