CN113802417B - Emulsion type mildew preventive, preparation process thereof, preparation process of mildew-proof impregnated bond paper and mildew-proof veneer - Google Patents

Emulsion type mildew preventive, preparation process thereof, preparation process of mildew-proof impregnated bond paper and mildew-proof veneer Download PDF

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Publication number
CN113802417B
CN113802417B CN202111184667.8A CN202111184667A CN113802417B CN 113802417 B CN113802417 B CN 113802417B CN 202111184667 A CN202111184667 A CN 202111184667A CN 113802417 B CN113802417 B CN 113802417B
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mildew
proof
bond paper
impregnated bond
emulsion type
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CN113802417A (en
Inventor
骆意
王春平
李琳琪
曾高康
龙玲
刘如
徐建峰
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Guangdong Tianyuan Huibang New Material Co ltd
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Guangdong Tianyuan Huibang New Material Co ltd
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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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27D—WORKING VENEER OR PLYWOOD
    • B27D1/00—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/02—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board the layer being formed of fibres, chips, or particles, e.g. MDF, HDF, OSB, chipboard, particle board, hardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/04—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B21/06—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B29/00—Layered products comprising a layer of paper or cardboard
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1284—Application of adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/07—Nitrogen-containing compounds
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/09—Sulfur-containing compounds
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/36—Polyalkenyalcohols; Polyalkenylethers; Polyalkenylesters
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/47—Condensation polymers of aldehydes or ketones
    • D21H17/49—Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen
    • D21H17/51—Triazines, e.g. melamine
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/53—Polyethers; Polyesters
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54—Synthetic 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
    • D21H17/57—Polyureas; Polyurethanes
    • 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
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63—Inorganic compounds
    • D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
    • D21H17/68—Water-insoluble compounds, e.g. fillers, pigments siliceous, e.g. clays
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/22—Agents rendering paper porous, absorbent or bulky
    • D21H21/24—Surfactants
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B32B2307/7145—Rot proof, resistant to bacteria, mildew, mould, fungi
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Forests & Forestry (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Fluid Mechanics (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention relates to the technical field of mildew inhibitors, and discloses an emulsion type mildew inhibitor and a preparation process thereof, a preparation process of mildew-resistant impregnated bond paper and a mildew-resistant veneer, wherein the emulsion type mildew inhibitor is prepared from the following raw materials in percentage by mass: 20-30% of mildew-proof active ingredient, 6-10% of nonionic surfactant, 8-02% of anionic surfactant, 2-4% of chitosan, 5-8% of polyvinyl alcohol, 1-2% of sodium montmorillonite, 2-4% of sodium polyacrylate and the balance of deionized water. The transparent emulsion type mildew preventive prepared by matching sodium-based montmorillonite, chitosan, polyvinyl alcohol and sodium polyacrylate with the effective components of the surfactant and the mildew preventive has better adsorption and slow release effects, can be uniformly dispersed into urea-formaldehyde resin and melamine-formaldehyde resin, does not influence the curing performance and the bonding performance of an adhesive, and does not change the appearance of impregnated bond paper after impregnation.

Description

Emulsion type mildew preventive, preparation process thereof, preparation process of mildew-proof impregnated bond paper and mildew-proof veneer
Technical Field
The invention relates to the technical field of mildew inhibitors, in particular to an emulsion type mildew inhibitor and a preparation process thereof, a preparation process of mildew-proof impregnated bond paper and a mildew-proof veneer.
Background
The impregnated bond paper is an important material for artificial board decorative surface, and is usually prepared by impregnating decorative base paper printed with patterns or pure colors in urea-formaldehyde resin (UF) or melamine-formaldehyde resin (MF), so that the artificial board can not only endow the artificial board with decorative aesthetic feeling, but also play a certain protection role in wear resistance, pollution resistance, corrosion resistance, scratch resistance and the like, and can be widely applied to the decorative surface field of furniture, floors, wallboards and the like.
Because the artificial board is prepared and processed by hot pressing of natural wood materials and adhesives, the artificial board has strong hygroscopicity and is easy to mildew in an environment with high humidity. Although the impregnated bond paper can prevent partial moisture from entering the artificial board, the veneer still has the potential risk of mildewing in the environment with higher isothermal humidity in plum rain seasons in south China. Mildew can not only affect the appearance of the product, but can even be a serious health hazard to the user. Therefore, the artificial board is usually required to be subjected to mildew-proof treatment, and the addition of the mildew-proof agent is a method for effectively preventing the mildew of the artificial board in the prior art, the existing mildew-proof agent is mostly added in the manufacturing process of the artificial board, for different types of artificial boards, the addition mode of the mildew-proof agent is greatly different, for example, a shaving board or a fiber board is directly mixed with wood shavings/wood fibers in an emulsion or powder form, and plywood and a laminated wood board are mostly mixed with an adhesive or impregnated with a veneer. Considering that different types of artificial boards have large temperature and pressure difference during preparation, no broad-spectrum applicable artificial board mildew preventive is provided, and meanwhile, when the broad-spectrum mildew preventive is mixed with an artificial board base material, a high-content mildew preventive needs to be added to achieve a good mildew preventive effect, but excessive mildew preventive affects the bonding strength of the artificial boards.
Disclosure of Invention
The invention aims to provide an emulsion type mildew inhibitor compatible with urea-formaldehyde resin or melamine-formaldehyde resin and a preparation method thereof, which can be used for producing mildew-proof impregnated bond paper and impregnated bond paper veneers and solve the technical problems of narrow application range, poor mildew-proof effect and poor bonding strength of the existing mildew inhibitor.
In order to achieve the aim, the invention provides an emulsion type mildew preventive which is prepared from the following raw materials in percentage by mass: 20-30% of mildew-proof active ingredient, 6-10% of nonionic surfactant, 8-12% of anionic surfactant, 2-4% of chitosan, 5-8% of polyvinyl alcohol, 1-2% of sodium montmorillonite, 2-4% of sodium polyacrylate and the balance of deionized water. The emulsion type mildew preventive in the scheme comprises mildew-proof effective components with mildew-proof effects, and 2 nonionic surfactants and anionic surfactants are added to play a synergistic effect, so that the emulsion type mildew preventive has a better mildew-proof effect; the emulsion type mildew preventive is in a capsule type, the particle size is 100-3000nm usually, the chitosan is used as a shell component of the capsule, and the deionized water is used as a solvent, so that the substances can be dissolved and dispersed conveniently. In addition, polyvinyl alcohol, sodium-based montmorillonite and sodium polyacrylate are added into the emulsion type mildew preventive, wherein the sodium-based montmorillonite has an interlayer ion adsorption effect and can keep long-term stability and release effects of mildew-proof active ingredients, and the sodium polyvinyl acetate, the polyvinyl alcohol, the chitosan and the sodium-based montmorillonite cooperate to form a shell structure of the emulsion type mildew preventive. The polyvinyl alcohol in the specific production of the scheme can be polyvinyl alcohol 1788 and the like.
Preferably, the mildew-proof active ingredient is at least one of isothiazolinone, 2- (thiocyanomethylmercapto) benzothiazole or 2- (2-hydroxyphenyl) -2H-benzotriazole. When the isothiazolinone is used as an effective mildew-proof component, the isothiazolinone can inhibit the growth of microorganisms and has a good mildew-proof and antibacterial effect; the 2- (thiocyanic acid methyl mercapto) benzothiazole and the 2- (2-hydroxyphenyl) -2H-benzotriazole can also play a better mildew-proof effect, the mildew-proof effective components can be used independently or optionally mixed by two or three, and the mildew-proof effect after mixing is better.
Preferably, the nonionic surfactant is at least one of fatty acid polyoxyethylene ester, fatty alcohol polyoxyethylene ether or polyether; the anionic surfactant is at least one of sodium alkyl benzene sulfonate or succinate sulfonate. When fatty acid polyoxyethylene ester, fatty alcohol polyoxyethylene ether and polyether are used as the nonionic surfactant, the nonionic surfactant has better solubilizing property, wettability, dispersibility and emulsibility, and can prevent aggregation of raw materials. The sodium alkyl benzene sulfonate and the succinate sulfonate are used as anionic surfactants, have good dispersing ability, and can promote the emulsion type mildew preventive to be added into the impregnating resin when being compounded with the nonionic surfactants for use, so that the bonding strength of the impregnating resin is improved.
In addition, the invention also discloses a preparation process of the emulsion type mildew inhibitor, which comprises the following steps:
s1, placing deionized water in a container according to mass percent in a constant-temperature water bath for heating, sequentially adding a nonionic surfactant, an anionic surfactant, chitosan, polyvinyl alcohol, sodium montmorillonite and sodium polyacrylate, and uniformly stirring to obtain a mixture;
s2, adding the mildew-proof effective component into the mixture, and uniformly dispersing to obtain the emulsion type mildew inhibitor.
Preferably, in the step S1, the temperature of the thermostatic water bath is 50-80 ℃, and the stirring speed is 100-200r/min.
Preferably, the step S2 includes the steps of: s21, adding the mildew-proof effective component into the mixture, and stirring and dispersing uniformly at 800-1000 r/min;
and S22, shearing in a homogenizer for 1-5min to obtain the emulsion type mildew preventive, wherein the pressure of the homogenizer is 600-1200bar.
When the emulsion type mildew preventive is prepared, the heating condition of a constant-temperature water bath is required to be maintained, the temperature of the water bath is specifically 50-80 ℃, and under the condition of relatively high temperature, all raw materials are promoted to be dissolved and dispersed uniformly, so that a better mildew preventive effect is exerted. Besides conventional stirring and dispersion, the emulsion type mildew preventive disclosed by the scheme also needs to be homogenized under high pressure (600-1200 bar) through the shearing action of a homogenizer, so that the raw materials can be obviously refined, the mildew-proof effect is improved, the layering of feed liquid can be reduced, and the good stability of the emulsion type mildew preventive during storage is ensured.
In addition, the invention also discloses a preparation process of the mildew-proof impregnated bond paper, which comprises the following steps:
s01, mixing the emulsion type mildew inhibitor with urea-formaldehyde resin or melamine-formaldehyde resin to obtain impregnating resin;
s02, dipping base paper in the dipping resin for 30-60s, and drying at 010-160 ℃ to obtain a semi-finished product;
s03, coating an adhesive on the front side or the back side of the semi-finished product; or, secondarily soaking the semi-finished product in an adhesive, and then drying at 010-160 ℃ until the pre-curing degree of the adhesive is 40-60%, thus obtaining the mildew-proof impregnated bond paper.
Considering that most of artificial boards or other decorative board products need to be finally decorated by coating, decorative paper, decorative film and the like, the scheme adds the mildew preventive into the outermost decorative material, namely the mildew-proof impregnated bond paper, so that the addition amount of the mildew preventive can be reduced, and the broad-spectrum adaptability to mildew prevention of the artificial boards can be improved. In order to realize efficient mildew resistance of the impregnated bond paper, the addition of the mildew preventive in the impregnating adhesive is an effective method for preparing the mildew-resistant impregnated bond paper relatively simply and conveniently, and at the moment, the compatibility of the mildew preventive and the impregnating adhesive (urea resin or melamine-formaldehyde resin) and the influence on the curing performance, the adhesive performance and the appearance quality of the impregnating resin need to be considered. The base paper in the scheme refers to paper which is not subjected to any treatment after preparation.
The prepared emulsion type mildew preventive is a transparent material, so when the emulsion type mildew preventive is used in the impregnated bond paper, the surface quality of the impregnated bond paper is not influenced, the emulsion type mildew preventive can have a long-term mildew preventive effect on the impregnated bond paper, the influence on the physical and chemical properties of an adhesive (melamine-formaldehyde resin) is small, and the subsequent processing is facilitated.
Preferably, the addition amount of the emulsion type mildew inhibitor is 0.1-0.5% of the total mass of the impregnating resin. The emulsion type mildew preventive prepared by the scheme has a good mildew prevention effect under the condition of small using amount.
Preferably, the adhesive is melamine formaldehyde resin; the application amount of the adhesive is 30-60% of the base paper weight.
The invention also provides a mildew-proof veneer which is obtained by hot-pressing any one of the mildew-proof impregnated bond paper on an artificial board for 0.5-2min under the pressure of 4-6Mpa and the temperature of 140-200 ℃. After the emulsion type mildew preventive is added, the performance change of the mildew-proof impregnated bond paper is very small, the mildew-proof veneer is specifically prepared by pressing the mildew-proof impregnated bond paper with an artificial board at the temperature of 140-200 ℃ and under the pressure of 4-6Mpa, the preparation process is simple, and the production cost is low.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1. the transparent emulsion type mildew preventive prepared by matching sodium-based montmorillonite, chitosan, polyvinyl alcohol and sodium polyacrylate with the effective components of a surfactant and the mildew preventive has good adsorption and slow release effects, can be uniformly dispersed into urea-formaldehyde resin and melamine-formaldehyde resin, does not influence the curing performance and the bonding performance of an adhesive (melamine-formaldehyde resin), and does not change the appearance of the impregnated bond paper after impregnation.
2. The mildew-proof veneer made of the mildew-proof impregnated bond paper as the raw material only adds a small amount of mildew preventive in the surface decorative material, can prevent the growth of mildew from entering the interior of the artificial board, has broad-spectrum adaptability to the artificial board, and does not influence the physical and chemical properties of the artificial board base material.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.
It should be noted that, if directional indications such as up, down, left, right, front, and back … … are involved in the embodiment of the present invention, the directional indications are only used to explain the relative position relationship between the components, the motion situation, and the like in a specific posture, and if the specific posture changes, the directional indications also change accordingly. In addition, technical solutions between the embodiments may be combined with each other, but must be based on the realization of the technical solutions by a person skilled in the art, and when the technical solutions are contradictory to each other or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention.
A preparation process of an emulsion type mildew preventive comprises the following steps:
s1, putting deionized water into a container according to mass percentage, heating the deionized water in a constant-temperature water bath at 50-80 ℃, sequentially adding 6-10% of nonionic surfactant, 8-12% of anionic surfactant, 2-4% of chitosan, 5-8% of polyvinyl alcohol, 1-2% of sodium montmorillonite and 2-4% of sodium polyacrylate, and uniformly stirring to obtain a mixture, wherein the stirring speed is 100-200r/min;
the mildew-proof active ingredient is at least one of isothiazolinone, 2- (thiocyanic acid methyl mercapto) benzothiazole or 2- (2-hydroxyphenyl) -2H-benzotriazole;
the nonionic surfactant is at least one of fatty acid polyoxyethylene ester, fatty alcohol polyoxyethylene ether or polyether; the anionic surfactant is at least one of sodium alkyl benzene sulfonate or succinate sulfonate;
s21, adding the mildew-proof effective component into the mixture, and stirring and dispersing uniformly at 800-1000 r/min;
and S22, shearing in a homogenizer for 1-5min to obtain the emulsion type mildew preventive, wherein the pressure of the homogenizer is 600-1200bar.
A preparation process of mildew-proof impregnated bond paper comprises the following steps:
s01, mixing the emulsion type mildew inhibitor with urea-formaldehyde resin or melamine-formaldehyde resin to obtain impregnating resin; the addition amount of the emulsion type mildew preventive is 0.1-0.5% of the total mass of the impregnating resin;
s02, impregnating base paper in the impregnating resin for 30-60s, and drying at 110-160 ℃ to obtain a semi-finished product;
s03, coating an adhesive on the front side or the back side of the semi-finished product; or, secondarily soaking the semi-finished product in an adhesive, and then drying at 110-160 ℃ until the pre-curing degree of the adhesive is 40-60%, so as to obtain the mildew-proof impregnated bond paper, wherein the adhesive is melamine formaldehyde resin; the application amount of the adhesive is 30-60% of the base paper weight.
A mildew-proof veneer is obtained by hot-pressing any one of the mildew-proof impregnated bond paper on an artificial board for 0.5-2min at the pressure of 4-6Mpa and the temperature of 140-200 ℃.
The technical solutions of the present invention are further described in detail with reference to the following specific examples, which should be understood as merely illustrative and not limitative.
Example 1
A mildew-proof veneer is prepared by hot pressing mildew-proof impregnated bond paper on artificial board (medium density fiberboard) at 190 deg.C under 6Mpa for 0.7 min.
The preparation process of the mildew-proof impregnated bond paper comprises the following steps: s01, mixing the emulsion type mildew preventive with urea-formaldehyde resin to obtain impregnating resin; the addition amount of the emulsion type mildew preventive is 0.3 percent of the total mass of the impregnating resin;
s02, impregnating base paper in the impregnating resin for 60s, and drying at 160 ℃ to obtain a semi-finished product;
s03, coating adhesive melamine formaldehyde resin on the front side and the back side of the semi-finished product; then drying at 150 ℃ until the precuring degree of the adhesive is 55% (at the moment, no flowing adhesive liquid exists on the paper surface, and the paper surface is not sticky), and obtaining the mildew-proof impregnated bond paper; the application amount of the adhesive is 40% of the base paper weight.
The preparation process of the emulsion type mildew preventive comprises the following steps: s1, according to mass percentage, 45% of deionized water is placed in a container and heated in a constant-temperature water bath at 60 ℃, 10% of fatty acid polyoxyethylene ester nonionic surfactant, 10% of sodium lauryl sulfosuccinate anionic surfactant, 2% of chitosan, 5% of polyvinyl alcohol, 1% of sodium montmorillonite and 2% of sodium polyacrylate are sequentially added, and the mixture is obtained by uniformly stirring, wherein the stirring speed is 150r/min;
s21, adding 25% of mildew-proof effective component [10% isothiazolinone +15%2- (thiocyanomethylmercapto) benzothiazole ] into the mixture, and stirring and dispersing uniformly at 830 r/min;
and S22, shearing in a homogenizer for 3min to obtain the emulsion type mildew preventive, wherein the pressure of the homogenizer is 800bar.
Example 2
A mildew-proof veneer is prepared by hot pressing mildew-proof impregnated bond paper on artificial board at 200 deg.C under 6Mpa for 0.5 min.
The preparation process of the mildew-proof impregnated bond paper comprises the following steps: s01, mixing the emulsion type mildew preventive with urea-formaldehyde resin to obtain impregnating resin; the addition amount of the emulsion type mildew preventive is 0.1 percent of the total mass of the impregnating resin;
s02, impregnating base paper in the impregnating resin for 40s, and drying at 140 ℃ to obtain a semi-finished product;
s03, coating melamine formaldehyde resin adhesive on the front side and the back side of the semi-finished product; then drying at 160 ℃ until the pre-curing degree of the adhesive is 50 percent (at the moment, no flowing glue solution exists on the paper surface, and the paper surface is not sticky), and obtaining the mildew-proof impregnated bond paper; the application amount of the adhesive is 60% of the base paper weight.
The preparation process of the emulsion type mildew preventive comprises the following steps: s1, placing 32% of discharged deionized water into a container according to mass percentage, heating the mixture in a constant-temperature water bath at 60 ℃, sequentially adding 8% of fatty acid polyoxyethylene ester nonionic surfactant, 12% of sodium dodecyl benzene sulfonate anionic surfactant, 4% of chitosan, 8% of polyvinyl alcohol, 2% of sodium montmorillonite and 4% of sodium polyacrylate, and uniformly stirring to obtain a mixture, wherein the stirring speed is 200r/min;
s21, adding 30% of mildew-proof active ingredient (isothiazolinone) into the mixture, and stirring and dispersing uniformly at 900 r/min;
and S22, shearing in a homogenizer for 5min to obtain the emulsion type mildew preventive, wherein the pressure of the homogenizer is 1000bar.
Example 3
A mildew-proof veneer is prepared by hot-pressing mildew-proof impregnated bond paper on artificial board at 140 deg.C and 4Mpa for 2 min.
The preparation process of the mildew-proof impregnated bond paper comprises the following steps: s01, mixing the emulsion type mildew preventive with urea-formaldehyde resin to obtain impregnating resin; the addition amount of the emulsion type mildew preventive is 0.5 percent of the total mass of the impregnating resin;
s02, soaking base paper in the impregnating resin for 50s, and drying at 150 ℃ to obtain a semi-finished product;
s03, secondarily soaking the semi-finished product in a melamine-formaldehyde resin adhesive, and then drying at 160 ℃ until the pre-curing degree of the adhesive is 40% to obtain the mildew-proof impregnated bond paper; the application amount of the adhesive is 40% of the base paper weight.
The preparation process of the emulsion type mildew inhibitor comprises the following steps: s1, placing 51% of deionized water into a container, heating the deionized water in a constant-temperature water bath at 80 ℃, sequentially adding 6% of fatty alcohol-polyoxyethylene ether nonionic surfactant, 2% of nonylphenol polyoxyethylene ether nonionic surfactant, 6% of sodium dodecyl benzene sulfonate anionic surfactant, 4% of nonylphenol polyoxyethylene ether sodium sulfosuccinate anionic surfactant, 3% of chitosan, 5% of polyvinyl alcohol, 1% of sodium montmorillonite and 2% of sodium polyacrylate, and uniformly stirring to obtain a mixture, wherein the stirring rate is 120r/min;
s21, adding 20% of mildew-proof effective component [12% of 2- (thiocyanic acid methyl mercapto) benzothiazole +8%2- (2-hydroxyphenyl) -2 hydrogen-benzotriazole ] into the mixture, and stirring and uniformly dispersing at 1000 r/min;
and S22, shearing in a homogenizer for 2min to obtain the emulsion type mildew preventive, wherein the pressure of the homogenizer is 600bar.
Example 4
A mildew-proof veneer is prepared by hot pressing mildew-proof impregnated bond paper on artificial board at 170 deg.C and 5Mpa for 1.5 min.
The preparation process of the mildew-proof impregnated bond paper comprises the following steps: s01, mixing the emulsion type mildew preventive with urea-formaldehyde resin to obtain impregnating resin; the addition amount of the emulsion type mildew preventive is 0.4 percent of the total mass of the impregnating resin;
s02, dipping base paper in the dipping resin for 30s, and drying at 110 ℃ to obtain a semi-finished product;
s03, secondarily soaking the semi-finished product in a melamine-formaldehyde resin adhesive, and then drying at 110 ℃ until the pre-curing degree of the adhesive is 40% to obtain the mildew-proof impregnated bond paper; the application amount of the adhesive is 60% of the base paper weight.
The preparation process of the emulsion type mildew inhibitor comprises the following steps: s1, according to mass percentage, 41% of deionized water is placed in a container and heated in a constant-temperature water bath at 50 ℃, 6% of nonylphenol polyoxyethylene ether nonionic surfactant, 8% of nonylphenol polyoxyethylene ether sodium sulfonate succinate anionic surfactant, 4% of chitosan, 7% of polyvinyl alcohol, 1% of sodium montmorillonite and 3% of sodium polyacrylate are sequentially added, and the mixture is obtained by uniformly stirring, wherein the stirring speed is 100r/min;
s21, adding 30% of mildew-proof active ingredient [2- (2-hydroxyphenyl) -2H-benzotriazole ] into the mixture, and stirring and dispersing uniformly at 860 r/min;
and S22, shearing in a homogenizer for 1min to obtain the emulsion type mildew preventive, wherein the pressure of the homogenizer is 1200bar.
Comparative example 1
The comparative example was conducted under the same conditions as in example 1 except that: the emulsion type mildew inhibitor is not added to the impregnating resin in the step S01.
Comparative example 2
The comparative example was conducted under the same conditions as in example 2 except that: in step S1, only the fatty acid polyoxyethylene ester nonionic surfactant (20%) is added.
Comparative example 3
The comparative example was conducted under the same conditions as in example 2 except that: in step S1, only sodium dodecylbenzenesulfonate anionic surfactant (20%) is added.
Example 5
The conditions in this example are the same as in example 4, except that: in step S21, 30% of the mildew-proof active ingredient is obtained by compounding 12% of isothiazolinone and 18% of 2- (thiocyanomethylmercapto) benzothiazole.
Example 6
The conditions in this example are the same as in example 4, except that: in step S21, 30% of the antifungal active ingredient is prepared by compounding 10% of isothiazolinone, 7% of 2- (thiocyanomethylmercapto) benzothiazole and 13% of 2- (2-hydroxyphenyl) -2H-benzotriazole.
Comparative example 4
The comparative example was conducted under the same conditions as in example 3 except that: and step S22, shearing without a homogenizer, and stirring and dispersing to obtain the emulsion type mildew preventive. When the homogenizing machine is not used for shearing, the prepared mildew preventive is layered after being placed for 3min, and cannot be normally used.
The performance tests were performed on examples 1-6 and comparative examples 1-3, and the specific performance test parameters are shown in the following table:
Figure BDA0003298240740000091
Figure BDA0003298240740000101
as can be seen from the above table, compared with the comparative example, the mildew-proof veneer prepared from the mildew-proof impregnated bond paper (added with the emulsion mildew preventive) of the scheme can keep better appearance quality, and simultaneously can ensure that after the emulsion mildew preventive is added, the mildew-proof impregnated bond paper has better surface bonding strength (bonding strength) and abrasion resistance also can be maintained in a better range, the mildew-proof grades of examples 1-4 can reach 0 grade, and the mildew-proof of the groups of comparative examples 1-4 without the slow-release transparent emulsion mildew preventive is poorer and is 3-4 grade; after the veneer is placed for 6 months, the mildew-proof grade is still 0 grade, and the mildew-proof veneer added with the emulsion mildew inhibitor in the scheme still has a very excellent mildew-proof effect.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all equivalent structural changes made by using the content of the present specification or other related technical fields within the spirit of the present invention are included in the scope of the present invention.

Claims (8)

1. A preparation process of mildew-proof impregnated bond paper is characterized by comprising the following steps:
s01, mixing the emulsion type mildew preventive with urea-formaldehyde resin or melamine-formaldehyde resin to obtain impregnating resin;
s02, dipping base paper in the dipping resin for 30-60s, and drying at 110-160 ℃ to obtain a semi-finished product;
s03, coating an adhesive on the front side or the back side of the semi-finished product; or, secondarily soaking the semi-finished product in an adhesive, and then drying at 110-160 ℃ until the pre-curing degree of the adhesive is 40-60%, thus obtaining the mildew-proof impregnated bond paper;
the emulsion type mildew preventive is prepared from the following raw materials in percentage by mass: 20-30% of mildew-proof active ingredients, 6-10% of nonionic surfactant, 8-12% of anionic surfactant, 2-4% of chitosan, 5-8% of polyvinyl alcohol, 1-2% of sodium montmorillonite, 2-4% of sodium polyacrylate and the balance of deionized water;
the nonionic surfactant is at least one of fatty acid polyoxyethylene ester and fatty alcohol polyoxyethylene ether; the anionic surfactant is at least one of sodium alkyl benzene sulfonate or succinate sulfonate.
2. The process for preparing a mildewproof impregnated bond paper according to claim 1, wherein the mildewproof active ingredient is at least one of isothiazolinone, 2- (thiocyanomethylmercapto) benzothiazole or 2- (2-hydroxyphenyl) -2H-benzotriazole.
3. The preparation process of the mildewproof impregnated bond paper according to claim 1, wherein the preparation process of the emulsion mildewproof agent comprises the following steps:
s1, placing deionized water in a container according to mass percent in a constant-temperature water bath for heating, sequentially adding a nonionic surfactant, an anionic surfactant, chitosan, polyvinyl alcohol, sodium montmorillonite and sodium polyacrylate, and uniformly stirring to obtain a mixture;
s2, adding the mildew-proof effective component into the mixture, and uniformly dispersing to obtain the emulsion type mildew inhibitor.
4. The process for preparing the mildewproof impregnated bond paper according to claim 3, wherein in the step S1, the temperature of the thermostatic water bath is 50-80 ℃, and the stirring speed is 100-200r/min.
5. The process for preparing the mildewproof impregnated bond paper according to claim 3, wherein the step S2 comprises the following steps:
s21, adding the mildew-proof effective component into the mixture, and stirring and dispersing uniformly at 800-1000 r/min;
and S22, shearing in a homogenizer for 1-5min to obtain the emulsion type mildew preventive, wherein the pressure of the homogenizer is 600-1200bar.
6. The process for preparing the mildewproof impregnated bond paper according to claim 1, wherein the addition amount of the emulsion mildewproof agent is 0.1 to 0.5 percent of the total mass of the impregnating resin.
7. The preparation process of the mildewproof impregnated bond paper according to claim 1, wherein the adhesive is melamine formaldehyde resin; the application amount of the adhesive is 30-60% of the base paper weight.
8. A mildew-proof veneer, characterized in that, the mildew-proof impregnated bond paper of claim 1 is hot-pressed on an artificial board for 0.5-2min at a pressure of 4-6Mpa and a temperature of 140-200 ℃.
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