CN111590700A - High-strength composite board with antibacterial and mildew-proof functions and production method thereof - Google Patents

High-strength composite board with antibacterial and mildew-proof functions and production method thereof Download PDF

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Publication number
CN111590700A
CN111590700A CN202010360475.7A CN202010360475A CN111590700A CN 111590700 A CN111590700 A CN 111590700A CN 202010360475 A CN202010360475 A CN 202010360475A CN 111590700 A CN111590700 A CN 111590700A
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China
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antibacterial
carbon material
composite board
wood
strength composite
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CN111590700B (en
Inventor
许静
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Xinyi Tianhao Wood Industry Co ltd
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Xinyi Tianhao Wood Industry Co ltd
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    • 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
    • B27D1/04—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring to produce plywood or articles made therefrom; Plywood sheets
    • 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
    • B27D1/04—Joining wood veneer with any material; Forming articles thereby; Preparatory processing of surfaces to be joined, e.g. scoring to produce plywood or articles made therefrom; Plywood sheets
    • B27D1/08—Manufacture of shaped articles; Presses specially designed therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27D—WORKING VENEER OR PLYWOOD
    • B27D5/00—Other working of veneer or plywood specially adapted to veneer or plywood
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27G—ACCESSORY MACHINES OR APPARATUS FOR WORKING WOOD OR SIMILAR MATERIALS; TOOLS FOR WORKING WOOD OR SIMILAR MATERIALS; SAFETY DEVICES FOR WOOD WORKING MACHINES OR TOOLS
    • B27G11/00—Applying adhesives or glue to surfaces of wood to be joined
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27L—REMOVING BARK OR VESTIGES OF BRANCHES; SPLITTING WOOD; MANUFACTURE OF VENEER, WOODEN STICKS, WOOD SHAVINGS, WOOD FIBRES OR WOOD POWDER
    • B27L5/00—Manufacture of veneer ; Preparatory processing therefor
    • B27L5/02—Cutting strips from a rotating trunk or piece; Veneer lathes
    • 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
    • B32B21/13—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board all layers being exclusively wood
    • 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
    • B32B21/14—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood board or veneer
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • B32B7/02—Physical, chemical or physicochemical properties
    • B32B7/022—Mechanical properties
    • 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
    • B32B7/08—Interconnection of layers by mechanical means
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09J161/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C09J161/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
    • 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
    • B32B2037/1269—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives multi-component 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/546—Flexural strength; Flexion stiffness
    • 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
    • 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
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • 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
    • C08K2003/2231—Oxides; Hydroxides of metals of tin
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Mechanical Engineering (AREA)
  • Forests & Forestry (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Chemical And Physical Treatments For Wood And The Like (AREA)
  • Dry Formation Of Fiberboard And The Like (AREA)
  • Laminated Bodies (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention belongs to the technical field of composite board manufacturing, and particularly relates to a high-strength composite board with antibacterial and mildewproof functions and a production method thereof. The composite board is formed by gluing a plurality of layers of wood veneers, the textures of the wood veneers on the adjacent layers are mutually vertical, and the adhesive used for bonding the wood veneers on the adjacent layers is a modified urea-formaldehyde resin adhesive added with an antibacterial component; the antibacterial component is a composite of silver nanoparticles and a carbon material. The invention improves the adhesive used in the manufacturing process deeply on the basis of the common commercially available composite board, adds the specially-made antibacterial agent in the conventionally used urea-formaldehyde resin, adds the proper auxiliary agent in a matching way, and also optimizes the adaptability of the production process of the composite board. Through the series of improvement measures, the produced composite board shows excellent antibacterial and mildew-proof performance, and simultaneously shows very balanced and excellent comprehensive performance in the aspects of formaldehyde release amount, bonding strength, bending strength and the like.

Description

High-strength composite board with antibacterial and mildew-proof functions and production method thereof
Technical Field
The invention belongs to the technical field of composite board manufacturing, and particularly relates to a high-strength composite board with antibacterial and mildewproof functions and a production method thereof.
Background
The composite board is a three-layer or multi-layer plate material formed by rotary cutting wood sections into single boards or slicing battens into thin wood and gluing the single boards by using an adhesive, and the composite board is usually formed by vertically arranging the fiber directions of the single boards of the adjacent layers and gluing the single boards. The composite board has the advantages of high strength, low cost, resource recycling and the like, and is a material widely applied to the fields of packaging, furniture, building materials and the like. With the increase of application fields and the diversification of application environments, people put forward higher requirements on the composite board, such as certain antibacterial performance, capability of resisting humid environment without mildewing, higher strength, more environmental protection, durability and the like. Conventional composite panels have been difficult to adapt to the increasing demands of functionalization and the increasingly demanding environments of use.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a high-strength composite board with antibacterial and mildewproof functions and a production method thereof. The high-strength composite board with the antibacterial and mildew-proof functions is formed by gluing a plurality of layers of wood veneers, the textures of the wood veneers on the adjacent layers are mutually vertical, and the adhesive used for bonding the wood veneers on the adjacent layers is a modified urea-formaldehyde resin adhesive added with an antibacterial component; the antibacterial component is a compound of silver nanoparticles and a carbon material and is marked as an Ag @ C antibacterial agent.
Further, in the high-strength composite board with the antibacterial and mildewproof functions, the modified urea-formaldehyde resin adhesive is prepared by mixing the following components:
urea-formaldehyde resin: 100 portions of
Talc powder: 5-8 parts of
Tin dioxide: 1-2 parts of
Zinc sulfide: 1-2 parts of
Ag @ C antibacterial agent: 0.2 to 0.5 portion
Sodium butylnaphthalenesulfonate: 0.5 to 1 portion
Polyvinyl alcohol: 3-4 parts of
Polypropylene glycol diglycidyl ether: 2-3 parts of
Sodium dodecylbenzenesulfonate: 2-3 parts.
Further, in the high-strength composite board with antibacterial and mildewproof functions, the Ag @ C antibacterial agent is prepared by the following steps:
a1: reacting p-hydroxybiphenyl with cyanuric chloride to generate a precursor required by the preparation of the carbon material through a hypercrosslinking reaction;
a2: placing the precursor of the carbon material obtained from A1 in a calcining furnace, and calcining the precursor into the carbon material in a nitrogen atmosphere;
a3: and loading silver nanoparticles on the carbon material obtained in the step A2 by an impregnation method to obtain the Ag @ C antibacterial agent.
Further, in the step A1, 1 part of p-hydroxybiphenyl, 1 part of cyanuric chloride, 5 parts of anhydrous aluminum trichloride and 12 parts of chloroform are uniformly mixed by weight, and the temperature is controlled to be lower than 5 ℃ in the mixing process; heating the mixture to 60 ℃, preserving the heat for 12 hours, and cooling to room temperature; filtering to obtain black solid, washing in 20% hydrochloric acid for 2h, washing in deionized water for 2h, and washing twice; drying for 24 hours in a drying oven at 100 ℃ to obtain a precursor of the carbon material;
further, in the step a2, the calcination procedure is to heat up to 550 ℃ from room temperature at a rate of 5 ℃/min and to keep the temperature for 3 hours, to heat up to 680 ℃ at a rate of 2 ℃/min and to keep the temperature for 3 hours, and then to naturally cool to room temperature, thereby obtaining the carbon material.
Further, in the step a3, 100g of the carbon material is added into 2L of silver nitrate solution with a concentration of 0.1mmol/L to be soaked for 3 hours, filtered and dried, then the obtained product is placed in a calcining furnace to be calcined for 2 hours at a temperature of 420 ℃, and the obtained product is naturally cooled to room temperature, so as to obtain the Ag @ C antibacterial agent.
The production method of the high-strength composite board with the antibacterial and mildewproof functions comprises the following steps:
b1: rotary cutting the wood into thin slices by using a rotary cutter, and feeding the thin slices into a hot-blast stove for drying to obtain a wood veneer;
b2: the modified urea-formaldehyde resin adhesive is sprayed on the surface of the wood veneer by using a glue sprayer, and the single-side glue coating amount is 160-180g/m2(ii) a 5-11 layers of wood veneers are bonded together by hot pressing according to the principle that the grains of the wood veneers on the adjacent layers are mutually vertical;
b3: and naturally cooling the plate obtained in the step B2 to room temperature, and then carrying out static pressure aging.
Further, in the above method for producing a high-strength composite board with antibacterial and antifungal functions, in step B1, a rotary cutter is used to rotary cut the wood into sheets with a thickness of 1.2-1.8mm, and the moisture content of the dried wood veneer is 7-9%.
Further, in the above method for producing a high-strength composite board with antibacterial and antifungal functions, in step B2, the hot pressing temperature is 125-.
Further, in the above method for producing a high-strength composite board with antibacterial and antifungal functions, in step B3, the static pressure aging time is 12-24 hours, and the static pressure aging pressure is 0.8-1.2 Mpa.
Has the advantages that: the invention provides a high-strength composite board with antibacterial and mildewproof functions and a production method thereof, which are characterized in that on the basis of a common commercially available composite board, an adhesive used in the manufacturing process is deeply improved, a specially-made Ag @ C antibacterial agent is added into a conventionally used urea-formaldehyde resin, a proper auxiliary agent is added in a matching manner, and meanwhile, the production process of the composite board is adaptively optimized. Through the series of improvement measures, the produced composite board shows excellent antibacterial and mildew-proof performance, and simultaneously shows very balanced and excellent comprehensive performance in the aspects of formaldehyde release amount, bonding strength, bending strength and the like.
Detailed Description
Example 1
A high-strength composite board with antibacterial and mildew-proof functions is formed by gluing a plurality of layers of wood veneers, the textures of the wood veneers on the adjacent layers are mutually vertical, and the adhesive used for bonding the wood veneers on the adjacent layers is a modified urea-formaldehyde resin adhesive added with an antibacterial component; the antibacterial component is a compound of silver nanoparticles and a carbon material and is marked as an Ag @ C antibacterial agent.
In the embodiment, the modified urea-formaldehyde resin adhesive is prepared by mixing the following components:
urea-formaldehyde resin: 100 portions of
Talc powder: 5 portions of
Tin dioxide: 1 part of
Zinc sulfide: 1 part of
Ag @ C antibacterial agent: 0.2 part
Sodium butylnaphthalenesulfonate: 0.5 portion
Polyvinyl alcohol: 3 portions of
Polypropylene glycol diglycidyl ether: 2 portions of
Sodium dodecylbenzenesulfonate: 2 portions of
Wherein the granularity of the Ag @ C antibacterial agent is 400 meshes.
In this example, the Ag @ C antimicrobial was prepared by the following steps:
a1: reacting p-hydroxybiphenyl with cyanuric chloride to generate a precursor required by the preparation of the carbon material through a hypercrosslinking reaction;
a2: placing the precursor of the carbon material obtained from A1 in a calcining furnace, and calcining the precursor into the carbon material in a nitrogen atmosphere;
a3: and loading silver nanoparticles on the carbon material obtained in the step A2 by an impregnation method to obtain the Ag @ C antibacterial agent.
In the embodiment, in the step A1, 1 part of p-hydroxybiphenyl, 1 part of cyanuric chloride, 5 parts of anhydrous aluminum trichloride and 12 parts of chloroform are uniformly mixed by weight, and the temperature needs to be controlled to be lower than 5 ℃ in the mixing process; heating the mixture to 60 ℃, preserving the heat for 12 hours, and cooling to room temperature; filtering to obtain black solid, washing in 20% hydrochloric acid for 2h, washing in deionized water for 2h, and washing twice; drying for 24 hours in a drying oven at 100 ℃ to obtain a precursor of the carbon material;
in this embodiment, in step a2, the calcination procedure is to heat up to 550 ℃ from room temperature at a rate of 5 ℃/min and keep the temperature for 3 hours, then heat up to 680 ℃ at a rate of 2 ℃/min and keep the temperature for 3 hours, and then naturally cool to room temperature to obtain the carbon material.
In the embodiment, in the step a3, 100g of carbon material is added into 2L of silver nitrate solution with the concentration of 0.1mmol/L to be soaked for 3 hours, and after being filtered and dried, the carbon material is placed into a calcining furnace to be calcined for 2 hours at the temperature of 420 ℃, and then the carbon material is naturally cooled to the room temperature, so that the Ag @ C antibacterial agent is obtained.
In this embodiment, the high-strength composite board with antibacterial and mildewproof functions is manufactured by the following steps:
b1: rotary cutting the wood into thin slices by using a rotary cutter, and feeding the thin slices into a hot-blast stove for drying to obtain a wood veneer;
b2: the modified urea-formaldehyde resin adhesive is sprayed on the surface of a wood veneer by using a glue sprayer, and the single-side gluing amount is 160g/m2(ii) a Bonding 5 layers of wood veneers together by hot pressing according to the principle that the grains of the adjacent layers of wood veneers are mutually vertical;
b3: and naturally cooling the plate obtained in the step B2 to room temperature, and then carrying out static pressure aging.
In this example, in step B1, wood was rotary-cut into 1.8mm thick sheets by using a rotary cutter, and the moisture content of the dried wood veneers was 7%.
In this example, in step B2, the hot pressing temperature was 125 ℃, the pressure was 4.5MPa, and the pressure holding time was 35 min.
In this example, in step B3, the time for the static pressure aging was 12 hours, and the pressure for the static pressure aging was 1.2 MPa.
Example 2
A high-strength composite board with antibacterial and mildew-proof functions is formed by gluing a plurality of layers of wood veneers, the textures of the wood veneers on the adjacent layers are mutually vertical, and the adhesive used for bonding the wood veneers on the adjacent layers is a modified urea-formaldehyde resin adhesive added with an antibacterial component; the antibacterial component is a compound of silver nanoparticles and a carbon material and is marked as an Ag @ C antibacterial agent.
In the embodiment, the modified urea-formaldehyde resin adhesive is prepared by mixing the following components:
urea-formaldehyde resin: 100 portions of
Talc powder: 8 portions of
Tin dioxide: 2 portions of
Zinc sulfide: 2 portions of
Ag @ C antibacterial agent: 0.5 portion
Sodium butylnaphthalenesulfonate: 1 part of
Polyvinyl alcohol: 4 portions of
Polypropylene glycol diglycidyl ether: 3 portions of
Sodium dodecylbenzenesulfonate: 3 parts of a mixture;
wherein the granularity of the Ag @ C antibacterial agent is 400 meshes.
In this example, the Ag @ C antimicrobial was prepared by the following steps:
a1: reacting p-hydroxybiphenyl with cyanuric chloride to generate a precursor required by the preparation of the carbon material through a hypercrosslinking reaction;
a2: placing the precursor of the carbon material obtained from A1 in a calcining furnace, and calcining the precursor into the carbon material in a nitrogen atmosphere;
a3: and loading silver nanoparticles on the carbon material obtained in the step A2 by an impregnation method to obtain the Ag @ C antibacterial agent.
In the embodiment, in the step A1, 1 part of p-hydroxybiphenyl, 1 part of cyanuric chloride, 5 parts of anhydrous aluminum trichloride and 12 parts of chloroform are uniformly mixed by weight, and the temperature needs to be controlled to be lower than 5 ℃ in the mixing process; heating the mixture to 60 ℃, preserving the heat for 12 hours, and cooling to room temperature; filtering to obtain black solid, washing in 20% hydrochloric acid for 2h, washing in deionized water for 2h, and washing twice; drying for 24 hours in a drying oven at 100 ℃ to obtain a precursor of the carbon material;
in this embodiment, in step a2, the calcination procedure is to heat up to 550 ℃ from room temperature at a rate of 5 ℃/min and keep the temperature for 3 hours, then heat up to 680 ℃ at a rate of 2 ℃/min and keep the temperature for 3 hours, and then naturally cool to room temperature to obtain the carbon material.
In the embodiment, in the step a3, 100g of carbon material is added into 2L of silver nitrate solution with the concentration of 0.1mmol/L to be soaked for 3 hours, and after being filtered and dried, the carbon material is placed into a calcining furnace to be calcined for 2 hours at the temperature of 420 ℃, and then the carbon material is naturally cooled to the room temperature, so that the Ag @ C antibacterial agent is obtained.
In this embodiment, the high-strength composite board with antibacterial and mildewproof functions is manufactured by the following steps:
b1: rotary cutting the wood into thin slices by using a rotary cutter, and feeding the thin slices into a hot-blast stove for drying to obtain a wood veneer;
b2: the modified urea-formaldehyde resin adhesive is sprayed on the surface of a wood veneer by using a glue sprayer, and the single-side gluing amount is 180g/m2(ii) a Bonding 11 layers of wood veneers together by hot pressing according to the principle that the grains of the wood veneers on the adjacent layers are mutually vertical;
b3: and naturally cooling the plate obtained in the step B2 to room temperature, and then carrying out static pressure aging.
In this example, in step B1, wood was rotary-cut into 1.2mm thick sheets by using a rotary cutter, and the moisture content of the dried wood veneers was 9%.
In this example, in step B2, the hot pressing temperature was 130 ℃, the pressure was 3.2MPa, and the pressure holding time was 25 min.
In this example, in step B3, the time for the static pressure aging was 24 hours, and the pressure for the static pressure aging was 0.8 MPa.
Example 3
A high-strength composite board with antibacterial and mildew-proof functions is formed by gluing a plurality of layers of wood veneers, the textures of the wood veneers on the adjacent layers are mutually vertical, and the adhesive used for bonding the wood veneers on the adjacent layers is a modified urea-formaldehyde resin adhesive added with an antibacterial component; the antibacterial component is a compound of silver nanoparticles and a carbon material and is marked as an Ag @ C antibacterial agent.
In the embodiment, the modified urea-formaldehyde resin adhesive is prepared by mixing the following components:
urea-formaldehyde resin: 100 portions of
Talc powder: 6 portions of
Tin dioxide: 2 portions of
Zinc sulfide: 1 part of
Ag @ C antibacterial agent: 0.3 part
Sodium butylnaphthalenesulfonate: 1 part of
Polyvinyl alcohol: 3 portions of
Polypropylene glycol diglycidyl ether: 2 portions of
Sodium dodecylbenzenesulfonate: 3 parts of a mixture;
wherein the granularity of the Ag @ C antibacterial agent is 400 meshes.
In this example, the Ag @ C antimicrobial was prepared by the following steps:
a1: reacting p-hydroxybiphenyl with cyanuric chloride to generate a precursor required by the preparation of the carbon material through a hypercrosslinking reaction;
a2: placing the precursor of the carbon material obtained from A1 in a calcining furnace, and calcining the precursor into the carbon material in a nitrogen atmosphere;
a3: and loading silver nanoparticles on the carbon material obtained in the step A2 by an impregnation method to obtain the Ag @ C antibacterial agent.
In the embodiment, in the step A1, 1 part of p-hydroxybiphenyl, 1 part of cyanuric chloride, 5 parts of anhydrous aluminum trichloride and 12 parts of chloroform are uniformly mixed by weight, and the temperature needs to be controlled to be lower than 5 ℃ in the mixing process; heating the mixture to 60 ℃, preserving the heat for 12 hours, and cooling to room temperature; filtering to obtain black solid, washing in 20% hydrochloric acid for 2h, washing in deionized water for 2h, and washing twice; drying for 24 hours in a drying oven at 100 ℃ to obtain a precursor of the carbon material;
in this embodiment, in step a2, the calcination procedure is to heat up to 550 ℃ from room temperature at a rate of 5 ℃/min and keep the temperature for 3 hours, then heat up to 680 ℃ at a rate of 2 ℃/min and keep the temperature for 3 hours, and then naturally cool to room temperature to obtain the carbon material.
In the embodiment, in the step a3, 100g of carbon material is added into 2L of silver nitrate solution with the concentration of 0.1mmol/L to be soaked for 3 hours, and after being filtered and dried, the carbon material is placed into a calcining furnace to be calcined for 2 hours at the temperature of 420 ℃, and then the carbon material is naturally cooled to the room temperature, so that the Ag @ C antibacterial agent is obtained.
In this embodiment, the high-strength composite board with antibacterial and mildewproof functions is manufactured by the following steps:
b1: rotary cutting the wood into thin slices by using a rotary cutter, and feeding the thin slices into a hot-blast stove for drying to obtain a wood veneer;
b2: the modified urea-formaldehyde resin adhesive is sprayed on the surface of a wood veneer by using a glue sprayer, and the single-side gluing amount is 170g/m2(ii) a Bonding 9 layers of wood veneers together by hot pressing according to the principle that the grains of the adjacent layers of wood veneers are mutually vertical;
b3: and naturally cooling the plate obtained in the step B2 to room temperature, and then carrying out static pressure aging.
In this example, in step B1, a rotary cutter was used to rotary cut the wood into 1.5mm thick sheets, and the moisture content of the dried wood veneers was 8%.
In this example, in step B2, the hot pressing temperature was 125 ℃, the pressure was 3.6MPa, and the pressure holding time was 30 min.
In this example, in step B3, the time for the static pressure aging was 18 hours, and the pressure for the static pressure aging was 1 MPa.
Example 4
A high-strength composite board with antibacterial and mildew-proof functions is formed by gluing a plurality of layers of wood veneers, the textures of the wood veneers on the adjacent layers are mutually vertical, and the adhesive used for bonding the wood veneers on the adjacent layers is a modified urea-formaldehyde resin adhesive added with an antibacterial component; the antibacterial component is a compound of silver nanoparticles and a carbon material and is marked as an Ag @ C antibacterial agent.
In the embodiment, the modified urea-formaldehyde resin adhesive is prepared by mixing the following components:
urea-formaldehyde resin: 100 portions of
Talc powder: 5 portions of
Tin dioxide: 52 portions of
Zinc sulfide: 1 part of
Ag @ C antibacterial agent: 0.4 portion of
Sodium butylnaphthalenesulfonate: 0.5 portion
Polyvinyl alcohol: 4 portions of
Polypropylene glycol diglycidyl ether: 2 portions of
Sodium dodecylbenzenesulfonate: 2 parts of (1);
wherein the granularity of the Ag @ C antibacterial agent is 400 meshes.
In this example, the Ag @ C antimicrobial was prepared by the following steps:
a1: reacting p-hydroxybiphenyl with cyanuric chloride to generate a precursor required by the preparation of the carbon material through a hypercrosslinking reaction;
a2: placing the precursor of the carbon material obtained from A1 in a calcining furnace, and calcining the precursor into the carbon material in a nitrogen atmosphere;
a3: and loading silver nanoparticles on the carbon material obtained in the step A2 by an impregnation method to obtain the Ag @ C antibacterial agent.
In the embodiment, in the step A1, 1 part of p-hydroxybiphenyl, 1 part of cyanuric chloride, 5 parts of anhydrous aluminum trichloride and 12 parts of chloroform are uniformly mixed by weight, and the temperature needs to be controlled to be lower than 5 ℃ in the mixing process; heating the mixture to 60 ℃, preserving the heat for 12 hours, and cooling to room temperature; filtering to obtain black solid, washing in 20% hydrochloric acid for 2h, washing in deionized water for 2h, and washing twice; drying for 24 hours in a drying oven at 100 ℃ to obtain a precursor of the carbon material;
in this embodiment, in step a2, the calcination procedure is to heat up to 550 ℃ from room temperature at a rate of 5 ℃/min and keep the temperature for 3 hours, then heat up to 680 ℃ at a rate of 2 ℃/min and keep the temperature for 3 hours, and then naturally cool to room temperature to obtain the carbon material.
In the embodiment, in the step a3, 100g of carbon material is added into 2L of silver nitrate solution with the concentration of 0.1mmol/L to be soaked for 3 hours, and after being filtered and dried, the carbon material is placed into a calcining furnace to be calcined for 2 hours at the temperature of 420 ℃, and then the carbon material is naturally cooled to the room temperature, so that the Ag @ C antibacterial agent is obtained.
In this embodiment, the high-strength composite board with antibacterial and mildewproof functions is manufactured by the following steps:
b1: rotary cutting the wood into thin slices by using a rotary cutter, and feeding the thin slices into a hot-blast stove for drying to obtain a wood veneer;
b2: the modified urea-formaldehyde resin adhesive is sprayed on the surface of a wood veneer by using a glue sprayer, and the single-side gluing amount is 180g/m2(ii) a Bonding 9 layers of wood veneers together by hot pressing according to the principle that the grains of the adjacent layers of wood veneers are mutually vertical;
b3: and naturally cooling the plate obtained in the step B2 to room temperature, and then carrying out static pressure aging.
In this example, in step B1, a rotary cutter was used to rotary cut the wood into 1.6mm thick sheets, and the moisture content of the dried wood veneers was 8%.
In this example, in step B2, the hot pressing temperature was 125 ℃, the pressure was 4.2MPa, and the pressure holding time was 35 min.
In this example, in step B3, the time for the static pressure aging was 24 hours, and the pressure for the static pressure aging was 1.2 MPa.
Comparative example 1
In the production process of the composite board, the Ag @ C antibacterial agent is not added into the urea resin adhesive, and other components and the production method are completely the same as those in the example 4.
Comparative example 2
In the production process of the composite board, the silver nano powder with equal mass is used for replacing the Ag @ C antibacterial agent, and other components and the production method are completely the same as those in the example 4.
Comparative example 3
In the production process of the composite board, silver nitrate with equal quality is used for replacing the Ag @ C antibacterial agent, and other components and the production method are completely the same as those in the example 4.
Comparative example 4
In the production process of the composite board, silver chloride with equal quality is used for replacing the Ag @ C antibacterial agent, and other components and the production method are completely the same as those in example 4.
Comparative example 5
In the production process of the composite plate, activated carbon with equal quality is used for replacing carbon materials prepared by the steps of A1 and A2 in the preparation of the Ag @ C antibacterial agent, and other components and a production method are completely the same as those in example 4.
Comparative example 6
In the production process of the composite plate, activated carbon with equal quality is used for replacing a carbon material prepared in the step A1 in the preparation of the Ag @ C antibacterial agent, and other components and a production method are completely the same as those in example 4.
Comparative example 7
In the production process of the composite plate, equal-quality carbon material prepared by two steps of A1 and A2 is used for replacing the Ag @ C antibacterial agent, and other components and the production method are completely the same as those in example 4.
Performance testing
Comprehensive performance tests were conducted for examples 1 to 4 and comparative examples 1 to 6. The formaldehyde emission, the bonding strength, the bending strength and the antibacterial ratio are shown in table 1, and the mildew resistance is shown in table 2. The formaldehyde emission and the bond strength were tested according to the regulations of GB/T17657-1999. The bending strength was tested according to the specifications of GB/T29418-2012. The mildew-proof performance is tested according to the GB/T18261-2000 specification, the composite board samples with the same size are respectively placed in the environment with the temperature of 25-30 ℃ and the humidity of 65-75%, after 5 weeks, the fungus infection area and the mildew growth condition of the plywood are visually observed, the fungus infection area and the mildew growth condition are observed once every 4 weeks and recorded, and the damage value is graded according to the table 3, so that the mildew-proof effect is evaluated (the specification of the plywood is 200mm multiplied by 200 mm). The antibacterial performance test is that gram-positive staphylococcus aureus and gram-negative escherichia coli are selected as test strains, the two kinds of bacteria are respectively suspended in phosphate buffer solution with the concentration of 100 mu mol/L and the pH value of 7 to prepare required bacterial liquid, the bacterial liquid is dripped on a composite board pattern, superposing the same composite board patterns in a sandwich manner, applying pressure by using a sterile pressing iron to ensure that bacteria fully contact the composite board patterns, placing the antibacterial and mildew-proof wood-plastic composite board prepared in the antibacterial test receiving embodiment into a centrifugal tube of a sterile sodium thiosulfate solution with the concentration of 0.02mol/L after the bacteria contact for 30min, oscillating for 2min, continuously diluting the solution by using a phosphate buffer solution with the concentration of 100 mu mol/L and the pH value of 7, placing the solution in a culture medium, and (4) culturing at a constant temperature of 37 ℃ for 24h, and finally counting the number of surviving bacterial colonies and calculating to obtain the antibacterial rate.
TABLE 1
Figure BDA0002474823270000151
Figure BDA0002474823270000161
TABLE 2
5 weeks 9 weeks 13 weeks 17 weeks For 21 weeks
Example 1 0 0 0 1 1
Example 2 0 0 0 0 1
Example 3 0 0 0 0 0
Example 4 0 0 0 0 0
Comparative example 1 1 1 2 3 4
Comparative example 2 0 1 1 2 3
Comparative example 3 0 1 1 2 4
Comparative example 4 1 1 2 2 3
Comparative example 5 0 1 2 2 3
Comparative example 6 0 1 2 2 3
Comparative example 7 1 1 2 2 4
TABLE 3
Figure BDA0002474823270000162
Figure BDA0002474823270000171
As can be seen from table 1, each example is significantly superior to each comparative example in terms of antimicrobial performance, and further, as analyzed in conjunction with the various comparative examples, the Ag @ C antimicrobial agent is a key factor in the performance of the composite panel in terms of antimicrobial performance, and the antimicrobial performance of the final composite panel product is significantly altered whether the carbon material is omitted, the type of carbon material is changed, or the method of preparation is changed, or the silver-loading step of a3 is omitted, or other forms of silver-containing components are used. As can be seen from table 2, the mildew resistance performance exhibited by each example in the simulated mildew environment is significantly better than that of each comparative example, and the mildew resistance performance of each example and each comparative example has a strong correlation with the antibacterial performance exhibited in table 1. In addition, as can be seen from table 1, each example and each pair of proportions show relatively excellent comprehensive properties in the aspects of formaldehyde emission, bonding strength, bending strength and the like, and no obvious difference is shown between each example and each pair of proportions, which indicates that the manufacturing method provided by the invention has relatively wide applicability, and also indicates that the Ag @ C antibacterial agent specially prepared by the invention does not adversely affect other properties of the composite board while exerting excellent antibacterial and antifungal effects.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that modifications can be made by those skilled in the art without departing from the principle of the present invention, and these modifications should also be construed as the protection scope of the present invention.

Claims (10)

1. The utility model provides a high strength composite sheet with antibiotic mould proof function which characterized in that: the wood veneer is formed by gluing a plurality of layers of wood veneers, the textures of the wood veneers on the adjacent layers are mutually vertical, and the adhesive used for bonding the wood veneers on the adjacent layers is a modified urea-formaldehyde resin adhesive added with an antibacterial component; the antibacterial component is a compound of silver nanoparticles and a carbon material and is marked as an Ag @ C antibacterial agent.
2. The high-strength composite panel having antibacterial and mildewproof functions according to claim 1, wherein: the modified urea-formaldehyde resin adhesive is prepared by mixing the following components:
urea-formaldehyde resin: 100 portions of
Talc powder: 5-8 parts of
Tin dioxide: 1-2 parts of
Zinc sulfide: 1-2 parts of
Ag @ C antibacterial agent: 0.2 to 0.5 portion
Sodium butylnaphthalenesulfonate: 0.5 to 1 portion
Polyvinyl alcohol: 3-4 parts of
Polypropylene glycol diglycidyl ether: 2-3 parts of
Sodium dodecylbenzenesulfonate: 2-3 parts.
3. The high-strength composite panel having antibacterial and mildewproof functions according to claim 1, wherein: the Ag @ C antibacterial agent is prepared by the following steps:
a1: reacting p-hydroxybiphenyl with cyanuric chloride to generate a precursor required by the preparation of the carbon material through a hypercrosslinking reaction;
a2: placing the precursor of the carbon material obtained from A1 in a calcining furnace, and calcining the precursor into the carbon material in a nitrogen atmosphere;
a3: and loading silver nanoparticles on the carbon material obtained in the step A2 by an impregnation method to obtain the Ag @ C antibacterial agent.
4. The high-strength composite board having antibacterial and mildewproof functions according to claim 3, wherein: in the step A1, 1 part of p-hydroxy biphenyl, 1 part of cyanuric chloride, 5 parts of anhydrous aluminum trichloride and 12 parts of chloroform are uniformly mixed by weight, and the temperature is required to be controlled to be lower than 5 ℃ in the mixing process; heating the mixture to 60 ℃, preserving the heat for 12 hours, and cooling to room temperature; filtering to obtain black solid, washing in 20% hydrochloric acid for 2h, washing in deionized water for 2h, and washing twice; and drying for 24 hours in a drying oven at 100 ℃ to obtain the precursor of the carbon material.
5. The high-strength composite board having antibacterial and mildewproof functions according to claim 3, wherein: in the step A2, the calcining procedure is to heat up to 550 ℃ from room temperature at a rate of 5 ℃/min and keep the temperature for 3h, then heat up to 680 ℃ at a rate of 2 ℃/min and keep the temperature for 3h, and then naturally cool to room temperature to obtain the carbon material.
6. The high-strength composite board having antibacterial and mildewproof functions according to claim 3, wherein: in the step A3, 100g of carbon material is added into 2L of silver nitrate solution with the concentration of 0.1mmol/L for soaking for 3h, the carbon material is filtered and dried, then the carbon material is placed into a calcining furnace for calcining for 2h at the temperature of 420 ℃, and the Ag @ C antibacterial agent is obtained after natural cooling to the room temperature.
7. The method for producing a high-strength composite panel having antibacterial and antifungal functions as claimed in any one of claims 1 to 6, wherein: the method comprises the following steps:
b1: rotary cutting the wood into thin slices by using a rotary cutter, and feeding the thin slices into a hot-blast stove for drying to obtain a wood veneer;
b2: the modified urea-formaldehyde resin adhesive is sprayed on the surface of the wood veneer by using a glue sprayer, and the single-side glue coating amount is 160-180g/m2(ii) a 5-11 layers of wood veneers are bonded together by hot pressing according to the principle that the grains of the wood veneers on the adjacent layers are mutually vertical;
b3: and naturally cooling the plate obtained in the step B2 to room temperature, and then carrying out static pressure aging.
8. The method for producing a high-strength composite panel having antibacterial and mildewproof functions according to claim 7, wherein the method comprises the following steps: in step B1, the wood is rotary cut into slices with thickness of 1.2-1.8mm by a rotary cutter, and the moisture content of the dried wood veneer is 7-9%.
9. The method for producing a high-strength composite panel having antibacterial and mildewproof functions according to claim 7, wherein the method comprises the following steps: in the step B2, the hot-pressing temperature is 125-.
10. The method for producing a high-strength composite panel having antibacterial and mildewproof functions according to claim 7, wherein the method comprises the following steps: and in the step B3, the static pressure aging time is 12-24h, and the pressure of the static pressure aging is 0.8-1.2 Mpa.
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