CN111335069B - Impregnated paper and preparation method thereof - Google Patents

Impregnated paper and preparation method thereof Download PDF

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Publication number
CN111335069B
CN111335069B CN202010215724.3A CN202010215724A CN111335069B CN 111335069 B CN111335069 B CN 111335069B CN 202010215724 A CN202010215724 A CN 202010215724A CN 111335069 B CN111335069 B CN 111335069B
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net
glue
shadowless
melamine
adhesive
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CN111335069A (en
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黄建超
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Fujian Minqing Shuangleng Paper Co ltd
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Fujian Minqing Shuangleng Paper 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/33Synthetic macromolecular compounds
    • D21H17/46Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/47Condensation polymers of aldehydes or ketones
    • D21H17/49Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen
    • D21H17/51Triazines, e.g. melamine
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G12/00Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/26Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
    • C08G12/34Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds and acyclic or carbocyclic compounds
    • C08G12/36Ureas; Thioureas
    • C08G12/38Ureas; Thioureas and melamines
    • 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/33Synthetic macromolecular compounds
    • D21H17/46Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/52Epoxy resins
    • 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/33Synthetic macromolecular compounds
    • D21H17/46Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/57Polyureas; Polyurethanes

Abstract

The invention relates to the technical field of impregnated paper, and particularly discloses impregnated paper and a preparation method thereof, wherein the impregnated paper can be impregnated on two sides, and is sequentially provided with a raw paper layer, a shadowless adhesive net and a melamine adhesive layer from inside to outside; the raw paper layer is raw paper or balance paper; the shadowless glue net is composed of a fine cotton wire net or a silk wire net which is soaked with shadowless glue and then cured by ultraviolet irradiation and melamine glue, and the mesh density is 8-28 meshes; the melamine glue is mainly prepared by compounding melamine and formaldehyde. The impregnated paper has prestress through the tensioned shadowless adhesive net, is not only a pollution-free and volatile adhesive material, but also can improve the tensile strength and the shock resistance of the impregnated paper through the net, so that the paper is not easy to damage and deform.

Description

Impregnated paper and preparation method thereof
Technical Field
The invention relates to the technical field of impregnated paper, and particularly discloses impregnated paper and a preparation method thereof.
Background
The existing impregnated paper is basically prepared by mixing non-woven wood pulp, PE and plant fiber, has strong absorption force and dissolution resistance, is widely applied to veneers of cabinets, wardrobes and composite floors, is mostly prepared from raw paper layers, plain color layers and the like, has insufficient interlayer adhesive force, is easy to generate interlayer separation phenomenon, has low impact resistance and tensile resistance, is easy to cause the whole sheet of the impregnated paper to be partially damaged due to external impact force, even falls off from the cabinets, wardrobes and bottom plates in a large area, has short service life, and is difficult to achieve good hardness and flexibility.
Disclosure of Invention
The present invention is directed to a impregnated paper and a method for preparing the same, which solves the problems set forth above in the background art.
The technical scheme of the invention is as follows:
in order to achieve the purpose, the invention provides the following technical scheme: an impregnated paper characterized by: the impregnated paper can be impregnated on two sides, and is sequentially provided with a raw paper layer, a shadowless adhesive net and a melamine adhesive layer from inside to outside; the raw paper layer is raw paper or balance paper; the shadowless adhesive net consists of a fine cotton wire net or silk wire net which is soaked with shadowless adhesive and then cured by ultraviolet irradiation and melamine adhesive; the melamine glue is mainly prepared by compounding melamine and formaldehyde.
7. The shadowless adhesive formula used for the shadowless adhesive net comprises the following components in parts by weight: 40-60 parts of prepolymer, 20-40 parts of monomer, 4-8 parts of photoinitiator and 15-25 parts of curing agent.
Preferably, the formula of the shadowless adhesive also comprises 3-6 parts of heat-conducting filler; the prepolymer comprises epoxy acrylate and polyurethane acrylic resin in the ratio of (1; the monomer is one or more of isobornyl acrylate, tripropylene glycol diacrylate and trimethylolpropane triacrylate; the photoinitiator is 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO) or benzophenone; the heat conducting filler is carbon nano tube.
The fine cotton wire net or silk wire net used by the shadowless adhesive net is water-absorbing cotton wire or water-absorbing silk wire, the diameter is 0.08-0.13mm, and the mesh density is 8-28 meshes.
Preferably, the fine cotton wire net or silk wire net used for the shadowless adhesive net is made of superfine fibers and has the diameter of 0.10mm.
The shadowless adhesive net is prepared by the following method:
(1) Weighing the raw materials according to the weight percentage of the formula;
(2) Fully mixing epoxy acrylate and polyurethane acrylic resin at a stirring speed of 1000-1200r/min, then sequentially adding a monomer, a photoinitiator and a heat-conducting filler, stirring for 30-45min to obtain shadowless glue, and maintaining the stirring speed of a glue pool at 300-500r/min;
(3) And (3) fully soaking the fine cotton wire mesh or the silk wire mesh into a glue pool filled with the shadowless glue water in the step (2) and continuously stirring, taking out after 10-20min, unfolding and tensioning to obtain the shadowless glue net.
The melamine glue layer and the melamine glue filled in the shadowless glue net comprise the following raw materials in parts by weight: 5-10 parts of melamine, 15-30 parts of formaldehyde aqueous solution, 3-6 parts of p-toluenesulfonamide, 2-4 parts of curing agent, 2-4 parts of urea and 30-50 parts of water; the mass fraction of the formaldehyde aqueous solution is 37wt%; the curing agent is prepared from the following components in percentage by weight: hexamethylenetetramine: phthalic anhydride is 1 (1-1.5): (1.6-2.4).
The preparation method of the melamine adhesive layer and the melamine adhesive filled with the shadowless adhesive net comprises the following steps:
(1) Adding hexamethylenetetramine and phthalic anhydride into deionized water at 70-80 ℃, and stirring for 30-40min to obtain a curing agent;
(2) At the temperature of 35-40 ℃, adding melamine and urea into the stirred formaldehyde aqueous solution, heating to 80-90 ℃ within 45min while stirring, and then carrying out heat preservation reaction for 40-50min. Then cooling to 50-60 ℃ to prepare a mixture A;
(3) Adding p-toluenesulfonamide, nano alumina particles and water into the mixture A at 40-55 ℃, and stirring for 30-50min to obtain a mixture B;
(4) Before coating, adding the curing agent prepared in the step (1) into the mixture B, uniformly stirring to prepare the melamine-formaldehyde composite adhesive, and coating or dipping.
The preparation method of the impregnated paper comprises the following steps:
(1) Taking a raw paper layer, coating or completely dipping melamine-formaldehyde composite glue on the upper and lower surfaces of the raw paper layer, respectively pressing a tensioned shadowless glue net prepared in advance into the melamine-formaldehyde composite glue on the upper and lower surfaces of the raw paper layer, mechanically clamping the shadowless glue net on the upper and lower surfaces of the raw paper layer, scraping redundant melamine-formaldehyde composite glue on the surface of the shadowless glue net by using a scraper, drying the dipped paper by using a drying oven at 120-150 ℃, wherein the drying time is 30-60 seconds, the melamine-formaldehyde composite glue is preliminarily solidified and fixed on the shadowless glue net, then irradiating and curing the shadowless glue net for 3-8 minutes by using an ultraviolet lamp, and then drying and curing the undried melamine-formaldehyde composite glue in the drying oven at 120-150 ℃, so that a fixing clamp can be removed;
(2) Dipping the melamine-formaldehyde composite adhesive again, scraping the surface by using a scraper, and drying by using a drying oven at the temperature of 150-160 ℃ for 5-10 minutes;
(3) And cooling the impregnated paper to room temperature, and then cutting according to requirements and specifications.
The invention has the following beneficial effects:
compared with the prior art, the invention has the beneficial effects of good hardness and toughness and strong impact resistance:
1. the shadowless adhesive net is fixed on two sides of the raw paper layer after the shadowless adhesive is fully soaked by the water absorption cotton thread/the water absorption silk thread and is solidified by ultraviolet irradiation. On one hand, the water-absorbent cotton thread/water-absorbent silk thread net has the advantages that after the water-absorbent cotton thread/water-absorbent silk thread net fully absorbs the shadowless glue, the water-absorbent cotton thread/water-absorbent silk thread net is tensioned on four sides and respectively pressed into the well-coated melamine-formaldehyde composite glue from two sides of the paper, the shadowless glue net is primarily fixed through the temporary drying of the melamine-formaldehyde composite glue, the shadowless glue is fixed into the thread net through the full ultraviolet irradiation, and then the shadowless glue net and the melamine-formaldehyde composite glue form firm bonding through the complete drying. The base of the net layer is a tensioned net, so that the flexibility of the attached impregnated paper can be greatly improved under the condition of keeping tension, the impregnated paper is not easy to break, and meanwhile, the impact strength and the hardness of the impregnated paper can be enhanced by the net structure. On the other hand, the reason why the shadowless adhesive net covers the upper surface and the lower surface of the raw paper layer is that if the shadowless adhesive net only covers one side of the raw paper layer, the net is solidified under the condition of tensioning, so that the paper is easy to tilt from the edge to the center, the double-sided covering net not only can balance the tilting force of the edge tilting to the center, but also can obviously improve the tensile strength of the impregnated paper because the shadowless adhesive net is solidified under the condition of tensioning and has prestress.
2. The water-absorbing cotton thread/water-absorbing silk thread adsorbs the shadowless glue, and has the advantages of wide application range and excellent bonding effect on bonding of various materials such as plastics and the like; high adhesion strength, low temperature resistance, and high temperature and humidity resistance. The glue is stable and easy to store under the condition of no ultraviolet irradiation initiation, and the highest strength is achieved within a short time under the initiation of ultraviolet irradiation. On one hand, the melamine-formaldehyde composite adhesive can be well adhered and tightly fixed with melamine-formaldehyde composite adhesive filled into mesh holes of a shadowless adhesive net, after the shadowless adhesive is cured, the surface of the adhesive is in contact with air, and due to the inhibition effect of the air, the surface of the adhesive can not be debonded, and the adhesion degree of a melamine adhesive layer which is coated or impregnated subsequently can also be increased. On the other hand, the shadowless glue is a green, environment-friendly and economic chemical product, contains one hundred percent of solid content glue, has no VOC volatile matter, has no pollution to the ambient air, has low flammability, has no damage to the tension of the tensioned wire mesh while fixing the tensioned wire mesh, and does not produce any toxic, carcinogenic, pathogenic and denaturing hazards to human bodies while ensuring the lifting effect of the impregnated paper.
3. The formula of the shadowless adhesive is also added with a heat-conducting filler such as a carbon nano tube, so that the shadowless adhesive is high-temperature resistant and has excellent heat-conducting property. The advantages of the shadowless adhesive net are that the heat conductivity of the shadowless adhesive net is improved, heat is conducted fully when the oven is dried, and the heat can be uniformly transferred to the melamine-formaldehyde composite adhesive of the shadowless adhesive net and the glue of the melamine adhesive layer through the net-shaped structure, so that the shadowless adhesive net is fully solidified without dead angles.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Table 1 ratio table of different shadowless glue formulas
Figure BDA0002424341680000051
Shadowless adhesive net 1: (1) weighing raw materials according to the weight percentage of the formula in table 1;
(2) Fully mixing epoxy acrylate and polyurethane acrylic resin at a stirring speed of 1000r/min, then sequentially adding a monomer, a photoinitiator and a heat-conducting filler, stirring for 30min to obtain shadowless glue water, and maintaining the stirring speed of a glue pool at 300r/min;
(3) And (3) fully soaking a fine cotton wire mesh (made of common fibers, the diameter of the fine cotton wire mesh is 0.13mm, and the mesh density is 8 meshes) into a glue pool filled with the shadowless glue water in the step (2) and continuously stirring, taking out after 10min, unfolding and tensioning to obtain the shadowless glue mesh.
Shadowless glue net 2: (1) weighing the raw materials according to the weight percentage of the formula in the table 1;
(2) Fully mixing epoxy acrylate and polyurethane acrylic resin at a stirring speed of 1100r/min, then sequentially adding a monomer, a photoinitiator and a heat-conducting filler, stirring for 38min to obtain shadowless glue, and maintaining the stirring speed of a glue pool at 400r/min;
(3) And (3) fully soaking a fine cotton wire mesh (made of superfine fibers, the diameter of which is 0.10mm, and the mesh density of which is 18 meshes) into a glue pool filled with the shadowless glue water in the step (2) and continuously stirring, taking out after 15min, unfolding and tensioning to obtain the shadowless glue net.
Shadowless glue net 3: (1) weighing raw materials according to the weight percentage of the formula in table 1;
(2) Fully mixing epoxy acrylate and polyurethane acrylic resin at a stirring speed of 1200r/min, then sequentially adding a monomer, a photoinitiator and a heat-conducting filler, stirring for 45min to obtain shadowless glue water, and maintaining the stirring speed of a glue pool at 500r/min;
(3) And (3) fully soaking a fine cotton wire mesh (made of superfine fibers, the diameter of the fine cotton wire mesh is 0.08mm, and the mesh density is 28 meshes) into a glue pool filled with the shadowless glue water in the step (2) and continuously stirring, taking out after 20min, unfolding and tensioning to obtain the shadowless glue mesh.
A shadowless glue net 4: (1) weighing the raw materials according to the weight percentage of the formula in the table 1;
(2) Fully mixing epoxy acrylate and polyurethane acrylic resin at a stirring speed of 1100r/min, then sequentially adding a monomer and a photoinitiator, stirring for 38min to obtain shadowless glue water, and maintaining the stirring speed of a glue pool at 400r/min;
(3) And (3) fully soaking a fine cotton wire mesh (made of superfine fibers, the diameter of which is 0.10mm, and the mesh density of which is 18 meshes) into a glue pool filled with the shadowless glue water in the step (2) and continuously stirring, taking out after 15min, unfolding and tensioning to obtain the shadowless glue net.
Table 2 proportions of different melamine glue formulations
Figure BDA0002424341680000071
1, melamine glue: (1) Weighing the raw materials according to the weight percentage of the formula in the table 2, adding hexamethylenetetramine and phthalic anhydride (the proportion of ionized water: hexamethylenetetramine: phthalic anhydride is 1;
(2) At the temperature of 35 ℃, the melamine and the urea are added into the formaldehyde aqueous solution which is stirred, the temperature is raised to 80 ℃ within 45min while stirring, and then the temperature is preserved for reaction for 40min. Then cooling to 50 ℃ to obtain a mixture A;
(3) Adding p-toluenesulfonamide, nano alumina particles and water into the mixture A at 40 ℃, and stirring for 30min to prepare a mixture B;
(4) Before coating, adding the curing agent prepared in the step (1) into the mixture B, uniformly stirring to prepare the melamine-formaldehyde composite adhesive, and coating or dipping.
Melamine glue 2: (1) Weighing the raw materials according to the weight percentage of the formula in the table 2, adding hexamethylenetetramine and phthalic anhydride (the proportion of ionized water: hexamethylenetetramine: phthalic anhydride is 1.3;
(2) At 38 ℃, adding melamine and urea into the stirred formaldehyde aqueous solution, heating to 85 ℃ within 45min while stirring, and then carrying out heat preservation reaction for 45min. Then cooling to 55 ℃ to obtain a mixture A;
(3) Adding p-toluenesulfonamide, nano alumina particles and water into the mixture A at 50 ℃, and stirring for 40min to prepare a mixture B;
(4) Before coating, adding the curing agent prepared in the step (1) into the mixture B, uniformly stirring to prepare the melamine-formaldehyde composite adhesive, and coating or dipping.
Melamine adhesive 3: (1) Weighing the raw materials according to the weight percentage of the formula in the table 2, adding hexamethylenetetramine and phthalic anhydride (the proportion of ionized water: hexamethylenetetramine: phthalic anhydride is 1.5;
(2) At 40 ℃, adding melamine and urea into the stirred formaldehyde aqueous solution, heating to 90 ℃ within 45min while stirring, and then carrying out heat preservation reaction for 50min. Then cooling to 60 ℃ to obtain a mixture A;
(3) Adding p-toluenesulfonamide, nano alumina particles and water into the mixture A at 55 ℃, and stirring for 50min to prepare a mixture B;
(4) Before coating, adding the curing agent prepared in the step (1) into the mixture B, uniformly stirring to prepare the melamine-formaldehyde composite adhesive, and coating or dipping.
TABLE 3 materials for the formulations of the different examples and comparative examples
Figure BDA0002424341680000081
Figure BDA0002424341680000091
Example 1:
(1) Taking a raw paper layer, coating or completely dipping melamine-formaldehyde composite glue on the upper and lower surfaces of the raw paper layer, respectively pressing a tensioned shadowless glue net prepared in advance into the melamine-formaldehyde composite glue on the upper and lower surfaces of the raw paper layer, mechanically clamping the shadowless glue net on the upper and lower surfaces of the raw paper, scraping redundant melamine-formaldehyde composite glue on the surface of the shadowless glue net by using a scraper, drying the dipped paper by using a drying oven at 120 ℃, wherein the drying time is 30 seconds, the melamine-formaldehyde composite glue is preliminarily solidified and fixed on the shadowless glue net, then irradiating and curing the shadowless glue net by using an ultraviolet lamp for 3 minutes, and then drying and curing the undried melamine-formaldehyde composite glue in the drying oven at 120 ℃ by using the dipped paper, so that a fixing clamp can be removed;
(2) And dipping the melamine-formaldehyde composite adhesive again, scraping the surface by using a scraper, and drying by using a drying oven at the temperature of 150 ℃ for 5 minutes.
(3) The impregnated paper was cooled to room temperature and cut as required and specified to obtain the impregnated paper of example 1.
Example 2:
(1) Taking a raw paper layer, coating or completely dipping melamine-formaldehyde composite glue on the upper and lower surfaces of the raw paper layer, respectively pressing a tensioned shadowless glue net prepared in advance into the melamine-formaldehyde composite glue on the upper and lower surfaces of the raw paper layer, mechanically clamping the shadowless glue net on the upper and lower surfaces of the raw paper, scraping redundant melamine-formaldehyde composite glue on the surface of the shadowless glue net by using a scraper, drying the dipped paper by using a 135 ℃ drying oven for 45 seconds to enable the melamine-formaldehyde composite glue to be preliminarily solidified and fixed on the shadowless glue net, irradiating and curing the shadowless glue net by using an ultraviolet lamp for 6 minutes, and then drying and curing the undried melamine-formaldehyde composite glue in the 135 ℃ drying oven by using the dipped paper, so that a fixing clamp can be removed;
(2) Dipping the melamine-formaldehyde composite adhesive again, scraping the surface by using a scraper, and drying by using an oven at 155 ℃ for 8 minutes;
(3) And cooling the impregnated paper to room temperature, and then cutting according to requirements and specifications.
Example 3:
(1) Taking a raw paper layer, coating or completely dipping melamine-formaldehyde composite glue on the upper and lower surfaces of the raw paper layer, respectively pressing a tensioned shadowless glue net prepared in advance into the melamine-formaldehyde composite glue on the upper and lower surfaces of the raw paper layer, mechanically clamping the shadowless glue net on the upper and lower surfaces of the raw paper, scraping redundant melamine-formaldehyde composite glue on the surface of the shadowless glue net by using a scraper, drying the dipped paper by using a drying oven at 150 ℃, wherein the drying time is 60 seconds, the melamine-formaldehyde composite glue is preliminarily solidified and fixed on the shadowless glue net, then irradiating and curing the shadowless glue net by using an ultraviolet lamp for 8 minutes, and then drying and curing the undried melamine-formaldehyde composite glue in the drying oven at 150 ℃ by using the dipped paper, so that a fixing clamp can be removed;
(2) Dipping the melamine-formaldehyde composite adhesive again, scraping the surface by using a scraper, and drying by using a drying oven at 160 ℃ for 10 minutes;
(3) And cooling the impregnated paper to room temperature, and then cutting according to requirements and specifications.
Examples 4-5, comparative example the preparation method used was the same as in example 2.
And (3) performance test aspect: impregnated papers were prepared according to the methods of examples 1 to 5 and comparative examples, and the properties of the impregnated papers thus prepared were measured according to the following methods, and the results are shown in Table 4:
1. and (3) impact resistance: setting blank artificial board set of 300.0 × 180.0 size without impregnated paper, setting 3 pieces of impregnated paper of 300.0 × 180.0 size cut in each set, and compounding the paper on the same artificial board to make 3 standard partsA cushion layer (made of foam polyethylene, the breadth is 300 multiplied by 300mm, the thickness is 2.5 +/-0.2 mm, and the surface density is 75g/m 2 ) The sample was placed on a smooth floor in a horizontal position, the impregnated paper was placed on the mat with the paper facing up, and a blue copy paper was placed on the decorative surface of the sample. The steel ball (diameter 42.8 +/-0.2 mm, mass 324.0 +/-5.0 g, smooth spherical surface, no concave damage, rust spot and other defects) is dropped freely from the height of 1.75m to impact the surface of the test piece (to prevent the steel ball from jumping repeatedly on the surface of the test piece), each test piece is tested only once, and the dropping point of the steel ball is within 2.5mm from the center point of the test piece. The diameter of the pit was measured to 0.1mm with a vernier caliper.
Tensile strength properties: a blank set was set without using a shadowless adhesive net to impregnate only two layers of melamine-formaldehyde composite adhesive of the same thickness, 3 pieces of impregnated paper samples were set for each of the examples and the comparative examples, and the tensile strength of the paper was measured by a tensile strength tester.
Table 4 results of performance tests of examples 1 to 5, comparative example and blank group
Figure BDA0002424341680000111
From the experimental results in table 4 we can see that:
in combination with the comparison of the blank, control and examples 1-5, we can find that the addition of the shadowless adhesive web provides a significant improvement in tensile strength (toughness) and impact resistance (hardness) of the impregnated paper, and in particular, the effect of the application of a tensioned shadowless adhesive web on both sides of the impregnated paper on the performance enhancement of the impregnated paper is verified from the comparison of the control and blank. In these cases, the best performance is example 3 followed by example 4, and the performance is not much different from that of example 3, and the best suitable production example can be determined according to the actual demand for impregnated paper and the cost. In addition, the melamine glue layer can also be added with wear-resistant components, high-gloss components, green and environment-friendly aldehyde-removing components and the like, or the melamine glue layer is dipped and coated with other functional and decorative coatings.
Comparing the comparative example with example 2, it can be seen that the addition of the heat conductive filler (carbon nanotubes) in the shadowless glue formulation significantly improves the impact resistance and tensile strength of the impregnated paper by sufficient heat conduction.
Comparing examples 1-3, it can be seen that the impact resistance and tensile strength of the prepared impregnated paper are gradually increased, and considering from the shadowless adhesive net, on one hand, compared with the common fiber, the base net of the shadowless adhesive net has stronger water absorption and toughness of the superfine fiber, and can absorb more shadowless adhesive to make the net tougher and firmer; on the other hand, the mesh density of the shadowless adhesive net also influences the strength and toughness of the adhesive net, and the denser mesh can improve the impact resistance and tensile strength of the prepared impregnated paper.
Compared with examples 2-5, it can be found that under the condition that the shadowless adhesive net is the same, the melamine-formaldehyde composite adhesive used by the shadowless adhesive net and the melamine adhesive layer have different formulas, and have influence on the performance of the prepared impregnated paper, but the influence is smaller compared with the shadowless adhesive net, which indicates that if a higher-quality impregnating coating formula is used, the strength and toughness of the impregnated paper can be better improved, and the further improvement can be performed according to actual needs.

Claims (7)

1. A preparation method of impregnated paper is characterized by comprising the following steps: the method comprises the following steps:
(1) Taking a raw paper layer, wherein the raw paper layer is raw paper; after the melamine-formaldehyde composite glue is coated or completely impregnated on the upper surface and the lower surface of the raw paper layer, tensioned shadowless glue nets prepared in advance are respectively pressed into the melamine-formaldehyde composite glue on the upper surface and the lower surface of the raw paper layer, the shadowless glue nets on the upper surface and the lower surface are fixed by being clamped around the raw paper by a machine, and each shadowless glue net comprises a fine cotton net or a silk thread net soaked with the shadowless glue; scraping redundant melamine-formaldehyde composite glue on the surface of the shadowless adhesive net by using a scraper, drying the impregnated paper by using a drying oven at 120-150 ℃, wherein the drying time is 30-60 seconds, so that the melamine-formaldehyde composite glue is preliminarily solidified and fixed on the shadowless adhesive net, irradiating and curing the shadowless adhesive net for 3-8 minutes by using an ultraviolet lamp, then drying and curing the undried melamine-formaldehyde composite glue in the drying oven at 120-150 ℃, and removing a fixing clamp;
(2) Dipping the melamine-formaldehyde composite adhesive again, scraping the surface by using a scraper, and drying by using a drying oven at the temperature of 150-160 ℃ for 5-10 minutes;
(3) Cooling the impregnated paper to room temperature, and then cutting according to requirements and specifications;
the shadowless adhesive formula used for the shadowless adhesive net comprises the following components in parts by weight: 40-60 parts of prepolymer, 20-40 parts of monomer, 4-8 parts of photoinitiator and 15-25 parts of curing agent; the formula of the shadowless adhesive also comprises 3-6 parts of heat-conducting filler; the prepolymer comprises epoxy acrylate and polyurethane acrylic resin in the ratio of (1; the monomer is one or more of isobornyl acrylate, tripropylene glycol diacrylate and trimethylolpropane triacrylate; the photoinitiator is 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO) or benzophenone; the heat conducting filler is carbon nano tube.
2. An impregnated paper produced by the method according to claim 1, wherein: the impregnated paper is impregnated on both sides and comprises a raw paper layer and melamine glue layers attached to both sides of the raw paper layer; the raw paper layer is raw paper; a shadowless adhesive net is embedded in the melamine adhesive layer; the shadowless adhesive net comprises a fine cotton wire net or a silk wire net which is soaked with shadowless adhesive and then cured by ultraviolet irradiation.
3. Impregnated paper according to claim 2, characterized in that: the fine cotton wire net or silk wire net used by the shadowless adhesive net is water-absorbing cotton wire or water-absorbing silk wire, the diameter is 0.08-0.13mm, and the mesh density is 8-28 meshes.
4. Impregnated paper according to claim 2, characterized in that: the fine cotton wire net or silk wire net used by the shadowless adhesive net is made of superfine fibers, and the diameter of the fine cotton wire net or silk wire net is 0.10mm.
5. Impregnated paper according to claim 2, characterized in that: the shadowless glue net is prepared by the following method:
(1) Weighing the raw materials according to the weight percentage of the formula;
(2) Fully mixing epoxy acrylate and polyurethane acrylic resin at a stirring speed of 1000-1200r/min, then sequentially adding a monomer, a photoinitiator and a heat-conducting filler, stirring for 30-45min to obtain shadowless glue, and maintaining the stirring speed of a glue pool at 300-500r/min;
(3) And (3) fully soaking the fine cotton wire mesh or the silk wire mesh in a glue pool filled with the shadowless glue water obtained in the step (2), taking out after 10-20min, unfolding and tensioning to obtain the shadowless glue net.
6. Impregnated paper according to claim 2, characterized in that: the melamine glue layer comprises the following raw materials in parts by weight: 5-10 parts of melamine, 15-30 parts of formaldehyde aqueous solution, 3-6 parts of p-toluenesulfonamide, 2-4 parts of curing agent, 2-4 parts of urea and 30-50 parts of water; the mass fraction of the formaldehyde aqueous solution is 37wt%; the curing agent is prepared from the following components in percentage by weight: hexamethylenetetramine: phthalic anhydride is 1 (1-1.5): (1.6-2.4).
7. Impregnated paper according to claim 6, characterized in that: the preparation method of the melamine glue layer comprises the following steps:
(1) Adding hexamethylenetetramine and phthalic anhydride into deionized water at 70-80 ℃, and stirring for 30-40min to obtain a curing agent;
(2) At the temperature of 35-40 ℃, adding melamine and urea into the stirred formaldehyde aqueous solution, heating to 80-90 ℃ within 45min while stirring, then carrying out heat preservation reaction for 40-50min, and then cooling to 50-60 ℃ to obtain a mixture A;
(3) Adding p-toluenesulfonamide, nano alumina particles and water into the mixture A at 40-55 ℃, and stirring for 30-50min to obtain a mixture B;
(4) Before coating, adding the curing agent prepared in the step (1) into the mixture B, uniformly stirring to prepare the melamine-formaldehyde composite adhesive, and coating or dipping.
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CN115008558B (en) * 2022-05-16 2023-05-26 东莞市惠乔力装饰材料有限公司 Plate bending process with bending structure and composite plate manufactured by plate bending process
CN115182201B (en) * 2022-06-16 2023-04-07 东莞市高益装饰材料有限公司 Silver powder impregnated paper and production process thereof
CN116005485B (en) * 2022-12-29 2024-02-13 福建省闽清双棱纸业有限公司 High-strength impregnated paper and preparation method thereof

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CN103952948A (en) * 2014-04-28 2014-07-30 陕西师范大学 Environment-friendly low-cost method for reinforcing fragile paper by using cotton fiber silk screen
CN106497469A (en) * 2016-09-09 2017-03-15 南京林业大学 Immersion-type high heat conducting nano fluid adhesive, preparation method and its application in wood-based plate decoration
CN106564263A (en) * 2016-10-28 2017-04-19 浙江欧仁新材料有限公司 Ultrasonic fusion film and preparation method thereof
CN109306246A (en) * 2018-10-11 2019-02-05 广东福美新材料科技有限公司 A kind of shock proof automatically cleaning impregnated paper and preparation method thereof

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CN106497469A (en) * 2016-09-09 2017-03-15 南京林业大学 Immersion-type high heat conducting nano fluid adhesive, preparation method and its application in wood-based plate decoration
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