CN114181659A - Adhesive and application thereof - Google Patents

Adhesive and application thereof Download PDF

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Publication number
CN114181659A
CN114181659A CN202111554464.3A CN202111554464A CN114181659A CN 114181659 A CN114181659 A CN 114181659A CN 202111554464 A CN202111554464 A CN 202111554464A CN 114181659 A CN114181659 A CN 114181659A
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Prior art keywords
component
adhesive
triethanolamine
mass
atomization
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CN202111554464.3A
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Inventor
范丽颖
涂松
胡兵波
张梓军
孙鹏
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Wanhua Chemical Group Co Ltd
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Wanhua Chemical Group Co Ltd
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Priority to CN202111554464.3A priority Critical patent/CN114181659A/en
Publication of CN114181659A publication Critical patent/CN114181659A/en
Priority to CN202211068852.5A priority patent/CN115160973B/en
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04Polyurethanes
    • C09J175/08Polyurethanes from polyethers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B27WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27NMANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N1/00Pretreatment of moulding material
    • B27N1/02Mixing the material with binding agent
    • B27N1/0209Methods, e.g. characterised by the composition of the agent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B27WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27NMANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N3/00Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/002Manufacture of substantially flat articles, e.g. boards, from particles or fibres characterised by the type of binder
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B27WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
    • B27NMANUFACTURE BY DRY PROCESSES OF ARTICLES, WITH OR WITHOUT ORGANIC BINDING AGENTS, MADE FROM PARTICLES OR FIBRES CONSISTING OF WOOD OR OTHER LIGNOCELLULOSIC OR LIKE ORGANIC MATERIAL
    • B27N3/00Manufacture of substantially flat articles, e.g. boards, from particles or fibres
    • B27N3/08Moulding or pressing
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/50Polyethers having heteroatoms other than oxygen
    • C08G18/5021Polyethers having heteroatoms other than oxygen having nitrogen
    • C08G18/5024Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00Compositions for adhesives
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Wood Science & Technology (AREA)
  • Forests & Forestry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention relates to an adhesive and application thereof, wherein the adhesive comprises a component A and a component B; the component A comprises polymethylene polyphenyl polyisocyanate and/or polymethylene polyphenyl polyisocyanate-based polyurethane; the component B comprises a combination of triethanolamine, diethanolamine, monoethanolamine and triethanolamine derivatives; the total mass percentage of the triethanolamine, the diethanolamine and the monoethanolamine is 50-90% based on 100% of the total mass of the component B; the triethanolamine derivative accounts for 10-50% by mass; in the polymethylene polyphenyl polyisocyanate, the functionality of isocyanate is at least 2, and the number of methylene is at least 2. The adhesive disclosed by the invention is used in a base material, particularly a wood material, and has the characteristics of high curing speed, no edge breakage and difficulty in cracking after being pasted.

Description

Adhesive and application thereof
Technical Field
The invention relates to the technical field of adhesives, and particularly relates to an adhesive and application thereof.
Background
Currently, synthetic adhesives for artificial boards are formaldehyde-based adhesives, including "tri-aldehyde adhesives" represented by urea-formaldehyde resins, phenol-formaldehyde resins, melamine-formaldehyde resins, and the like. The three adhesives all adopt formaldehyde as a synthetic raw material, and the adhesive bonding product has formaldehyde escaping in the production and use processes, so that the adhesive bonding product is regarded as one of main sources of indoor air pollution, has long pollution period and is difficult to remove fundamentally.
Due to environmental concerns, aldehyde-free isocyanate adhesives have become more and more widely used in recent years. Besides containing no formaldehyde, the isocyanate adhesive has many advantages, such as high adhesive bonding strength, low adhesive consumption, low requirement on water content of the wood straw material, excellent board physical properties and the like.
However, the use of isocyanates as adhesives in wood-based panels also has disadvantages. The hot pressing process involves complex energy changes, including heat and mass transfer processes. The surface layer is preferentially heated, and the water in the unit is heated into water vapor to carry heat to the core layer for transmission. And (3) along with the prolonging of time, the temperature of the core layer rises, and after the curing temperature of the adhesive is reached, the adhesive is cured and molded under the action of pressure. Because the wood material is a poor conductor of heat, the main heat transfer during hot pressing is carried by water vapor. Under the condition of producing the board with the same density, the board blank adopting the isocyanate adhesive has slower heat transfer due to different using amounts of the wood raw materials. In general, when the water content of the pavement is the same, the time for raising the temperature of the core layer of the three-aldehyde glue slab to 100 ℃ is 5-10s shorter than that of the time for raising the temperature of the core layer of the three-aldehyde glue slab to 100 ℃ by adopting isocyanate glue. The main factors for restricting the hot pressing efficiency are that the temperature rise speed of the core layer and the curing speed of the adhesive are also important factors, and the curing speed of the isocyanate adhesive at 100 ℃ is about 30 seconds slower than that of the urea-formaldehyde resin.
Therefore, by combining the two points, the hot pressing efficiency of the shaving board adopting the isocyanate adhesive is reduced by 35-50% compared with that of the shaving board adopting the urea-formaldehyde resin. The problem can greatly influence the production efficiency and the benefit of a production factory, and the development and the expansion of the industry for producing the formaldehyde-free added artificial board by adopting the isocyanate adhesive are seriously hindered.
The problem is solved, the heat transfer speed of the core layer can be effectively improved by adjusting the pavement water content gradient and improving the hot pressing temperature, and the hot pressing efficiency is improved to a certain extent. However, how to improve the curing speed of the isocyanate adhesive is still a major problem which restricts the production efficiency of the board.
CN1196374A discloses a process for preparing a binder for lignocellulosic pressboards, which process comprises bringing a first stream consisting of (A) an organic isocyanate compound and a second stream consisting of (B) a reactive emulsifier and (C) an emulsifying medium and optionally a mould release agent, at an elevated pressure of 40-300kg/cm2Lower jet into the mixing chamber and then mix them. Since the binder disclosed therein has excellent releasability at the time of hot pressing, the binder is suitable for industrial production of high-quality and inexpensive lignocellulose pressed boards having excellent productivity. According to the scheme, the agent B and the agent C are mainly synthesized into an emulsifier, and react with the agent A in advance to generate an emulsifiable isocyanate adhesive, and then the emulsifiable isocyanate adhesive is mixed with water to improve the sizing uniformity, but the scheme can cause serious precuring of an adhesive system, and when a plate is not formed, a large amount of effective components of the adhesive react, so that the production efficiency of the plate can be seriously influenced.
Meanwhile, when the isocyanate adhesive is used for producing the shaving board, due to the problems of low consumption of the adhesive, high hardness after curing and the like, the phenomena of easy edge breakage and easy cracking after facing are easily caused when the non-aldehyde added artificial board is produced by using the isocyanate adhesive.
In conclusion, there is an urgent need to develop an adhesive, which has the characteristics of high curing speed, no edge breakage and no cracking after being pasted when being used for producing an artificial board without aldehyde addition.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an adhesive and application thereof, wherein when the adhesive is used for producing an artificial board without aldehyde addition, the adhesive is used in a base material, especially a wood material, and has the characteristics of high curing speed, no edge breakage and difficult cracking after facing.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an adhesive, comprising a component a and a component B;
the component A comprises polymethylene polyphenyl polyisocyanate and/or polymethylene polyphenyl polyisocyanate derivatives;
the component B comprises a combination of triethanolamine, diethanolamine, monoethanolamine and triethanolamine derivatives;
the total mass percentage of the triethanolamine, the diethanolamine and the monoethanolamine is 50-98%, such as 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% and the like, based on 100% of the total mass of the component B;
the triethanolamine derivative is 2-50% by mass, such as 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45% and the like;
the polymethylene polyphenyl polyisocyanates have an isocyanate functionality of at least 2 (e.g., 2, 3, 4, etc.) and a methylene number of at least 2 (e.g., 2, 3, 4, etc.).
In the invention, the adhesive comprises a component A and a component B, wherein the component A comprises polymethylene polyphenyl polyisocyanate and/or polyol modifier (polyurethane) thereof, is a main component of the adhesive and belongs to an aldehyde-free adhesive; the component B comprises three kinds of alcohol amines and derivatives of one kind of alcohol amine, and is used by matching with the component A, because the reaction activities of the components in the component B are different and the reaction products are different, when the components are matched under a specific proportion, the curing speed of an adhesive system can be effectively improved, the curing speed of the adhesive system is improved, the total mass of the ethanolamine, the diethanolamine and the monoethanolamine is too high, the hardness of the reaction products of the adhesive system is high, and the processing performance of the plate is poor; the proportion is too light, the curing speed of an adhesive system is reduced, so that the formed aldehyde-free adhesive has the characteristics of high curing speed, no edge breakage and difficult cracking after the adhesive is pasted.
Preferably, the structure of the triethanolamine derivative is shown as formula I:
Figure BDA0003418705940000041
wherein a, b and c are each a positive integer of 0 to 20 (e.g., 2, 4, 6, 8, 10, 12, 14, 16, 18, etc.), and at least one of a, b and c is not 0, and more preferably at least one of a, b and c is 2 to 5 (e.g., 3, 4, etc.).
The structure of the triethanolamine derivative is shown as a formula I, at least one ether bond is arranged in the structure, when a hot-press formed plate is subjected to external force, the ether bond can rotate, the external force has a good absorption and buffering effect, the flexibility of a molecular chain of the cured adhesive is improved, the process phenomena of edge breakage and the like in the cutting and processing process of the plate are improved, and the processing performance of the plate is improved.
Preferably, the triethanolamine derivative has a number average molecular weight of 200-3000g/mol (e.g., 500g/mol, 1000g/mol, 1500g/mol, 2000g/mol, 2500g/mol, etc.), and more preferably 300-1000g/mol (e.g., 400g/mol, 500g/mol, 600g/mol, 700g/mol, 800g/mol, 900g/mol, etc.).
Preferably, the mass percentage of the triethanolamine, diethanolamine, and monoethanolamine is 75% to 90%, such as 76%, 78%, 80%, 82%, 84%, 86%, 88%, etc., based on 100% of the total mass of the B component.
The triethanolamine derivative is 10-25% by mass, such as 12%, 14%, 16%, 18%, 20%, 22%, 24% and the like.
In the invention, the mass percentage of the triethanolamine, the diethanolamine and the monoethanolamine is further preferably 75-90% based on 100% of the total mass of the component B, because in the proportion range, the curing rate of the adhesive system and the proportion of the cured product can best meet the requirements of plate production and processing performance.
Preferably, the preparation raw material of the triethanolamine derivative comprises triethanolamine and ethylene oxide.
Preferably, the mass ratio of the triethanolamine to the ethylene oxide is 1 (1-20), wherein 1-20 can be 2, 4, 6, 8, 10, 12, 14, 16, 18 and the like, and 1 (3-10) is further preferred.
Illustratively, the preparation method of the triethanolamine derivative is that triethanolamine and ethylene oxide are subjected to polymerization reaction and post-treatment by a polyether adsorbent.
Preferably, the mass ratio of the A component to the B component is (3-15):1, wherein 3-15 can be 4, 6, 8, 10, 12, 14, and the like.
In the invention, the mass ratio of the component A to the component B is (3-15):1, and the reason for selecting the range is that the mass ratio of the component A to the component B is too high according to the balance between the use effect and the production cost, and the curing speed of an adhesive system is slow, so that the production capacity is influenced; the mass ratio of the two is too low, the curing speed of the adhesive system is too high, the pre-curing phenomenon is easy to occur, the effective components of the adhesive system are caused to react in advance, the production efficiency is reduced, and the integral dosage of the adhesive system is increased.
In the present invention, the polymethylene polyphenyl polyisocyanate and its derivatives in the A component are selected from Wannate series polyisocyanates of Wanhua chemical group GmbH, including any one or a combination of at least two of PM-100, PM-200, PM-400, PM-600, PM-700, CW20, CW30, PM300E or 9132FC, wherein typical but non-limiting combinations include: combinations of PM-100 and PM-200, combinations of PM-400, PM-600, and PM-700, combinations of CW20, CW30, PM300E, and 9132FC, and the like.
Preferably, the A component has an average functionality of 2.1 to 3.2 (e.g., 2.4, 2.6, 2.8, 3.0, etc.) and a mass percent of isocyanate groups of 16% to 33% (e.g., 18%, 20%, 22%, 24%, 26%, 28%, 30%, 32%, etc.). The mass percent of the isocyanate refers to the total proportion of the isocyanate related to the component A.
Preferably, the A component has a viscosity of 30-3000cp, e.g. 500cp, 1000cp, 1500cp, 2000cp, 2500cp, etc., at 25 ℃.
Preferably, the polymethylene polyphenyl polyisocyanate includes any one of diphenylmethane diisocyanate, triphenylmethane triisocyanate or polymethylene polyphenyl polyisocyanates having a functionality greater than three, or a combination of at least two thereof.
Preferably, the component A comprises the following components in percentage by mass of 100 percent of the total mass: 40% -60% (e.g., 42%, 44%, 46%, 48%, 50%, 52%, 54%, 56%, 58%, etc.) of diphenylmethane diisocyanate and/or polyurethane thereof, 25% -35% (e.g., 26%, 28%, 30%, 32%, 34%, etc.) of triphenylmethane triisocyanate and/or polyurethane thereof, and up to 100% of polymethylene polyphenyl polyisocyanate and/or polyurethane thereof having a functionality greater than three.
In a second aspect, the present invention provides an artificial board made of wood shavings, the artificial board comprising at least three layers of substrates;
the wood shavings are bonded by the adhesive of the first aspect.
Preferably, the total mass of the a component in the adhesive is 1% to 10% (e.g., 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 6%, 7%, 8%, 9%, etc.) based on 100% of the total mass of the substrate.
In a third aspect, the present invention provides a method for preparing an artificial board according to the second aspect, comprising the following steps:
and (3) respectively and independently applying the component A and the diluted component B, or respectively and independently applying the diluted component B and the diluted component A to at least two layers of base materials, and laminating the base materials containing the adhesive to obtain the artificial board.
Preferably, the diluent of the B-component comprises water.
Preferably, the mass ratio of the B component to water is (0.2-1):1, wherein 0.2-1 may be 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, etc.
Preferably, the manner in which the a and B components are applied to the substrate comprises atomization.
Preferably, the atomization comprises rotary atomization and/or high pressure atomization.
Preferably, the high pressure atomization is at a pressure of 2-30bar (e.g. 4bar, 5bar, 10bar, 15bar, 20bar, 25bar, etc.).
Preferably, the rotational atomization speed is 9000r/min to 11000r/min (e.g., 9500r/min, 1000r/min, 10500r/min, etc.).
In the invention, the application fields of the component A and the component B are selected from a closed roller or a closed cavity with a stirring paddle, which can complete stirring and mixing, so that the corresponding adhesive system and the artificial board base material unit are mixed more uniformly.
Preferably, the stacking manner includes pre-pressing and hot-pressing.
Preferably, the hot pressing temperature is 180-240 ℃, such as 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃ and the like.
Preferably, the pressure of the hot pressing is 0.5 to 5MPa, such as 1MPa, 1.5MPa, 2MPa, 2.5MPa, 3MPa, 3.5MPa, 4MPa, 4.5MPa, and the like.
Preferably, the pre-pressing is completed until the thickness of the base material is reduced by more than 30% (e.g., 32%, 34%, 36%, 38%, etc.).
In the invention, the base material comprises a plurality of raw material components, can be conventional wood, including wood particles and wood shavings produced by crushing poplar, pine, eucalyptus and the like, and can also be particles processed by non-wood units such as wheat, rice, bagasse, cotton stalks, reed and the like.
Preferably, the substrate comprises a wood material, further preferably a lignocellulosic material, most preferably a raw substrate for the production of particle board or oriented strand board.
Preferably, the wood material comprises wood shavings and/or straw shavings.
Preferably, the adhesive system is applied to all substrates.
Preferably, the artificial board base material unit added with the adhesive system is subjected to layered paving to prepare the board.
When the device is operated in a laboratory, the bottom layer material is paved on the metal base plate processed by the release agent, and is limited by the box body die with the limited size, so that the redundant material is prevented from scattering at the edge. After the adhesive is applied, the paving link should be performed at a low temperature as far as possible. Before pressing, the base material and the adhesive system are fully contacted and exposed in the air, the longer the time is, the larger the isocyanate pre-curing degree is, the adhesive for effectively bonding the base material is directly reduced, and the mechanical property of the formed plate is reduced. Since each process of the sheet making operation requires a certain time, the hot pressing is preferably performed within 1 hour (e.g., 0.8 hour, 0.7 hour, 0.6 hour, 0.5 hour, 0.2 hour, etc.) after the sizing, more preferably within 0.5 hour, and further preferably within 15 minutes.
In industrial production, an adhesive system is separately applied to a roller glue mixer, a ring glue mixer or a mushroom head glue mixer through a rotary atomizer, an air atomization nozzle or a high-pressure atomization nozzle respectively, and preferably, diluted agent B and process water are mixed through a static mixer and then applied to a dried artificial board substrate through a sizing nozzle or a rotary atomizer. After the material is placed in the packing box, the temperature of the material is maintained at 30-50 deg.C (e.g., 32 deg.C, 34 deg.C, 36 deg.C, 38 deg.C, 40 deg.C, 42 deg.C, 44 deg.C, 46 deg.C, 48 deg.C, etc.), more preferably 35-45 deg.C. The time of the material in the paving box is not more than 0.5 hour (such as 0.4 hour, 0.3 hour, 0.2 hour and the like), more preferably not more than 20 minutes, and even more preferably 5-10 minutes.
The base material unit is paved by using a paving head or a paving roller, and the paving water content is 12% -20% (such as 14%, 16%, 18% and the like) of the surface layer, 2% -6% (such as 3%, 4%, 5% and the like) of the core layer, more preferably 16% -18% of the paving water content of the surface layer, and 3.5% -4.5% of the core layer.
And (3) prepressing the paved plate blank before the plate blank enters a hot press to ensure that the plate blank has a relatively compact structure, internal gas is discharged, and the compression thickness is not less than 30% (such as 32%, 34%, 36%, 38% and the like).
Preferably, the slab is heated by microwave equipment, high temperature steam equipment, and high temperature air equipment before pre-pressing, and the core temperature is raised to 50-70 deg.C (such as 52 deg.C, 56 deg.C, 58 deg.C, 60 deg.C, 62 deg.C, 64 deg.C, 66 deg.C, and 68 deg.C), more preferably 55-60 deg.C.
The slab after paving and prepressing enters a press for hot pressing, the hot pressing temperature is 180 ℃ and 240 ℃ (such as 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃ and the like), the hot pressing pressure is 0.5-5MPa (1MPa, 1.5MPa, 2MPa, 2.5MPa, 3MPa, 3.5MPa, 4MPa, 4.5MPa and the like), and the preferable pressure is 0.5-3 MPa.
And (3) cutting the rough edges of the plate blank after hot pressing, cutting the plate blank into a fixed size according to requirements, ageing, and then sanding, veneering and the like to obtain a final product.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) mixing the component B with water according to the mass ratio of (0.2-1) to 1 to obtain a diluted component B;
(2) applying the component A and the diluted component B or the diluted component B and the diluted component A to at least two layers of wood materials respectively in an atomization mode;
(3) laminating and paving the wood material containing the adhesive, prepressing until the thickness of the wood material is reduced by more than 30 percent, and hot-pressing under the conditions that the temperature is 180-240 ℃ and the pressure is 0.5-5MPa to obtain the artificial board.
Compared with the prior art, the invention has the following beneficial effects:
(1) by adopting the adhesive system disclosed by the invention, the hot pressing time can be greatly reduced to improve the production efficiency, the production efficiency can be improved by 15-40%, meanwhile, the problems of virtual edges, softening, dark layering and the like at the edge part of a plate blank can be effectively solved, the paving width can be effectively reduced by 4-8cm, and the consumption of raw materials can be saved by 2-8%. Can greatly improve the production efficiency and reduce the cost of raw materials, production and financial affairs. And simultaneously, the problem that the edge is easy to collapse when the edge is sawed and the problem that impregnated paper is cracked after the surface is pasted is solved.
(2) The adhesive has the internal bonding strength with a base material of 0.31-0.71MPa, the 2h-TS of 2.98-4.18%, the static bending strength of 12.05-14.38MPa, the elastic modulus of 1905-2132MPa, the hot pressing factor of 5 or less, the number of cracks appearing in 30 blocks of 4 or less, the length of 30cm of 3 or less.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The sodium ion-containing polyisocyanate and/or polyol modified derivative thereof and the sources of the alcohol amine and the small molecular weight polyol related in the embodiment of the invention are as follows:
a1: the mixture of sodium ion-containing polyfunctional isocyanate and diphenylmethane diisocyanate has NCO content of 30.5-32.0%, functionality of 3.1-3.3, viscosity of 150-250cp at 25 ℃, iron content of less than or equal to 20ppm, sodium ion content of 5-15ppm, Vanhua chemical group Limited company with the trade name CW 20;
a2: a polyfunctional isocyanate derivative containing sodium ions, having an NCO content of 28.5 to 30.0 percent, a functionality of 2.9 to 3.1, a viscosity of 300 and 400cp at 25 ℃, a sodium ion content of 5 to 10ppm, and a mark of 9132FC by Wanhua chemical group Limited;
alcohol amine:
triethanolamine: industrially pure, Hubei Xiangliang chemical Limited;
diethanolamine: industrially pure, Hubei Xiangliang chemical Limited;
ethanolamine: industrially pure, Hubei Xiangliang chemical Limited;
ethylene oxide: industrially pure, Hubei Xiangliang chemical Limited;
sodium hydroxide: industrial purity, Shandong hongxiang chemical Co., Ltd;
magnesium silicate: industrial purity, Hubei Xingdong Chengcheng chemical Co., Ltd;
wood raw material: particle board, super-strong particle board uses surface core layer raw material, water content is about 2-3 wt%, poplar, miscellaneous tree, eucalyptus, etc., purchased from Wanhua fragrant wood board (Jingmen) Limited, and its brand is 20210125;
releasing agent: the brand is KC201, Wanhua chemical;
tackifier: the trade mark is KC367, Wanhua chemical.
The preparation method in the embodiment of the invention comprises two methods of preparing the particle boards in a laboratory and producing the particle boards in a factory.
Preparing a shaving board in a laboratory:
the wood shavings with certain mass are poured into a sealed cylinder with stirring equipment, and the material is added by utilizing an air atomization mode. The component A is added independently, and the component B is added after being diluted by process water needing to be added. Ensuring that the adhesive component is applied uniformly to the strands. The water content of the surface layer wood shavings is 17-18 wt%, and the water content of the core layer wood shavings is 3.5-4.5 wt%.
Placing a 50 x 50cm stainless steel metal base plate into a hot press, preheating, spraying a demolding agent, and paving a shaving board in a 35 x 30cm box body die in a manual paving mode, wherein the paving amounts of a surface core layer are 320g, 970g and 320g respectively. And hot pressing after paving, wherein the thickness is 18 mm. The hot pressing process adopts 3-section pressure, which is divided into a high section, a low section and a middle section, and the hot pressing pressure is respectively 3MPa, 1.5MPa and 0.5MPa, and the pressure maintaining time ratio is 4: 4: 3, the hot pressing factor is 5s/mm (adjusted according to different plates), and the hot pressing temperature is 230 ℃.
The method comprises the following steps of (1) preparing shaving boards in factories:
drying the water content of the wood shavings of the surface core layer to about 2%, then screening the wood shavings and respectively conveying the wood shavings to a glue applicator of the surface core layer, independently adding the agent A into the glue mixer through a glue applying nozzle or a rotary atomizer, diluting the agent B independently or adding the agent B into the glue mixer through a static mixer and then through the glue applying nozzle or the rotary atomizer. The wood shavings after glue application are conveyed into a paving bin through a scraper blade or a belt conveyor, and are paved on a belt through a paving head or a paving roller, wherein the paving proportion of a lower surface layer, a core layer and an upper surface layer is respectively 17.2%, 65% and 17.8% by taking a plate with the thickness of 18mm as an example. The paved plate enters a hot press after being pre-pressed, the temperature of the hot press is gradually reduced from 240 plus 190 ℃ according to the temperature interval distribution, the hot pressing pressure is adjusted from 3.5 to 0.5MPa according to the frame distribution, and the hot pressing speed is adjusted according to the specific hot pressing condition of the plate.
Example 1
The embodiment provides an adhesive, which comprises a component A and a component B in a mass ratio of 3.2: 0.6;
the component A comprises: a mixture of sodium ion-containing polyfunctional isocyanate and diphenylmethane diisocyanate, a raw material A1;
and B component: composed of triethanolamine, diethanolamine, monoethanolamine and triethanolamine derivatives;
the mass percent of the triethanolamine, the diethanolamine and the monoethanolamine is 90% (based on the total mass of the triethanolamine, the diethanolamine and the monoethanolamine being 100%, the triethanolamine is 92%, the diethanolamine is 6% and the monoethanolamine is 2%);
the triethanolamine derivative is 10% by mass, and the structural formula is as follows:
Figure BDA0003418705940000121
wherein the average values of a, b and c are each 13.55.
The synthesis process of the triethanolamine derivative is as follows, adding 50% aqueous solution prepared from triethanolamine and potassium hydroxide into a reaction kettle, heating to 130 ℃, vacuum dehydrating for 2 hours, then adding ethylene oxide, cooling to 80 ℃ after reaction is completed at 135-140 ℃, adding distilled water, phosphoric acid and polyether adsorbent, heating to 120 ℃, dehydrating for 2 hours, cooling to 80 ℃ and discharging. The weight ratios of the substances are shown in the table below
TABLE 1
Components Triethanolamine Potassium hydroxide Ethylene oxide Distilled water Phosphoric acid Polyether adsorbent
Weight ratio of 1 0.084 12 1.88 0.19 0.38
Example 2
The embodiment provides an adhesive, which comprises a component A and a component B in a mass ratio of 3.2: 0.6;
the component A comprises: a mixture of sodium ion-containing polyfunctional isocyanate and diphenylmethane diisocyanate, a raw material A1;
and B component: composed of triethanolamine, diethanolamine, monoethanolamine and triethanolamine derivatives;
the mass percent of the triethanolamine, the diethanolamine and the monoethanolamine is 85% (based on the total mass of the triethanolamine, the diethanolamine and the monoethanolamine being 100%, the triethanolamine is 92%, the diethanolamine is 6% and the monoethanolamine is 2%);
the triethanolamine derivative is 15% by mass and has the following structural formula:
Figure BDA0003418705940000131
wherein the average values of a, b and c are each 9.03.
The synthesis process of the triethanolamine derivative is as follows, adding 50% aqueous solution prepared from triethanolamine and potassium hydroxide into a reaction kettle, heating to 130 ℃, vacuum dehydrating for 2 hours, then adding ethylene oxide, cooling to 80 ℃ after reaction is completed at 135-140 ℃, adding distilled water, phosphoric acid and polyether adsorbent, heating to 120 ℃, dehydrating for 2 hours, cooling to 80 ℃ and discharging. The weight ratios of the substances are shown in the table below
TABLE 2
Components Triethanolamine Potassium hydroxide Ethylene oxide Distilled water Phosphoric acid Polyether adsorbent
Weight ratio of 1 0.058 8 1.30 0.13 0.26
Example 3
The embodiment provides an adhesive, which comprises a component A and a component B in a mass ratio of 3.2: 0.6;
the component A comprises: mixing sodium ion-containing polyfunctional isocyanate with diphenylmethane diisocyanate, and obtaining a raw material A1;
the mass percent of the triethanolamine, the diethanolamine and the monoethanolamine is 80% (based on the total mass of the triethanolamine, the diethanolamine and the monoethanolamine being 100%, the triethanolamine is 92%, the diethanolamine is 6% and the monoethanolamine is 2%);
the triethanolamine derivative has the following structural formula, wherein the weight percentage of the triethanolamine derivative is 20 percent:
Figure BDA0003418705940000141
wherein the average values of a, b and c are each 4.52.
The synthesis process of the triethanolamine derivative is as follows, adding 50% aqueous solution prepared from triethanolamine and potassium hydroxide into a reaction kettle, heating to 130 ℃, vacuum dehydrating for 1 hour, then adding ethylene oxide, cooling to 80 ℃ after reaction is completed at 135-140 ℃, adding distilled water, phosphoric acid and polyether adsorbent, heating to 120 ℃, dehydrating for 1 hour, cooling to 80 ℃ and discharging. The weight ratios of the respective substances are shown in the following table.
TABLE 3
Components Triethanolamine Potassium hydroxide Ethylene oxide Distilled water Phosphoric acid Polyether adsorbent
Weight ratio of 1 0.032 4 0.72 0.072 0.14
Example 4
The embodiment provides an adhesive, which comprises a component A and a component B in a mass ratio of 3.2: 0.6;
the component A comprises: mixing sodium ion-containing polyfunctional isocyanate with diphenylmethane diisocyanate, and obtaining a raw material A1; sodium ion-containing polyfunctional isocyanate derivative and a raw material A2, wherein the mass ratio of the sodium ion-containing polyfunctional isocyanate derivative to the raw material A2 is 1.4:1.8, A1 is applied to a surface layer raw material, and A2 is applied to a core layer material;
the component B is the same as in example 1;
example 5
The embodiment provides an adhesive, which comprises a component A and a component B in a mass ratio of 3.2: 0.6;
the component A comprises: mixing sodium ion-containing polyfunctional isocyanate with diphenylmethane diisocyanate, and obtaining a raw material A1; sodium ion-containing polyfunctional isocyanate derivative and a raw material A2, wherein the mass ratio of the sodium ion-containing polyfunctional isocyanate derivative to the raw material A2 is 1.4:1.8, A1 is applied to a surface layer raw material, and A2 is applied to a core layer material;
the component B is the same as in example 2;
example 6
The embodiment provides an adhesive, which comprises a component A and a component B in a mass ratio of 3.2: 0.6;
the component A comprises: mixing sodium ion-containing polyfunctional isocyanate with diphenylmethane diisocyanate, and obtaining a raw material A1; sodium ion-containing polyfunctional isocyanate derivative and a raw material A2, wherein the mass ratio of the sodium ion-containing polyfunctional isocyanate derivative to the raw material A2 is 1.4:1.8, A1 is applied to a surface layer raw material, and A2 is applied to a core layer material;
the component B is the same as in example 3;
example 7
The embodiment provides an adhesive, which comprises a component A and a component B in a mass ratio of 3.2: 0.5;
the component A comprises: mixing sodium ion-containing polyfunctional isocyanate with diphenylmethane diisocyanate, and obtaining a raw material A1;
the B component was the same as in example 3.
Example 8
The embodiment provides an adhesive, which comprises a component A and a component B in a mass ratio of 3.2: 0.5;
the component A comprises: mixing sodium ion-containing polyfunctional isocyanate with diphenylmethane diisocyanate, and obtaining a raw material A1; sodium ion-containing polyfunctional isocyanate derivative and a raw material A2, wherein the mass ratio of the sodium ion-containing polyfunctional isocyanate derivative to the raw material A2 is 1.3:2.0, A1 is applied to a surface layer raw material, and A2 is applied to a core layer material;
the B component was the same as in example 3.
Examples 9 to 10
Examples 9 to 10 are different from example 1 in that the triethanolamine derivative was 2% (example 9) and 50% (example 10) in percentage by mass, respectively, and the rest was the same as example 1.
Comparative example 1
This comparative example differs from example 1 in that the B component is not included, and the rest is the same as example 1.
Comparative example 2
This comparative example differs from example 4 in that the B component is not included, and the rest is the same as example 1.
Comparative examples 3 to 4
Comparative examples 3 to 4 are different from example 1 in that the triethanolamine derivative was 1% (comparative example 3) and 55% (comparative example 4) in mass%, respectively, and the rest was the same as example 1.
Application example 1
The application example provides an artificial board, wherein the artificial board is wood shavings which consist of a surface layer and a core layer;
the wood materials are bonded by the adhesive in the embodiment 1, wherein the addition mass of the component B is 0.6 percent of that of the wood shavings.
The artificial board is prepared by pressing a board by adopting a preparation scheme of a shaving board in a laboratory, and the hot pressing factor is 5 s/mm.
Application examples 2 to 6
The difference between the application example and the application example 1 is that the adhesive is the adhesive described in the embodiments 2-6, the details are shown in the table 1, and the rest is the same as the application example 1.
Application example 7
The application example provides an artificial board, wherein the artificial board is wood shavings which consist of a surface layer and a core layer;
the wood materials are bonded by the adhesive in the embodiment 7, wherein the addition mass of the component B is 0.5 percent of that of the wood shavings.
The artificial board is prepared by pressing a board by adopting a scheme of producing a shaving board in a factory.
Application example 8
The difference between the application example and the application example 7 is that the adhesive is the adhesive described in the embodiment 8, and the rest is the same as the application example 7.
Application examples 9 to 10, application comparative examples 1 to 4, and application comparative examples 5 to 6
Application examples 9 to 10, application comparative examples 1 to 4, and application comparative examples 5 to 6 are different from application example 1 in that the adhesives were the adhesives described in examples 9 to 10, comparative examples 1 to 4, and comparative examples 5 to 6, respectively, and the rest was the same as application example 1.
Comparative application example 5
The comparative application example is different from the comparative application example 3 in the preparation method, and the rest is the same as the comparative application example 3, and the comparative application example is the same as the application example 7.
Comparative application example 6
The comparative application example is different from the comparative application example 4 in the preparation method, the rest is the same as the comparative application example 4, and the comparative application example is the same as the comparative application example 7.
Performance testing
The artificial boards in application examples 1-10 and application comparative examples 1-6 are tested according to GB/T17657-2013, the specific parameters of the boards are summarized in Table 1, and the test results are summarized in tables 4-6.
TABLE 4
Figure BDA0003418705940000171
Figure BDA0003418705940000181
Note: the dosage of the component A and the component B are the weight ratio of absolutely dry wood shavings, and the weight ratio of absolutely dry wood shavings of the surface core layer is 4: 6.
When the hot pressing factor is produced, the product performance reaches the quality standard of a factory, the hot pressing factor can be continuously and stably produced, the hot pressing factor reflects the curing efficiency of the adhesive system, and the lower the hot pressing factor is, the higher the curing efficiency of the adhesive system is.
TABLE 5
Figure BDA0003418705940000182
Figure BDA0003418705940000191
TABLE 6
Figure BDA0003418705940000192
The curing degree of the adhesive is mainly reflected in the internal bonding strength and the thickness of the plate, and has a certain correlation with static bending strength and elastic modulus, but the influence is not obvious in the internal bonding strength.
The processing performance of the plate is mainly reflected in whether the plate is cracked or not and whether cracks appear or not after veneering, and the plate with good processing performance is not subjected to the conditions of cracking and cracking.
The data in tables 4-5 are analyzed, and the adhesive disclosed by the invention has the characteristics of high curing speed, no edge breakage and difficulty in cracking after being pasted when being used for a base material, particularly a wood material, the internal bonding strength of the adhesive and the base material is 0.31-0.71MPa, the 2h-TS is 2.98-4.18%, the static bending strength is 12.05-14.38MPa, the elastic modulus is 1905-2132MPa, the hot pressing factor is below 5, the number of cracks appearing in 30 blocks is below 4, the length of 30cm is within the range, and the number of edge breakage is below 3.
Analysis of application examples 1 and 2 and application comparative example 1 shows that, under the condition of not adding the component B of the adhesive, the curing speed is higher and the plate performance is better by using the adhesive provided by the invention, but under the condition of not adding the component B, the plate processing performance is poor and the problems of edge breakage and cracking are easy to occur.
The above conclusion can be similarly obtained by analyzing application example 4, application example 5 and application comparative example 2.
As shown in data in Table 6, the adhesive system of the invention can be applied to the industrial production of artificial boards, and the problems of poor processing performance and easy occurrence of edge chipping and cracking of boards can be found under the condition of not adding the component B.
According to the application example 7 and the application comparative example 5, according to the result of the hot pressing factor, when the agent A of the core layer in the adhesive system is A2, and the amount of the component B is 0.5% of the dry weight of the wood shavings, the hot pressing efficiency is improved by about 33% compared with that when the agent A is only used as the adhesive.
As can be seen from the analysis of application examples 9-10 and application comparative examples 5-6, the performance of application comparative examples 5-6 is inferior to that of application examples 9-10, and the adhesive performance formed by the triethanolamine derivative with the mass percent ranging from 2% to 50% is proved to be better.
The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. The adhesive is characterized by comprising a component A and a component B;
the component A comprises polymethylene polyphenyl polyisocyanate and/or polymethylene polyphenyl polyisocyanate derivatives;
the component B comprises a combination of triethanolamine, diethanolamine, monoethanolamine and triethanolamine derivatives;
the total mass percentage of the triethanolamine, the diethanolamine and the monoethanolamine is 50-98% based on 100% of the total mass of the component B;
the triethanolamine derivative accounts for 2-50% by mass;
in the polymethylene polyphenyl polyisocyanate, the functionality of isocyanate is at least 2, and the number of methylene is at least 2.
2. The adhesive of claim 1, wherein the triethanolamine derivative has the structure shown in formula I:
Figure FDA0003418705930000011
wherein a, b and c are positive integers of 0-20, and at least one of a, b and c is not 0;
preferably, the number average molecular weight of the triethanolamine derivative is 3000g/mol, and further preferably 300-1000 g/mol.
3. The adhesive according to claim 1 or 2, characterized in that the mass percent of the triethanolamine, the diethanolamine and the monoethanolamine is 75% -90% based on 100% of the total mass of the B component;
the triethanolamine derivative accounts for 10-25% by mass;
preferably, the preparation raw materials of the triethanolamine derivative comprise triethanolamine and ethylene oxide;
preferably, the mass ratio of the triethanolamine to the ethylene oxide is 1 (1-20).
4. The adhesive according to any one of claims 1 to 3, wherein the mass ratio of the component A to the component B is (3-15): 1.
5. The adhesive according to any one of claims 1 to 4, wherein sodium ions are contained in the component A, and the mass concentration of the sodium ions is 0.1 to 20 ppm;
preferably, the average functionality of the A component is 2.1-3.2, and the mass percent of isocyanate groups is 16-33%;
preferably, the viscosity of the A component is 30-3000cp at 25 ℃;
preferably, the polymethylene polyphenyl polyisocyanate comprises any one of diphenylmethane diisocyanate, triphenylmethane triisocyanate or polymethylene polyphenyl polyisocyanate with functionality greater than three or a combination of at least two of the same;
preferably, the component A comprises the following components in percentage by mass of 100 percent of the total mass: 40-60% of diphenylmethane diisocyanate and/or polyurethane thereof, 25-35% of triphenylmethane triisocyanate and/or polyurethane thereof, and up to 100% of polymethylene polyphenyl polyisocyanate and/or polyurethane thereof having a functionality greater than three.
6. An artificial board, characterized in that the artificial board comprises at least two layers of base materials;
the two adjacent substrates are bonded by the adhesive of any one of claims 1-5.
7. The artificial board according to claim 6, wherein the total mass of the A component in the adhesive system is 1-10% of the mass of the absolutely dry substrate, based on 100% of the total mass of the substrate.
8. A method for preparing artificial boards according to claim 6 or 7, comprising the following steps:
and (3) respectively and independently applying the component A and the diluted component B, or respectively and independently applying the diluted component B and the diluted component A to at least two layers of base materials, and laminating the base materials containing the adhesive to obtain the artificial board.
9. The method of claim 8, wherein the diluent of the B-component comprises water;
preferably, the mass ratio of the B component to the water is (0.2-1): 1;
preferably, the manner in which the a and B components are applied to the substrate comprises atomization;
preferably, the atomization comprises rotary atomization and/or high pressure atomization;
preferably, the high-pressure atomization pressure is 2-30 bar;
preferably, the rotating atomization rotating speed is 9000r/min-11000 r/min;
preferably, the stacking arrangement mode comprises pre-pressing and hot pressing;
preferably, the temperature of the hot pressing is 180-240 ℃;
preferably, the pressure of the hot pressing is 0.5-5 MPa;
preferably, the prepressing is finished until the thickness of the base material is reduced by more than 30%;
preferably, the substrate comprises a wood material;
preferably, the wood material comprises wood shavings and/or straw shavings.
10. The method of manufacturing according to claim 8 or 9, comprising the steps of:
(1) mixing the component B with water according to the mass ratio of (0.2-1) to 1 to obtain a diluted component B;
(2) applying the component A and the diluted component B or the diluted component B and the diluted component A to at least two layers of wood materials respectively in an atomization mode;
(3) laminating and paving the wood material containing the adhesive, prepressing until the thickness of the wood material is reduced by more than 30 percent, and hot-pressing under the conditions that the temperature is 180-240 ℃ and the pressure is 0.5-5MPa to obtain the artificial board.
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CN115160973B (en) * 2021-12-17 2023-03-10 万华化学集团股份有限公司 Curing agent composition and application thereof
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