CN115450068A - Non-formaldehyde facing paper solidified by electron beam and preparation method and application thereof - Google Patents
Non-formaldehyde facing paper solidified by electron beam and preparation method and application thereof Download PDFInfo
- Publication number
- CN115450068A CN115450068A CN202211212524.8A CN202211212524A CN115450068A CN 115450068 A CN115450068 A CN 115450068A CN 202211212524 A CN202211212524 A CN 202211212524A CN 115450068 A CN115450068 A CN 115450068A
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- Prior art keywords
- aldehyde
- free
- catalyst
- polyurethane
- product
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Images
Classifications
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- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
- D21H27/18—Paper- or board-based structures for surface covering
- D21H27/22—Structures being applied on the surface by special manufacturing processes, e.g. in presses
- D21H27/26—Structures being applied on the surface by special manufacturing processes, e.g. in presses characterised by the overlay sheet or the top layers of the structures
- D21H27/28—Structures being applied on the surface by special manufacturing processes, e.g. in presses characterised by the overlay sheet or the top layers of the structures treated to obtain specific resistance properties, e.g. against wear or weather
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The invention discloses an aldehyde-free facing paper cured by electron beams, a preparation method and application thereof, wherein polyurethane is used as a soaking aldehyde-free impregnating resin, polypropylene epoxy resin is used as a back gluing adhesive, polyacrylate is used as surface coating oil, the surface coating oil is tightly combined with the soaking aldehyde-free impregnating resin through a bridging layer, the adhesive force of the surface coating oil on the facing paper soaked with the soaking resin is improved, and then the surface coating oil is cured on the facing paper by Electron Beams (EB) to realize the preparation of the facing paper without formaldehyde addition. EB solidification has the characteristics of high performance, high efficiency, low temperature and low cost, resin is completely solidified due to high energy output in the solidification process, and facing decorative paper without formaldehyde addition is high in environmental protection value due to the adoption of EB solidification, so that the requirement of high-quality development is met.
Description
Technical Field
The invention belongs to the technical field of decorative paper, and particularly relates to formaldehyde-free decorative paper cured by electron beams, and a preparation method and application thereof.
Background
The decorative paper is an artificial board facing material widely applied, and the facing paper occupies the half-wall Jiangshan of the decorative paper. When the facing artificial board is produced, base papers with different quantitative and different colors are impregnated with different kinds of resin adhesives to produce facing paper, and the facing paper is pressed on the artificial board to endow the artificial board with rich colors, attractive and fashionable visual effects, and endow the artificial board with various performances such as scratch resistance, wear resistance, cold and heat cycle resistance, cigarette burning resistance, pollution corrosion resistance and the like. The decorative veneer paper has obvious protection effect on the artificial board, and is widely applied to the indoor decoration fields of customized furniture, floors, wallboards and the like.
Currently, the most widely used face paper impregnating resins in the market are mainly the three-aldehyde glue, i.e. phenolic resin, urea-formaldehyde resin and melamine-formaldehyde resin. In actual production, the three-aldehyde glue impregnated facing paper is generally prepared by adopting a two-section impregnation process, and is pressed and adhered to the surface of the artificial board in a high-temperature hot pressing mode. However, this conventional approach to finishing releases free formaldehyde during the manufacture and use of the impregnated facing paper. Formaldehyde is volatile when being heated, and free formaldehyde can volatilize when high temperature production and hot pressing are used, and then causes the harm to the practitioner of gumming mill, clamp plate factory and customized house manufacturing factory or even consumer. Formaldehyde is colorless gas with special pungent smell at normal temperature, is one of raw stock poisons, and can denature cells of partial organs of a human body. The gaseous formaldehyde has strong stimulation effect on the mucous membrane of the respiratory tract, and can cause serious pathological changes of the respiratory tract after excessive formaldehyde gas is inhaled; the formaldehyde is easy to dissolve in water, and the water solution of the formaldehyde can be combined with protein in a human body to destroy the structure of the protein; the skin directly contacts with formaldehyde to cause symptoms such as dermatitis, color spots, skin necrosis and the like; long term exposure to low doses (less than 0.1 mg/m) 3 ) Formaldehyde can cause chronic diseasesRespiratory diseases, colon cancer, nasopharyngeal carcinoma, gene mutation of cell nucleus, etc.
Along with the improvement of the requirements of people on indoor environment and the emergence of relevant national environmental laws and regulations, the formaldehyde-free artificial board products with the impregnated bond paper veneer are urgent, so that the development of the veneer paper and the artificial board without formaldehyde release is very important.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. The invention provides the formaldehyde-free facing paper cured by the electron beam and the preparation method and the application thereof, polyurethane is adopted as one-step formaldehyde-free impregnating resin, polypropylene epoxy resin is adopted as a back coating adhesive, polyacrylate is adopted as surface coating oil, the surface coating oil is tightly combined with the one-step formaldehyde-free impregnating resin through a bridging layer, the adhesion force of the surface coating oil on the facing paper impregnated with the one-step resin is improved, and then the surface coating oil is cured on the facing paper by the Electron Beam (EB) to realize the preparation of the facing paper without formaldehyde addition. Compared with the traditional urea-formaldehyde resin and melamine resin, formaldehyde is not released when no formaldehyde resin is impregnated, and the paper has strong toughness before curing and is beneficial to rolling and transportation. Meanwhile, EB curing has the characteristics of high performance, high efficiency, low temperature and low cost, and high energy output in the curing process enables resin curing to be more complete. Therefore, the veneer decorative paper without formaldehyde addition is solidified by EB, has high environmental protection value and simple operation, meets the requirement of high-quality development, and has promising future prospect.
According to one aspect of the invention, the invention provides aldehyde-free facing paper solidified by electron beams, which comprises a back coating, a first polyurethane aldehyde-free resin layer, base paper, a second polyurethane aldehyde-free resin layer, a bridging layer and a surface gloss oil coating layer from bottom to top in sequence;
the back coating is made of polypropylene epoxy resin, and the preparation raw materials of the back coating comprise: bisphenol A epoxy resin, methacrylic acid, acrylic acid, acrylate, an organic solvent, isocyanate, a first catalyst, a second catalyst, a first active agent, a coupling agent, a first initiator, a first polymerization inhibitor and water;
the first polyurethane aldehyde-free resin layer and the second polyurethane aldehyde-free resin layer are made of waterborne polyurethane, and the preparation raw materials comprise: isocyanate, polyester polyol, an alcohol chain extender, an acrylic acid active monomer, a third catalyst, a neutralizer, a second initiator and water;
the preparation raw materials of the bridging layer comprise: chlorinated polypropylene resin, acrylic ester, chlorinated polyethylene, guar gum, organic amine, titanate, epoxy silane and alcohol substances;
the material of the surface-coated oil layer is polyacrylate, and the preparation raw materials comprise: aliphatic epoxy resin, acrylic acid, acrylic ester, trimellitic anhydride, ethylene glycol, a fourth catalyst, a fifth catalyst, a second polymerization inhibitor, a second activator and water.
In some embodiments of the invention, the base paper has a basis weight of 70 to 150g/m 2 Plain paper or printing pattern paper.
In some embodiments of the invention, the first catalyst is at least one of tetrabutylammonium bromide or tetrabutylammonium chloride.
In some embodiments of the invention, the second catalyst is at least one of dibutyl tin dilaurate or stannous octoate.
In some embodiments of the invention, the third catalyst is at least one of N, N-dimethylcyclohexylamine or N-methyldicyclohexylamine.
In some embodiments of the invention, the fourth catalyst is at least one of tetramethylammonium chloride, tetramethylpropylenediamine, or N, N-dimethyl (hexadecyl) amine.
In some embodiments of the invention, the fifth catalyst is at least one of zinc chloride, potassium acetate, or tetrabutyl titanate.
In some embodiments of the invention, the first active agent is at least one of polyethylene glycol 400 or polyethylene glycol 800.
In some embodiments of the invention, the second active agent is at least one of a polyethylene glycol octylphenyl ether or a bis (dimethylaminoethyl) glycol ether.
In some embodiments of the invention, the first polymerization inhibitor is at least one of polyethylene glycol octylphenyl ether or p-hydroxyanisole.
In some embodiments of the invention, the second polymerization inhibitor is at least one of hydroquinone or 2, 6-di-tert-butyl-p-cresol.
In some embodiments of the invention, the coupling agent is at least one of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, anilinomethyltriethoxysilane, or gamma-glycidoxypropyltrimethoxysilane.
In some embodiments of the invention, the first initiator is at least one of ammonium persulfate or peroxydicarbonate.
In some embodiments of the invention, the second initiator is at least one of azobisisobutyronitrile or azobisisoheptonitrile.
In some embodiments of the invention, the isocyanate is at least one of isophorone diisocyanate, dicyclohexylmethane diisocyanate, or methylcyclohexyl diisocyanate. Preferably, the isocyanate selected for the back coating is isophorone diisocyanate.
In some embodiments of the invention, the polyester polyol is at least one of a polycarbonate diol or a polycaprolactone diol. Preferably, the molecular weight of the polyester polyol is 300-4000, and further preferably, the polyester polyol is polycaprolactone diol with the molecular weight of 500-1000 or polycarbonate diol with the molecular weight of 500-1000.
In some embodiments of the invention, the alcoholic chain extender is at least one of ethylene glycol, 1, 4-butanediol, or 1,2, 6-hexanetriol.
In some embodiments of the invention, the acrylic reactive monomer is at least one of methyl methacrylate or butyl acrylate. Preferably, the acrylic reactive monomer is present in a weight ratio (0.3-0.6): 1 of methyl methacrylate and butyl acrylate.
In some embodiments of the invention, the neutralizing agent is at least one of triethylamine or triethanolamine.
In some embodiments of the invention, the titanate is of the monoalkoxy type.
In some embodiments of the invention, the organic amine is monoethanolamine, monoisopropanolamine and N, N-dimethylethanolamine. Preferably, the weight ratio of monoethanolamine, monoisopropanolamine and N, N-dimethylethanolamine is 1: (0.5-1): (0.5-1).
In some embodiments of the invention, the alcohol is polyethylene glycol 200 and polyethylene glycol 800. Preferably, the weight ratio of the polyethylene glycol 200 to the polyethylene glycol 800 is 1: (0.5-1). The alcohol substance functions as a binder in the crosslinking layer, and polyethylene glycol 200 and polyethylene glycol 800 are preferable from the viewpoints of water solubility, viscosity, and price.
In some embodiments of the invention, the chlorinated polypropylene resin has a chlorine content of 20 to 40% and a viscosity of 250 to 650 mPa-s.
In some embodiments of the invention, the chlorinated polyethylene has a chlorine content of 20 to 40% and a surface density of 0.5 ± 0.1g/cm 3 。
In some embodiments of the invention, the acrylate is at least one of methyl methacrylate, ethyl methacrylate, or butyl acrylate. Preferably, the back coating layer is selected from the acrylate butyl acrylate. Preferably, the acrylate selected for the bridging layer is butyl acrylate. Preferably, the acrylic ester selected by the top-coating gloss oil layer is in a mass ratio of 1: (1-1.3): (1-1.3) methyl methacrylate, ethyl methacrylate and butyl acrylate.
In some embodiments of the present invention, the polypropylene epoxy resin is prepared from the following raw materials in percentage by weight: 25-35% of bisphenol A epoxy resin, 5-10% of methacrylic acid, 15-25% of acrylic acid, 5-10% of acrylate, 10-20% of organic solvent, 10-15% of isocyanate, 0.1-1% of first catalyst, 0.08-0.25% of second catalyst, 0.5-2% of first active agent, 2-5% of coupling agent, 1-5% of first initiator, 0.8-2% of first polymerization inhibitor and 5-30% of water. Further, the organic solvent is 5-10% of diethyl ether and 5-10% of tetrahydrofuran.
In some embodiments of the invention, the polypropylene epoxy resin is prepared by the following method: (1) Dripping a tetrahydrofuran aqueous solution dissolved with a first catalyst and part of a first polymerization inhibitor into a mixture of bisphenol A epoxy resin and methacrylic acid, and heating for reaction to obtain a product A; (2) Mixing the product A, acrylic acid, acrylate, an organic solvent, an initiator and an activator, and reacting in an ice salt bath to obtain a product B; (3) And under 40-50 water bath, adding a coupling agent solution into a mixture of isocyanate, an organic solvent, a second catalyst and the rest of the first polymerization inhibitor for reaction to obtain a product C, and then mixing and stirring the product B and the product C with water to obtain the catalyst. Further, in the step (1), the heating reaction temperature is 85-95 ℃, and the reaction time is 1.5-2.5h. Further, in the step (2), the organic solvent is diethyl ether. Further, in the step (2), the temperature of the ice salt bath is-15 to 0 ℃. Further, in the step (3), the temperature for mixing and stirring the product B and the product C with water is 40-45 ℃; the organic solvent in the step (3) is tetrahydrofuran.
In some embodiments of the present invention, the raw materials for preparing the waterborne polyurethane comprise the following weight percentages: 26-35% of isocyanate, 28-38% of polyester polyol, 1-3% of alcohol chain extender, 5-10% of acrylic acid active monomer, 0.1-1% of third catalyst, 0.5-1% of neutralizer, 1-3% of second initiator and 20-40% of water.
In some embodiments of the invention, the aqueous polyurethane is prepared by: (1) Mixing isocyanate, polyester polyol and an alcohol chain extender, adding a third catalyst under a protective atmosphere, and heating for reaction to obtain a product D; (2) And adding the acrylic acid active monomer, the second initiator and the neutralizing agent into the product D, heating and stirring for a period of time, adding water and stirring to obtain the acrylic acid active monomer. Further, in the step (1), the heating reaction temperature is 80-90 ℃, and the reaction time is 1.5-2.5h. Further, in the step (2), the acrylic acid active monomer, the second initiator and the neutralizing agent are added into the product D, the mixture is heated to 45-55 ℃ and stirred for 15-25min, and then water is added and stirred for 1.5-2.5h.
In some embodiments of the present invention, the bridging layer is prepared from the following raw materials in percentage by weight: 25-35% of chlorinated polypropylene resin, 15-20% of acrylate, 5-10% of chlorinated polyethylene, 5-10% of guar gum, 1-5% of organic amine, 5-10% of titanate, 5-10% of epoxy silane and 20-35% of alcohol substance.
In some embodiments of the present invention, the material of the bridging layer is prepared by the following method: (1) Mixing alcohol substances, acrylate and chlorinated polyethylene, heating and preserving heat for a period of time under a protective atmosphere, and then adding organic amine, titanate and epoxy silane for reaction; (2) Adding chlorinated polypropylene resin for continuous reaction, adding guar gum under stirring, and keeping the temperature for a period of time to obtain the guar gum. Further, in the step (1), heating to 55-65 ℃ in a protective atmosphere, preserving heat for 25-35min, and then adding organic amine, titanate and epoxy silane for reaction for 0.5-1.5h. Further, in the step (2), the temperature of adding the chlorinated polypropylene resin for reaction is 85-95 ℃, the reaction time is 0.5-1.5h, and the heat preservation time of adding the guar gum is 0.5-1.5h.
In some embodiments of the present invention, the raw materials for preparing the polyacrylate are calculated by the following weight percentages: 15-25% of aliphatic epoxy resin, 25-40% of acrylic acid, 10-20% of acrylate, 10-15% of trimellitic anhydride, 5-10% of ethylene glycol, 0.05-0.15% of fourth catalyst, 0.05-0.15% of fifth catalyst, 0.1-0.5% of second polymerization inhibitor, 1-2% of second active agent and 20-35% of water.
In some embodiments of the invention, the polyacrylate is prepared by the following method: (1) Under the conditions of protective atmosphere and heating, adding a mixed solution of partial acrylic acid, acrylic ester, a fourth catalyst and partial second polymerization inhibitor into the aliphatic epoxy resin for reaction to obtain a product E; (2) Mixing trimellitic anhydride and ethylene glycol, heating for reaction, cooling, adding a fifth catalyst, a second active agent, the rest of a second polymerization inhibitor and the rest of acrylic acid, and heating for reaction to obtain a product F; and (3) mixing and stirring the product E, the product F and water to obtain the catalyst. Further, in the step (1), the temperature of the reaction is 115-125 ℃. Further, in the step (2), the heating reaction temperature is 170-190 ℃, and the reaction time is 0.5-1.5h; the temperature for reducing the temperature is 75-85 ℃; the temperature of the temperature rise reaction is 115-125 ℃. Further, in the step (3), the temperature for mixing and stirring the product E, the product F and water is 45-55 ℃.
The invention also provides a preparation method of the aldehyde-free facing paper cured by adopting the electron beams, which comprises the following steps:
s1: dipping the base paper by using the waterborne polyurethane, heating and drying the base paper, and forming a first polyurethane aldehyde-free resin layer and a second polyurethane aldehyde-free resin layer on the upper surface and the lower surface of the base paper;
s2: coating the polypropylene epoxy resin on the first polyurethane formaldehyde-free resin layer, and heating and drying to form a back coating;
s3: and coating a bridging layer material on the second polyurethane formaldehyde-free resin layer, coating a gloss oil layer material on the second polyurethane formaldehyde-free resin layer, and then performing electron beam curing treatment to obtain the formaldehyde-free facing paper cured by electron beams.
The electron Beam curing treatment is an advanced material surface treatment technology which takes an Electron Beam (EB) as a radiation source (EB is the abbreviation of electron Beam Electronic Beam) and induces a specially configured reactive liquid to be rapidly transformed into a solid.
In some embodiments of the present invention, in step S1, the sizing amount of the aqueous polyurethane is 60-90g/m 2 . The amount of sizing here is the total amount of sizing on both sides.
In some embodiments of the present invention, in step S2, the sizing amount of the polypropylene epoxy resin is 25-50g/m 2 。
In some embodiments of the invention, in step S3, the amount of the bridging layer material applied is 1-5g/m 2 。
In some embodiments of the invention, in step S3, the amount of the topcoat gloss-coat material applied is 20 to 45g/m 2 。
In some embodiments of the present invention, in step S3, the conditions of the electron beam curing process are: voltage 90-110kV, radiation energy 40-100kGy, and oxygen content less than 200ppm.
The invention also provides an aldehyde-free veneer, which comprises a substrate plate and the aldehyde-free veneer paper, wherein the aldehyde-free veneer paper is attached to the substrate plate, and the back coating of the aldehyde-free veneer paper is in contact with the substrate plate.
In some embodiments of the present invention, the aldehyde-free veneer is produced by the following method: and pressing the aldehyde-free facing paper onto the base material plate in a hot pressing mode to obtain the aldehyde-free facing paper. Further, the hot pressing temperature is 120-150 ℃, the pressure is 10-15MPa, and the time is 10-20s.
According to a preferred embodiment of the present invention, at least the following advantages are provided:
1. the invention provides a novel aldehyde-free added decorative paper capable of being cured by Electron Beams (EB), wherein a back coating material, a resin dipping material and surface coating oil used by the decorative paper do not contain harmful components such as formaldehyde, and the like, replaces the traditional phenolic resin, urea resin and melamine formaldehyde resin, avoids the release of harmful substances of the decorative paper from the source, meets the requirements of consumers on environment protection, and is beneficial to high-value utilization of the decorative paper.
2. The back coating material of the invention has epoxy group, carbon-carbon double bond and hydroxyl group, and can be combined with the double bond and hydrogen bond of the polyurethane formaldehyde-free resin layer, thereby improving the bonding strength of back coating glue and gum dipping; meanwhile, carbon-carbon double bonds and hydroxyl groups of the back coating material can be combined with hydroxyl groups and amino groups in the substrate plate, so that the back glue can be crosslinked and cured with the substrate surface glue, the adhesive force of the back coating material on the substrate is enhanced, and the decorative paper can be firmly adhered to the substrate surface.
3. The resin matching system of the invention selects a special bridging layer and surface gloss oil, the bridging layer mainly plays a role of a coupling agent and a cross-linking agent, and the surface gloss oil and the polyurethane formaldehyde-free resin layer are firmly combined together by using unsaturated carbon-carbon double bonds and reactive groups in the material, so that the adhesion capability of the surface gloss oil is improved. The prepared decorative paper adopts an Electron Beam (EB) curing mode with high performance, high efficiency, low temperature and low cost, resin is cured more completely by high energy output in the curing process, the curing degree reaches 100%, energy is saved, the production efficiency is improved, and the decorative paper is worthy of popularization and use.
4. According to the prepared aldehyde-free added decorative paper capable of being cured by using the Electron Beam (EB), due to the particularity of an adhesive system, adhesive composition substances can permeate into paper, adhesive micromolecules permeating into the paper have a large number of hydroxyl groups, hydrogen bonds are formed between the hydroxyl groups and the hydroxyl groups on fibers in the paper, and the internal bonding force between the paper fibers is filled, so that the paper is high in overall toughness, can be rolled and stored, does not have the defect that the adhesive film paper prepared by using the traditional formaldehyde-free adhesive is extremely fragile, and is convenient to store and transport.
5. Unsaturated carbon-carbon double bonds in the surface coating gloss oil material can perform crosslinking reaction with unsaturated groups of the bridging layer, so that the self adhesive capacity is improved. And secondly, main polyacrylate of the surface-coated gloss oil belongs to an elastic high polymer material, can have good hydrophobic and oleophobic properties after being modified by acrylate and trimellitic anhydride, and endows the surface of the decorative paper with good hydrophobic and oleophobic effects after EB (Electron beam) curing, so that the water contact angle can reach more than 90 degrees, and finally the effects of fingerprint resistance and oil stain resistance are achieved.
Drawings
The invention is further described with reference to the following figures and examples, in which:
FIG. 1 is a schematic view of the process for preparing the aldehyde-free veneer according to the present invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Table 1 preparation of non-aldehyde face paper for examples 1-5 and comparative example 1 raw material composition
Note: comparative example 1 differs from example 5 in table 1 in that the ratio of aliphatic ERL-4221 to acrylic acid in the top-coated varnish starting material of comparative example 1 differs from example 5.
Examples 1-5 and comparative example 1 an aldehyde-free facing paper was prepared by weighing the components in the amounts specified in table 1, and sequentially comprising, from bottom to top, a back coating layer, a first polyurethane aldehyde-free resin layer, a base paper, a second polyurethane aldehyde-free resin layer, a bridging layer, and a top gloss oil layer. Referring to fig. 1, the specific preparation steps are as follows:
s1: preparing a polyurethane formaldehyde-free resin layer material for later use: (1) Adding metered iso-oxo acid ester, polyester polyol and alcohol chain extender into a three-neck round-bottom flask provided with a magnetic stirring device, a nitrogen pipe and a thermometer, introducing nitrogen, then adding a catalyst 3 in batches, and reacting at 85 ℃ for 2 hours to obtain a first-step product; (2) Adding metered acrylic acid active monomers, an initiator 2 and a neutralizer into a flask containing a product obtained in the first step, stirring for 20min at the temperature of 50 ℃, adding a certain amount of water, and performing high-speed dispersion for 2h to obtain a water-based emulsion; and (4) carrying out solvent removal treatment on the aqueous emulsion to obtain a final product.
S2: preparing surface coating gloss oil for later use: (1) Adding metered aliphatic ERL-4221 into a three-neck round-bottom flask provided with a magnetic stirring device, a nitrogen pipe and a thermometer, introducing nitrogen, then adding a mixed solution (acrylic acid, acrylic ester, a catalyst 4 and a polymerization inhibitor 2 (two thirds of the total metered amount of the formula polymerization inhibitor 2)) into a constant-pressure funnel, controlling the dropping speed of the constant-pressure funnel under the condition of 80 ℃, adding the mixed solution into the flask within 2 hours after use, then heating to 120 ℃ for reaction, and stopping the reaction when the acid value of the system is reduced to below 60 to obtain a first-step product; (2) Adding metered trimellitic anhydride and glycol into a three-neck round-bottom flask provided with a magnetic stirring device, a nitrogen pipe and a thermometer, stirring and heating to 180 ℃ for reaction for 1h, then cooling to 80 ℃, adding metered catalyst 5, activator 2 and polymerization inhibitor 2 (one third of the total metered amount of the polymerization inhibitor 2 in the formula), finally controlling the system temperature to be 80 ℃, adding acrylic acid for multiple times, raising the system temperature to 120 ℃ after adding the acrylic acid in a pending amount, reacting for 30 minutes, starting to detect the acid value of the system, and stopping the reaction when the acid value of the system is reduced to below 60 to obtain a second-step product; (3) Adding a certain amount of water into a reaction kettle with a stirring paddle under the water bath temperature of 50 ℃, gradually adding the first-step product and the second-step product into the reaction kettle, and stirring for 1 hour to obtain a final product.
S3: preparing a back coating material for later use: (1) Adding metered bisphenol A epoxy resin and methacrylic acid into a three-neck round-bottom flask provided with a magnetic stirring device, a condensing device and a thermometer, dripping a tetrahydrofuran solution dissolved with a metered catalyst 1 and a metered polymerization inhibitor 1 (two thirds of the total metered polymerization inhibitor 1 in the formula) into the flask, controlling the dripping speed, and reacting for 2 hours at a set reaction temperature of 90 ℃ to obtain a first-step product; (2) Weighing metered acrylic acid, butyl acrylate, ether, an initiator 1 and an active agent 1, pouring the weighed acrylic acid, butyl acrylate, ether, initiator 1 and active agent 1 into a constant pressure dropping funnel, slowly dropping the weighed acrylic acid, butyl acrylate, ether, initiator 1 and active agent 1 into a four-neck flask filled with a first-step product from the constant pressure dropping funnel, and reacting for 1 hour by using an ice salt bath to obtain a second-step product; (3) Weighing metered isophorone diisocyanate, tetrahydrofuran, a catalyst 2 and the rest polymerization inhibitor 1, pouring the materials into a four-neck flask provided with a mechanical stirring device, a condensing device, a thermometer and a constant-pressure dropping funnel, adopting an ice salt bath, slowly dropping tetrahydrofuran of gamma-aminopropyltriethoxysilane from the constant-pressure dropping funnel, monitoring the reaction process by using the content of isocyanate groups in an acetone-di-n-butylamine titration system, and stopping the reaction when the content of the isocyanate groups is lower than a theoretical value to obtain a third step product; and then stirring the second step product, the third step product and water at the temperature of 40-45 ℃ under mechanical stirring to obtain the final product.
S4: preparing a bridging layer material for later use: adding measured alcohol substances, butyl acrylate and chlorinated polyethylene into a three-neck round-bottom flask provided with a magnetic stirring device, a nitrogen pipe and a thermometer, introducing nitrogen, heating to 60 ℃, keeping the temperature for 30min, adding measured organic amine, titanate (monoalkoxyl type) and epoxy silane, reacting for 1h, heating to 90 ℃, adding chlorinated polypropylene resin, reacting for 1h, stirring, adding guar gum, and keeping the temperature for 1h to obtain the bridging layer material.
S5: preparing aldehyde-free facing paper: injecting the polyurethane formaldehyde-free resin layer material into a dipping machine, and selecting the polyurethane formaldehyde-free resin layer material with the quantitative of 90g/m 2 The printing paper is produced by dipping, and the dipping processing is carried out according to the sequence, which comprises the following steps:
(1) The printing paper is impregnated by using a polyurethane formaldehyde-free resin layer material, and the sizing amount is 70g/m 2 Drying the polyurethane resin by a section of drying oven, and dividing the drying oven into four sections of drying ovens, wherein the temperatures of the drying ovens are 130 ℃, 142 ℃ and 120 ℃, so as to form a first polyurethane aldehyde-free resin layer and a second polyurethane aldehyde-free resin layer;
(2) Coating a back coating material on the first polyurethane formaldehyde-free resin layer, wherein the back coating sizing amount is 35g/m 2 Then, two-stage drying is carried out, the temperature of an oven is 140 ℃, 135 ℃, 120 ℃ and 110 ℃, and the drying oven is coiled after a cooling section;
(3) Placing the impregnated decorative paper on a gravure coating machine containing EB equipment for coating a bridging layer, specifically, uncoiling the decorative paper impregnated with the polyurethane aldehyde-free resin layer material and the back coating material, introducing the decoated paper into the gravure coating machine containing EB equipment, coating the bridging layer material on a second polyurethane aldehyde-free resin layer, wherein the coating weight is 3g/m 2 Coating gloss oil on the surface of the cloth with the coating weight of 30g/m 2 And finally, enabling the finish paper coated with the surface gloss oil to enter an EB (Electron Beam) curing device, and curing the reactive gloss oil through electron beam induction through special configuration, wherein the EB curing condition is as follows: 100kV voltage, 60kGy radiation energy and oxygen content<200ppm, forming a protective top-coated gloss oil layer to obtain the aldehyde-free facing paper.
Comparative example 2
A facing paper is impregnated by a conventional urea-formaldehyde resin and melamine resin impregnation system. Selecting base paper with the same type and the same quantitative, and impregnating on a high-fiber-benefit impregnation line to produce facing paper, wherein the urea-formaldehyde resin sizing amount is 70g/m in the first impregnation 2 Drying the mixture in a first-stage oven at 145 ℃, 142 ℃ and 115 ℃. Then coating surface adhesive and back adhesive, wherein the surface adhesive and the back adhesive are melamine resin, and the gluing amount of the surface adhesive and the gluing amount of the back adhesive are respectively 33g/m 2 And 35g/m 2 . And (3) after coating, performing two-stage drying at the temperatures of 145 ℃, 143 ℃, 138 ℃, 125 ℃ and 120 ℃ respectively, and cooling to obtain the decorative paper.
Test examples
The facing papers of examples 1 to 5 and comparative examples 1 to 2 were respectively made into artificial facing boards according to the following methods: cutting the facing paper into required sizes of plates, placing a substrate plate, placing one side of the back coating of the examples 1-5 and the comparative examples 1-2 in contact with the substrate plate, placing the substrate plate into a hot press, and pressing for 15s under the conditions of 130 ℃ and 13MPa to obtain the artificial facing plate.
The obtained artificial veneer is subjected to physical property detection according to the following detection standards: GB 18580-2017 limit on formaldehyde release in artificial boards and products thereof for interior decoration and finishing materials; GB/T34722-2017 impregnated bond paper veneer plywood and laminated wood board GB/T15102-2017 impregnated bond paper veneer fiberboard and shaving board; JIS A1460-2001 "test method for formaldehyde emission amount for construction Board"; GB/T17657-2013 physicochemical property test method for artificial boards and veneer artificial boards. The test results are shown in table 2.
Table 2 results of measuring performance of artificial veneer for examples 1 to 5 and comparative examples 1 to 2
1. As can be seen from table 2, the EB-cured aldehyde-free artificial veneer prepared in examples 1 to 5 and comparative example 1 did not release formaldehyde.
2. As can be seen from table 2, the EB cured aldehyde-free wood-based boards prepared by examples 1 to 5 and comparative example 1 to which the present invention was applied exhibited excellent abrasion resistance, scratch resistance, stain resistance and corrosion resistance, light fastness and dry heat resistance, and peel strength was 45N/m or more, among which the best example of the present invention was the one in which the effect of example 5 was the most excellent.
3. Different from the ratio of the aliphatic ERL-4221 to the acrylic acid in the base varnish for the top-coated oil of the comparative example 1, the hydrophobic effect after curing is better when the content of unsaturated carbon-carbon double bonds is increased.
4. As can be seen from table 2, when the ratio of the bisphenol a epoxy resin to the methacrylic acid is high, the ratio of the carbon-carbon double bond of the back coating material is high, and the surface adhesive strength and peel strength between the face paper and the base sheet are increased. The adhesive film paper of the urea-formaldehyde adhesive system of the triamine glue is very brittle after being pressed and pasted, so that the peel strength can not be detected, but from the aspect of surface bonding strength, when the resin system is prepared properly, the artificial veneer prepared by pressing and pasting the electron beam curing aldehyde-free veneer paper of the invention can be comparable to or even superior to the traditional triamine glued artificial board in the aspect of surface bonding strength.
5. As can be seen from Table 2, the water contact angles of the artificial veneer prepared by pressing and pasting the electron beam curing formaldehyde-free veneer paper are all larger than 90 degrees, and the strong hydrophobic effect is shown, while the artificial veneer of the traditional triamine glue urea glue system (comparative example 2) has no hydrophobic phenomenon, and the strong hydrophobic property of the invention can endow the veneer with the fingerprint-resistant effect.
The embodiments of the present invention have been described in detail with reference to the drawings, but the present invention is not limited to the embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and features of the embodiments may be combined with each other without conflict.
Claims (10)
1. The aldehyde-free facing paper cured by electron beams is characterized by comprising a back coating, a first polyurethane aldehyde-free resin layer, base paper, a second polyurethane aldehyde-free resin layer, a bridging layer and a surface gloss oil coating from bottom to top in sequence;
the back coating is made of polypropylene epoxy resin, and the preparation raw materials of the back coating comprise: bisphenol A epoxy resin, methacrylic acid, acrylic acid, acrylate, an organic solvent, isocyanate, a first catalyst, a second catalyst, a first active agent, a coupling agent, a first initiator, a first polymerization inhibitor and water;
the first polyurethane aldehyde-free resin layer and the second polyurethane aldehyde-free resin layer are made of waterborne polyurethane, and the preparation raw materials comprise: isocyanate, polyester polyol, an alcohol chain extender, an acrylic acid active monomer, a third catalyst, a neutralizer, a second initiator and water;
the preparation raw materials of the bridging layer comprise: chlorinated polypropylene resin, acrylic ester, chlorinated polyethylene, guar gum, organic amine, titanate, epoxy silane and alcohol substances;
the material of the surface-coated oil layer is polyacrylate, and the preparation raw materials comprise: aliphatic epoxy resin, acrylic acid, acrylic ester, trimellitic anhydride, ethylene glycol, a fourth catalyst, a fifth catalyst, a second polymerization inhibitor, a second activator and water.
2. The aldehyde-free facing paper cured by electron beams as claimed in claim 1, wherein the polypropylene epoxy resin is prepared from the following raw materials in percentage by weight: 25-35% of bisphenol A epoxy resin, 5-10% of methacrylic acid, 15-25% of acrylic acid, 5-10% of acrylate, 10-20% of organic solvent, 10-15% of isocyanate, 0.1-1% of first catalyst, 0.08-0.25% of second catalyst, 0.5-2% of first active agent, 2-5% of coupling agent, 1-5% of first initiator, 0.8-2% of first polymerization inhibitor and 5-30% of water.
3. The aldehyde-free facing paper cured by electron beams according to claim 1, wherein the polypropylene epoxy resin is prepared by the following method: (1) Dripping a solution in which a first catalyst and part of first polymerization inhibitor are dissolved into a mixture of bisphenol A epoxy resin and methacrylic acid, and heating for reaction to obtain a product A; (2) Mixing the product A, acrylic acid, acrylate, an organic solvent, an initiator and an activator, and reacting in an ice salt bath to obtain a product B; (3) Adding a coupling agent solution into a mixture of isocyanate, an organic solvent, a second catalyst and the rest first polymerization inhibitor in 40-50 water bath for reaction to obtain a product C, and then mixing and stirring the product B and the product C with water to obtain the catalyst.
4. The aldehyde-free facing paper cured by electron beams as claimed in claim 1, wherein the waterborne polyurethane is prepared from the following raw materials in percentage by weight: 26-35% of isocyanate, 28-38% of polyester polyol, 1-3% of alcohol chain extender, 5-10% of acrylic acid active monomer, 0.1-1% of third catalyst, 0.5-1% of neutralizer, 1-3% of second initiator and 20-40% of water.
5. The aldehyde-free facing paper cured by electron beams according to claim 1, wherein the aqueous polyurethane is prepared by the following method: (1) Mixing isocyanate, polyester polyol and an alcohol chain extender, adding a third catalyst under a protective atmosphere, and heating for reaction to obtain a product D; (2) And adding the acrylic acid active monomer, the second initiator and the neutralizing agent into the product D, heating and stirring for a period of time, adding water and stirring to obtain the acrylic acid active monomer.
6. The aldehyde-free facing paper cured by electron beams as claimed in claim 1, wherein the material of the bridging layer is prepared by the following method: (1) Mixing alcohol substances, acrylate and chlorinated polyethylene, heating and preserving heat for a period of time under a protective atmosphere, and then adding organic amine, titanate and epoxy silane for reaction; (2) Adding chlorinated polypropylene resin for continuous reaction, then adding guar gum under stirring, and keeping the temperature for a period of time to obtain the guar gum.
7. The aldehyde-free facing paper cured by electron beams as claimed in claim 1, wherein the polyacrylate is prepared from the following raw materials in percentage by weight: 15-25% of aliphatic epoxy resin, 25-40% of acrylic acid, 10-20% of acrylate, 10-15% of trimellitic anhydride, 5-10% of ethylene glycol, 0.05-0.15% of fourth catalyst, 0.05-0.15% of fifth catalyst, 0.1-0.5% of second polymerization inhibitor, 1-2% of second active agent and 20-35% of water.
8. The aldehyde-free facing paper according to claim 1, wherein the polyacrylate is prepared by the following process: (1) Under the conditions of protective atmosphere and heating condition, adding a mixed solution of partial acrylic acid, acrylic ester, a fourth catalyst and partial second polymerization inhibitor into the aliphatic epoxy resin for reaction to obtain a product E; (2) Mixing trimellitic anhydride and ethylene glycol, heating for reaction, cooling, adding a fifth catalyst, a second active agent, the rest second polymerization inhibitor and the rest acrylic acid, and heating for reaction to obtain a product F; and (3) mixing and stirring the product E, the product F and water to obtain the catalyst.
9. The method for preparing the aldehyde-free facing paper cured by electron beam according to any one of claims 1 to 8, comprising the steps of:
s1: impregnating the base paper with the waterborne polyurethane, heating and drying the impregnated base paper, and forming a first polyurethane aldehyde-free resin layer and a second polyurethane aldehyde-free resin layer on the upper surface and the lower surface of the base paper;
s2: coating the polypropylene epoxy resin on the first polyurethane formaldehyde-free resin layer, and heating and drying to form a back coating;
s3: and coating a bridging layer material on the second polyurethane formaldehyde-free resin layer, coating a gloss oil layer material on the second polyurethane formaldehyde-free resin layer, and then performing electron beam curing treatment to obtain the formaldehyde-free facing paper cured by the electron beams.
10. An aldehyde-free veneer comprising a substrate sheet and the aldehyde-free veneer cured by an electron beam of any one of claims 1 to 8, wherein the aldehyde-free veneer is attached to the substrate sheet and a back coating layer of the aldehyde-free veneer is in contact with the substrate sheet.
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Effective date of registration: 20231121 Address after: 528137 planning of science and Technology Industrial Zone, Leping Town, Sanshui District, Foshan, Guangdong, 52, B (F1), (F2), (F3), (F5), (F7) Applicant after: GUANGDONG TIANYUAN HUIBANG NEW MATERIAL CO.,LTD. Applicant after: FOSHAN TIANYUAN HEJIN DECORATION MATERIAL CO.,LTD. Applicant after: Tianyuan Huibang (Foshan) New Materials Technology Co.,Ltd. Applicant after: Tianyuan Huibang New Materials (Chengdu) Co.,Ltd. Address before: 528137 planning of science and Technology Industrial Zone, Leping Town, Sanshui District, Foshan, Guangdong, 52, B (F1), (F2), (F3), (F5), (F7) Applicant before: GUANGDONG TIANYUAN HUIBANG NEW MATERIAL CO.,LTD. Applicant before: FOSHAN TIANYUAN HEJIN DECORATION MATERIAL CO.,LTD. |
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