CN109457536B - Formaldehyde-free decorative adhesive film paper and preparation method thereof - Google Patents
Formaldehyde-free decorative adhesive film paper and preparation method thereof Download PDFInfo
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- CN109457536B CN109457536B CN201811302724.6A CN201811302724A CN109457536B CN 109457536 B CN109457536 B CN 109457536B CN 201811302724 A CN201811302724 A CN 201811302724A CN 109457536 B CN109457536 B CN 109457536B
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/80—Paper comprising more than one coating
- D21H19/82—Paper comprising more than one coating superposed
- D21H19/824—Paper comprising more than one coating superposed two superposed coatings, both being non-pigmented
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/24—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/28—Polyesters
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/80—Paper comprising more than one coating
- D21H19/84—Paper comprising more than one coating on both sides of the substrate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
Abstract
The invention belongs to the technical field of decorative paper, and particularly relates to formaldehyde-free decorative adhesive film paper and a preparation method thereof. The formaldehyde-free decorative film adhesive paper sequentially comprises a back coating resin layer, a resin dipping layer, base material paper, a resin dipping layer and a surface coating resin layer from inside to outside. The formaldehyde-free decorative film adhesive paper provided by the invention adopts formaldehyde-free waterborne polyurethane resin as a preparation raw material, and replaces the traditional urea-formaldehyde resin and melamine resin, and the prepared decorative film adhesive paper is green and environment-friendly, does not release formaldehyde, is high in drying speed, has both hardness and toughness, is excellent in performance, is simple and convenient to construct, and can be popularized and applied.
Description
Technical Field
The invention belongs to the technical field of decorative paper, and particularly relates to formaldehyde-free decorative adhesive film paper and a preparation method thereof.
Background
The formaldehyde is a colorless gas with special pungent smell, is high in toxicity and easy to cause cancers, has a release period of 8-15 years, is more harmful to human bodies, particularly the old, children, pregnant women and other people with low immunity, and is on the priority control list of toxic chemicals in China. The formaldehyde is the most main pollutant in indoor air, has the widest source and the most serious harm, the high temperature of the indoor formaldehyde can cause serious damage to the immunologic function of a human body, meanwhile, the formaldehyde can cause nasal cavity cancer, sinus cancer and leukemia, can also cause female menstrual disorder, pregnancy syndrome, newborn physique reduction, chromosome abnormality and the like, and people can also gradually cause some chronic diseases when being in a low-dose formaldehyde environment for a long time. Formaldehyde is therefore known as the first killer of the living room space. At present, with the enhancement of the environmental awareness of the world, the requirements of people on the content of organic volatile matters, particularly formaldehyde, which are harmful to human bodies and are emitted into the air are more and more strict.
The indoor formaldehyde is mainly from some indoor decoration materials including plywood, particle board, decorative adhesive film paper and the like, and because the decoration materials are added with adhesives (such as urea-formaldehyde resin and melamine-formaldehyde resin adhesive) prepared by taking formaldehyde as raw materials in the production and decoration processes, the formaldehyde can be continuously released along with time when the decoration materials are used. Research shows that the release of formaldehyde is a long-term process, and the formaldehyde can be released to the outside continuously in the life cycle of the decoration material, so that serious indoor environmental pollution is caused, the health of people is seriously harmed, and the release concentration is greatly influenced by the environmental temperature and humidity. The formaldehyde of the existing decorative adhesive film paper is mainly released from the following sources: on one hand, an adhesive is required to be used in the impregnation production link, and the main components of the existing adhesive are urea-formaldehyde resin adhesive filling and melamine resin, wherein a large amount of free formaldehyde is released in the impregnation production process; on the other hand, in the process of storing and hot-pressing the decorative film adhesive paper, as the urea-formaldehyde resin is generated under the acidic condition, after free moisture contained in the decorative film adhesive paper and certain moisture are absorbed, partial cured resin can be subjected to hydrolysis reaction under the condition to release formaldehyde, and the progress of the hydrolysis reaction can be accelerated due to insufficient curing and poor storage condition. For example, chinese patent document CN 104018402a discloses an antibacterial, mildew-proof, and moisture-proof artificial board decorative paper, which comprises a base paper and a composite layer, wherein the composite layer sequentially comprises a first resin layer, a second resin layer, and an antibacterial and mildew-proof layer, wherein the first resin layer is a formaldehyde urea resin layer, the second resin layer is a melamine resin layer, and the antibacterial and mildew-proof layer is made of an organic antibacterial, inorganic antibacterial, and mildew-proof agent. Therefore, the traditional decorative film adhesive paper not only pollutes the production environment in the production process and threatens the health of operators, but also seriously affects the health of users due to formaldehyde released by the cured resin in the product, so that the development of the environment-friendly decorative film adhesive paper without formaldehyde release is urgently needed.
In recent years, in the preparation process of decorative adhesive film paper, the waterborne polyurethane adhesive is widely applied to the field of decorative adhesive film paper due to the self-safety and environment-friendly performance. For example, chinese patent document CN 104804168A discloses an aqueous polyurethane emulsion, a preparation method thereof, an application thereof on a wallpaper basement membrane, and a wallpaper basement membrane, wherein the emulsion comprises the following raw materials: the base film applied to the wallpaper has good waterproof and alkali-proof properties, but has poor scratch resistance, corrosion resistance and wear resistance, and meanwhile, the flexibility has certain problems, which brings difficulty to subsequent cutting and other processes. Chinese patent document CN 105368370A discloses a water-based polyurethane wallpaper adhesive, which comprises the following raw material components: the adhesive is safe and environment-friendly, and has excellent alkali resistance, but the adhesive has strong adhesive force, the adhesion problem is easy to occur during later construction, and meanwhile, the external scratch resistance and the wear resistance are poor.
The existing aqueous polyurethane adhesives for preparing the decorative film adhesive paper have the problems of slow drying speed, incompatible hardness and toughness, poor water resistance, poor wear resistance and scratch resistance and the like, so the defects of the existing traditional adhesives prepared by taking formaldehyde as a raw material and the existing aqueous polyurethane adhesives need to be overcome, and the formaldehyde-free decorative film adhesive paper with environmental protection, high drying speed, compatible hardness and toughness and excellent performance and the preparation method thereof are provided for people.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides the formaldehyde-free decorative film adhesive paper and the preparation method thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a formaldehyde-free decorative film adhesive paper comprises a back coating resin layer, a resin dipping layer, base paper, a resin dipping layer and a surface coating resin layer from inside to outside in sequence;
the back coating resin layer comprises the following preparation raw materials in parts by weight: 25-35 parts of isocyanate, 18-28 parts of polyester polyol, 2-5 parts of alcohol chain extender, 1-5 parts of hydrophilic chain extender, 0.2-0.6 part of aliphatic amine catalyst, 1-3 parts of neutralizer, 10-20 parts of composite active monomer, 0.6-2 parts of active monomer, 0.5-3 parts of initiator, 75-85 parts of deionized water and 15-25 parts of absolute ethyl alcohol;
the resin-impregnated layer comprises the following preparation raw materials in parts by weight: 26-35 parts of isocyanate, 28-38 parts of polyester polyol, 1-3 parts of alcohol chain extender, 2-6 parts of hydrophilic chain extender, 0.3-0.7 part of aliphatic amine catalyst, 2-5 parts of neutralizer, 10-20 parts of composite active monomer, 0.5-3 parts of initiator and 150-170 parts of deionized water;
the top coating resin layer comprises the following preparation raw materials in parts by weight: 25-35 parts of isocyanate, 15-25 parts of polyester polyol, 2-5 parts of alcohol chain extender, 3-7 parts of hydrophilic chain extender, 0.3-0.7 part of aliphatic amine catalyst, 1-3.5 parts of neutralizer, 15-20 parts of composite active monomer, 0.5-1.7 parts of active monomer, 0.5-3 parts of initiator, 110-130 parts of deionized water, 0.5-2 parts of release agent and 1-4 parts of wear-resisting agent.
Further, the back coating resin layer comprises the following preparation raw materials in parts by weight: 28 parts of isocyanate, 25 parts of polyester polyol, 3 parts of alcohol chain extender, 4 parts of hydrophilic chain extender, 0.5 part of aliphatic amine catalyst, 2.5 parts of neutralizer, 17 parts of composite active monomer, 1.2 parts of active monomer, 1.5 parts of initiator, 80 parts of deionized water and 20 parts of absolute ethyl alcohol.
Further, the resin-impregnated layer comprises the following preparation raw materials in parts by weight: 28 parts of isocyanate, 30 parts of polyester polyol, 2 parts of alcohol chain extender, 4 parts of hydrophilic chain extender, 0.5 part of aliphatic amine catalyst, 3.5 parts of neutralizer, 17 parts of composite active monomer, 1.5 parts of initiator and 160 parts of deionized water.
Further, the top coating resin layer comprises the following preparation raw materials in parts by weight: 28 parts of isocyanate, 21 parts of polyester polyol, 3 parts of alcohol chain extender, 4 parts of hydrophilic chain extender, 0.5 part of aliphatic amine catalyst, 2.2 parts of neutralizer, 17 parts of composite active monomer, 1.2 parts of active monomer, 1.5 parts of initiator, 120 parts of deionized water, 1 part of release agent and 3 parts of wear-resisting agent.
Further, the isocyanate is isophorone diisocyanate, dicyclohexylmethane diisocyanate, or methyl ethyl diisocyanate.
Further, the polyester polyol is a polycarbonate diol or a polycaprolactone diol.
Further, composite active monomers in the back coating resin layer are methyl methacrylate and butyl acrylate, the active monomers are glycidyl methacrylate, and the weight ratio of the methyl methacrylate to the butyl acrylate to the glycidyl methacrylate is (0.6-1): 1: (0.1-0.2). Further, the weight ratio of methyl methacrylate, butyl acrylate and glycidyl methacrylate is 0.89: 1: 0.13.
further, the composite active monomer in the resin-impregnated layer is methyl methacrylate and butyl acrylate, and the weight ratio of the methyl methacrylate to the butyl acrylate is (0.3-0.6): 1; further, the weight ratio of methyl methacrylate to butyl acrylate is 0.42: 1.
further, the composite active monomers in the top coating resin layer are methyl methacrylate and butyl acrylate, the active monomers are glycidyl methacrylate, and the weight ratio of the methyl methacrylate to the butyl acrylate to the glycidyl methacrylate is 1: (0.5-0.9): (0.05-0.16). Further, the weight ratio of the methyl methacrylate, the butyl acrylate and the glycidyl methacrylate is 1: 0.7: 0.12.
further, the hydrophilic chain extender is dimethylolbutyric acid, dihydroxy half ester or methyldiethanolamine; still further, the hydrophilic chain extender is dimethylolbutyric acid.
Further, the aliphatic amine catalyst is N, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, N, N, N ', N' -tetramethylalkylenediamine or N, N-dimethylbenzylamine; further, the aliphatic amine catalyst is N, N-dimethylcyclohexylamine.
Further, the neutralizing agent is triethylamine, ammonia water or potassium hydroxide; still further, the neutralizing agent is triethylamine.
Further, the initiator is azobisisobutyronitrile.
Further, the release agent is silicone oil.
Further, the wear-resisting agent is aluminum oxide.
The preparation method of the formaldehyde-free decorative adhesive film paper comprises the following steps:
s1, preparation of back coating resin: adding isocyanate, polyester polyol and an alcohol chain extender into a reaction kettle according to the formula amount for reaction, introducing nitrogen for protection, then adding an aliphatic amine catalyst, reacting at 80-90 ℃ for 1.5-2.5 h, adding a hydrophilic chain extender, continuing to react for 1.5-2.5 h, cooling to 45-55 ℃, adding a composite active monomer, adding a neutralizing agent for neutralization for 10-20 min, adding deionized water for high-speed dispersion to prepare an aqueous emulsion A, placing the aqueous emulsion A into the reaction kettle, adding the active monomer for uniform dispersion, dropwise adding an initiator for 2.5-3.5 h by a soap-free emulsion polymerization method, preserving heat for 1.5-2.5 h, cooling, and adding absolute ethyl alcohol to prepare a back coating resin for later use;
s2, preparation of one-step resin impregnation: adding isocyanate, polyester polyol and an alcohol chain extender into a reaction kettle according to the formula amount for reaction, introducing nitrogen for protection, then adding an aliphatic amine catalyst, reacting at 80-90 ℃ for 1.5-2.5 h, adding a hydrophilic chain extender, continuing to react for 1.5-2.5 h, cooling to 45-55 ℃, adding a composite active monomer, adding a neutralizing agent for neutralization for 10-20 min, adding deionized water for high-speed dispersion to prepare an aqueous emulsion B, placing the aqueous emulsion B into the reaction kettle, dropwise adding an initiator for 2.5-3.5 h, preserving heat for 1.5-2.5 h to prepare an aqueous emulsion C, removing the solvent from the aqueous emulsion C, cooling, and discharging to prepare a primary soaking resin for later use;
s3, preparation of top coating resin: adding isocyanate, polyester polyol and an alcohol chain extender into a reaction kettle according to the formula amount for reaction, introducing nitrogen for protection, adding an aliphatic amine catalyst for catalytic reaction, adding a hydrophilic chain extender for continuous reaction for 1.5-2.5 h after reacting at 80-90 ℃, cooling to 45-55 ℃, adding a composite active monomer, adding a neutralizing agent for neutralization for 10-20 min, adding deionized water for high-speed dispersion to prepare an aqueous emulsion D, placing the aqueous emulsion D into the reaction kettle, adding the active monomer for uniform dispersion, adopting a soap-free emulsion polymerization method, dropwise adding an initiator for 2.5-3.5 h, preserving heat for 1.5-2.5 h, cooling, adding a release agent and a wear-resisting agent, and stirring uniformly to prepare a top-coat resin for later use;
s4, dipping the base paper by using a dipping resin, and then drying the base paper by an oven with three temperature sections to form a dipping resin layer on each of two sides of the base paper; coating back coating resin on one of the resin impregnated layers, drying the resin impregnated layers in an oven with four temperature sections to prepare a back coating resin layer, coating surface coating resin on the other resin impregnated layer, drying the resin impregnated layers in the oven with four temperature sections to prepare a surface coating resin layer, and then processing the surface coating resin layer to prepare the formaldehyde-free decorative film adhesive paper.
Further, the oven temperatures with the three temperature sections were 100 ℃, 110 ℃ and 100 ℃, respectively.
Further, the oven temperatures with the four temperature sections were 140 ℃, 160 ℃, 180 ℃ and 160 ℃, respectively.
Further, the amount of the primary impregnating resin used in the step S4 is 70-90 g/m2The amount of the back coating resin is 30-50 g/m2The dosage of the top coating resin is 10-20 g/m2。
The formaldehyde-free decorative adhesive film paper adopts the waterborne polyurethane resin as a preparation raw material, specifically, the first-dipping resin is prepared by synthesizing a prepolymer by isocyanate and polyester polyol under the action of an alcohol chain extender, then adding a hydrophilic chain extender for chain extension, carrying out catalytic reaction under the action of a catalyst, then adding methyl methacrylate and butyl acrylate, adjusting the proportion of a hard section and a soft section, neutralizing and salifying after the reaction is finished, then adding deionized water, carrying out self-emulsification on the waterborne polyurethane in water to obtain an anionic waterborne polyurethane emulsion, and finally dripping an initiator to promote polymerization. In the preparation of the one-dip resin, the appropriate ratio of the hard segment (methyl methacrylate) to the soft segment (butyl acrylate) is found to be (0.3-0.6): 1, the prepared one-dip resin has primary water resistance and flexibility by cooperating with the addition amount of each preparation raw material, meets the requirements of coil drawing and cutting in the later period of the process, and is beneficial to construction;
the back coating resin is prepared from isocyanate, polyester polyol, an alcohol chain extender, a hydrophilic chain extender, methyl methacrylate, butyl acrylate and a neutralizing agent as preparation raw materials to obtain an anionic waterborne polyurethane emulsion, then glycidyl methacrylate is added to be uniformly dispersed for improving the adhesive property of the emulsion, then an initiator is dropwise added to promote polymerization reaction, and finally absolute ethyl alcohol is added. In the preparation of the back coating resin, the appropriate ratio of the hard segment (methyl methacrylate and glycidyl methacrylate) to the soft segment (butyl acrylate) is found to be (0.6-1): 1: (0.1-0.2), the addition amount of each preparation raw material is cooperated, and the prepared back coating resin is high in drying speed, good in water resistance and free of glue failure caused by moisture;
the surface coating resin is prepared from isocyanate, polyester polyol, an alcohol chain extender, a hydrophilic chain extender, methyl methacrylate, butyl acrylate and a neutralizing agent as raw materials, an anionic waterborne polyurethane emulsion is prepared, glycidyl methacrylate is added to be uniformly dispersed for improving the adhesive property of the emulsion, then an initiator is dropwise added to promote polymerization reaction, and finally a release agent and an abrasion-resistant agent are added. In the preparation of the top-coat resin, by searching for a suitable ratio of the hard segment (methyl methacrylate and glycidyl methacrylate) and soft segment (butyl acrylate) of 1: (0.5-0.9): (0.05-0.16), and the prepared top-coating resin has certain fluidity and good hardness by cooperating with the addition of each preparation raw material, so that the performances of wear resistance, scratch resistance, pollution resistance and corrosion resistance are improved.
The three layers of resins are all derived from one system, so that the three layers of resins have excellent binding force, the prepared decorative film adhesive paper is a whole with toughness and toughness, has excellent performances of wear resistance, scratch resistance, pollution resistance, corrosion resistance and the like, has good cohesiveness at the temperature of more than 120 ℃ and under the pressure of 14mpa, does not have cohesiveness at the temperature of less than 100 ℃, is favorable for storage and transportation, and avoids the adhesion of the upper layer of film adhesive paper and the lower layer of film adhesive paper during later cutting construction.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention provides a novel decorative adhesive film paper for the decoration industry, the raw material for preparing each resin layer of the decorative adhesive film paper is waterborne polyurethane resin without formaldehyde release, the traditional urea-formaldehyde resin and melamine resin are replaced, the release of harmful substances is stopped from the source, the prepared decorative adhesive film paper does not release formaldehyde, and the decorative adhesive film paper accords with the current green and environment-friendly consumption trend.
(2) The resin layers of the decorative film adhesive paper are derived from a formaldehyde-free waterborne polyurethane resin system, the resin layers have excellent performance and excellent binding force, the prepared decorative film adhesive paper is a whole with hardness and toughness, the drying speed is high, the laminating time is short, the construction is simple and convenient, the production efficiency is effectively improved, and the decorative film adhesive paper can be popularized and applied.
(3) In the preparation process of the decorative adhesive film paper, the prepared decorative adhesive film paper has excellent performances of wear resistance, scratch resistance, pollution resistance, corrosion resistance and the like by searching the proper proportion of the hard segment and the soft segment in each resin layer formula and cooperating with the addition amount of each preparation raw material, is suitable for being used as decorative paper for furniture, walls and the like, and has the advantages of simple preparation process, easily controlled conditions, stable process and industrial production.
Detailed Description
The present invention is further described in the following description of the specific embodiments, which is not intended to limit the invention, but various modifications and improvements can be made by those skilled in the art according to the basic idea of the invention, within the scope of the invention, as long as they do not depart from the basic idea of the invention.
The raw materials for preparing the invention are conventional commercial products.
Examples 1 to 3 Formaldehyde-free decorative film adhesive papers of the present invention
The formaldehyde-free decorative film adhesive paper of the embodiments 1 to 3 of the invention comprises a back coating resin layer, a resin impregnated layer, substrate paper, a resin impregnated layer and a surface coating resin layer from inside to outside in sequence, and comprises the following preparation raw materials by weight, specifically shown in table 1:
table 1 examples 1-3 preparation of formaldehyde-free decorative film adhesive paper
Remarking: a: a back coating resin layer; b: a resin-impregnated layer; c: top coating resin layer
The preparation method of the formaldehyde-free decorative film adhesive paper comprises the following steps:
s1, preparation of back coating resin: adding isophorone diisocyanate, polycarbonate diol and 1, 4-butanediol into a reaction kettle according to the formula amount for reaction, introducing nitrogen for protection, then adding N, N-dimethylcyclohexylamine, reacting for 2 hours at 85 ℃, adding dimethylolpropionic acid for continuous reaction for 2 hours, cooling to 50 ℃, adding methyl methacrylate and butyl acrylate, then adding triethylamine for neutralization for 15 minutes, adding deionized water for high-speed dispersion to obtain an aqueous emulsion A, placing the aqueous emulsion A into the reaction kettle, adding glycidyl methacrylate for uniform dispersion, adopting a soap-free emulsion polymerization method, dropwise adding an initiator for 3 hours, then preserving heat for 2 hours, cooling, adding absolute ethyl alcohol to obtain a back coating resin for later use;
s2, preparation of one-step resin impregnation: adding isophorone diisocyanate, polycarbonate diol and 1, 4-butanediol into a reaction kettle according to the formula amount for reaction, introducing nitrogen for protection, then adding N, N-dimethylcyclohexylamine, reacting for 2 hours at 85 ℃, then adding dimethylolpropionic acid for continuous reaction for 2 hours, cooling to 50 ℃, adding methyl methacrylate and butyl acrylate, then adding triethylamine for neutralization for 15 minutes, adding deionized water for high-speed dispersion to prepare aqueous emulsion B, placing the aqueous emulsion B into the reaction kettle, dropwise adding an initiator for 3 hours, then preserving heat for 2 hours to prepare aqueous emulsion C, removing a solvent from the aqueous emulsion C, cooling, and discharging to prepare primary dipping resin for later use;
s3, preparation of top coating resin: adding isophorone diisocyanate, polycarbonate diol and 1, 4-butanediol into a reaction kettle according to the formula amount for reaction, introducing nitrogen for protection, adding N, N-dimethylcyclohexylamine for catalytic reaction, adding dimethylolpropionic acid for continuous reaction for 2 hours after reacting for 2 hours at 85 ℃, cooling to 50 ℃, adding methyl methacrylate and butyl acrylate, then adding triethylamine for neutralization for 15 minutes, adding deionized water for high-speed dispersion to obtain an aqueous emulsion D, placing the aqueous emulsion D into the reaction kettle, adding glycidyl methacrylate for uniform dispersion, adopting a soap-free emulsion polymerization method, dropwise adding an initiator for 3 hours, then preserving heat for 2 hours, cooling, adding silicone oil and aluminum oxide, stirring uniformly, and preparing a top-coating resin for later use;
s4, use 80g/m2One resin impregnated to the base paperDipping glue, and then drying the paper by an oven with three temperature sections (100 ℃, 110 ℃ and 100 ℃), and respectively forming a resin dipping layer on each of two sides of the base paper; coating 40g/m on one of the resin-impregnated layers2The back coating resin is dried by an oven with four temperature sections (140 ℃, 160 ℃, 180 ℃ and 160 ℃) to prepare a back coating resin layer, and the other resin dipping layer is coated with 15g/m2The surface coating resin is dried by an oven with four temperature sections (140 ℃, 160 ℃, 180 ℃ and 160 ℃) to prepare a surface coating resin layer, namely the formaldehyde-free decorative film adhesive paper is prepared.
Example 4 Formaldehyde-free decorative film adhesive paper of the invention
Compared with embodiment 2, the present embodiment is different only in that: dicyclohexylmethane diisocyanate was used instead of isophorone diisocyanate.
Example 5 Formaldehyde-free decorative film adhesive paper of the invention
Compared with embodiment 2, the present embodiment is different only in that: polycaprolactone diols were used instead of polycarbonate diols.
Example 6 Formaldehyde-free decorative film adhesive paper of the invention
Compared with embodiment 2, the present embodiment is different only in that: instead of dimethylolpropionic acid, a dihydroxy half-ester was used.
Comparative example 1
The comparative example differs from example 2 only in that: diphenylmethane-4, 4-diisocyanate was used instead of isophorone diisocyanate.
Comparative example 2
The comparative example differs from example 2 only in that: polyether triols are used in place of polycarbonate diols.
Comparative example 3
The comparative example differs from example 2 only in that: the weight ratio of methyl methacrylate to butyl acrylate in the resin-impregnated layer was 0.7: 1.
comparative example 4
The comparative example differs from example 2 only in that: the weight ratio of methyl methacrylate, butyl acrylate and glycidyl methacrylate in the back coating resin layer is 1.5: 1: 0.5.
comparative example 5
The comparative example differs from example 2 only in that: the weight ratio of methyl methacrylate, butyl acrylate and glycidyl methacrylate in the top coating resin layer is 1: 1.2: 0.2.
test example I, detection of relevant Properties of decorative adhesive film paper of the present invention
The decorative film adhesive papers prepared in examples 1 to 6 and comparative examples 1 to 5 of the present invention were pressed and attached to the cereal grass incense board by a press at 120 ℃, 10s and 14mpa to prepare an aldehyde-free decorative board, and performance tests were performed according to the relevant national standards, and the test results are specifically shown in tables 2 and 3.
Table 2 decorative sheet performance test results of decorative adhesive film papers applied in examples 1 to 6 of the present invention
Table 3 decorative board performance test results of decorative adhesive film paper applied in comparative examples 1-5
(1) As can be seen from table 2, the decorative sheet prepared by applying the decorative adhesive film paper prepared in embodiments 1 to 6 of the present invention does not release formaldehyde, which indicates that the decorative adhesive film paper of the present invention is safe and environment-friendly, harmless to human body and environment, and suitable for popularization and use;
(2) as can be seen from table 2, the aldehyde-free decorative sheets prepared by applying the decorative adhesive film papers of examples 1 to 6 of the present invention have excellent wear resistance, scratch resistance, stain resistance, corrosion resistance, cigarette burning resistance, light color fastness and dry heat resistance, and the peel strength is 40N/m or more, wherein the best effect of example 2 is the best example of the present invention;
(3) as can be seen from Table 3, compared with example 2, in comparative example 1, diphenylmethane-4, 4-diisocyanate was used in place of isophorone diisocyanate, and in comparative example 2, polyether triol was used in place of polycarbonate diol, and the decorative sheet prepared had significantly reduced properties; the proportion of hard segments (methyl methacrylate and glycidyl methacrylate) and soft segments (butyl acrylate) in the formula is respectively adjusted in the comparative examples 3-5, all properties of the prepared decorative sheet are obviously reduced, and the decorative sheet is particularly shown in surface wear resistance, scratch resistance, peeling strength and the like.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (5)
1. The formaldehyde-free decorative film adhesive paper is characterized by comprising a back coating resin layer, a resin dipping layer, substrate paper, a resin dipping layer and a surface coating resin layer from inside to outside in sequence;
the back coating resin layer comprises the following preparation raw materials in parts by weight: 25-35 parts of isocyanate, 18-28 parts of polyester polyol, 2-5 parts of alcohol chain extender, 1-5 parts of hydrophilic chain extender, 0.2-0.6 part of aliphatic amine catalyst, 1-3 parts of neutralizer, 10-20 parts of composite active monomer, 0.6-2 parts of active monomer, 0.5-3 parts of initiator, 75-85 parts of deionized water and 15-25 parts of absolute ethyl alcohol; the composite active monomer is methyl methacrylate and butyl acrylate, the active monomer is glycidyl methacrylate, and the weight ratio of the methyl methacrylate to the butyl acrylate to the glycidyl methacrylate is (0.6-1): 1: (0.1 to 0.2);
the resin-impregnated layer comprises the following preparation raw materials in parts by weight: 26-35 parts of isocyanate, 28-38 parts of polyester polyol, 1-3 parts of alcohol chain extender, 2-6 parts of hydrophilic chain extender, 0.3-0.7 part of aliphatic amine catalyst, 2-5 parts of neutralizer, 10-20 parts of composite active monomer, 0.5-3 parts of initiator and 150-170 parts of deionized water; the composite active monomer is methyl methacrylate and butyl acrylate, and the weight ratio of the methyl methacrylate to the butyl acrylate is (0.3-0.6): 1;
the top coating resin layer comprises the following preparation raw materials in parts by weight: 25-35 parts of isocyanate, 15-25 parts of polyester polyol, 2-5 parts of alcohol chain extender, 3-7 parts of hydrophilic chain extender, 0.3-0.7 part of aliphatic amine catalyst, 1-3.5 parts of neutralizer, 15-20 parts of composite active monomer, 0.5-1.7 parts of active monomer, 0.5-3 parts of initiator, 110-130 parts of deionized water, 0.5-2 parts of release agent and 1-4 parts of wear-resisting agent; the composite active monomer is methyl methacrylate and butyl acrylate, the active monomer is glycidyl methacrylate, and the weight ratio of the methyl methacrylate to the butyl acrylate to the glycidyl methacrylate is 1: (0.5-0.9): (0.05-0.16);
the hydrophilic chain extender is dimethylolbutyric acid, dihydroxy half ester or methyldiethanolamine;
the preparation method of the formaldehyde-free decorative adhesive film paper comprises the following steps:
s1, preparation of back coating resin: adding isocyanate, polyester polyol and an alcohol chain extender into a reaction kettle according to the formula amount for reaction, introducing nitrogen for protection, then adding an aliphatic amine catalyst, reacting at 80-90 ℃ for 1.5-2.5 h, adding a hydrophilic chain extender, continuing to react for 1.5-2.5 h, cooling to 45-55 ℃, adding a composite active monomer, adding a neutralizing agent for neutralization for 10-20 min, adding deionized water for high-speed dispersion to prepare an aqueous emulsion A, placing the aqueous emulsion A into the reaction kettle, adding the active monomer for uniform dispersion, dropwise adding an initiator for 2.5-3.5 h by a soap-free emulsion polymerization method, preserving heat for 1.5-2.5 h, cooling, and adding absolute ethyl alcohol to prepare a back coating resin for later use;
s2, preparation of one-step resin impregnation: adding isocyanate, polyester polyol and an alcohol chain extender into a reaction kettle according to the formula amount for reaction, introducing nitrogen for protection, then adding an aliphatic amine catalyst, reacting at 80-90 ℃ for 1.5-2.5 h, adding a hydrophilic chain extender, continuing to react for 1.5-2.5 h, cooling to 45-55 ℃, adding a composite active monomer, adding a neutralizing agent for neutralization for 10-20 min, adding deionized water for high-speed dispersion to prepare an aqueous emulsion B, placing the aqueous emulsion B into the reaction kettle, dropwise adding an initiator for 2.5-3.5 h, preserving heat for 1.5-2.5 h to prepare an aqueous emulsion C, removing the solvent from the aqueous emulsion C, cooling, and discharging to prepare a primary soaking resin for later use;
s3, preparation of top coating resin: adding isocyanate, polyester polyol and an alcohol chain extender into a reaction kettle according to the formula amount for reaction, introducing nitrogen for protection, adding an aliphatic amine catalyst for catalytic reaction, adding a hydrophilic chain extender for continuous reaction for 1.5-2.5 h after reacting at 80-90 ℃, cooling to 45-55 ℃, adding a composite active monomer, adding a salt forming agent for neutralization for 10-20 min, adding water for high-speed dispersion to prepare an aqueous emulsion D, placing the aqueous emulsion D into the reaction kettle, adding the active monomer for uniform dispersion, dropwise adding an initiator for 2.5-3.5 h by a soap-free emulsion polymerization method, preserving heat for 1.5-2.5 h, cooling, adding a release agent and a wear-resisting agent, and stirring uniformly to prepare a top-coating resin for later use;
s4, dipping the base paper by using a dipping resin, and then drying the base paper by an oven with three temperature sections to form a dipping resin layer on each of two sides of the base paper; coating back coating resin on one of the resin dipping layers, drying the resin dipping layers by an oven with four temperature sections to prepare a back coating resin layer, coating surface coating resin on the other resin dipping layer, and drying the resin dipping layers by the oven with four temperature sections to prepare a surface coating resin layer, namely the formaldehyde-free decorative film adhesive paper is prepared.
2. The formaldehyde-free decorative adhesive film paper according to claim 1, wherein the isocyanate is isophorone diisocyanate, dicyclohexylmethane diisocyanate, or methylcycloethyl diisocyanate.
3. The formaldehyde-free decorative film adhesive of claim 1, wherein the polyester polyol is a polycarbonate diol or a polycaprolactone diol.
4. The method for preparing formaldehyde-free decorative bond paper according to claim 1, wherein the oven temperature of the three temperature sections is 100 ℃, 110 ℃ and 100 ℃.
5. The method for preparing formaldehyde-free decorative bond paper according to claim 1, wherein the oven temperature of the four temperature zones is 140 ℃, 160 ℃, 180 ℃ and 160 ℃.
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| CN110450239B (en) * | 2019-08-19 | 2021-06-25 | 万华生态科技有限公司 | Preparation method of novel formaldehyde-free impregnated membrane paper |
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| CN111411543B (en) * | 2020-05-09 | 2022-01-28 | 中国林业科学研究院木材工业研究所 | Adhesive for formaldehyde-free impregnated bond paper and preparation method thereof |
| CN113696570B (en) * | 2021-08-30 | 2023-09-22 | 江苏厚生新能源科技有限公司 | High-color-fastness water-washing-resistant polyethylene fabric and preparation process thereof |
| CN114687248B (en) * | 2022-04-06 | 2023-02-21 | 黄山兴伟反光材料有限公司 | Environment-friendly decorative paper and preparation method thereof |
| CN115450068B (en) * | 2022-09-29 | 2023-12-29 | 广东天元汇邦新材料股份有限公司 | Formaldehyde-free facing paper solidified by electron beam, its preparation method and application |
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