CN111234774B - Modified soybean formaldehyde-free flame retardant adhesive and preparation method thereof - Google Patents
Modified soybean formaldehyde-free flame retardant adhesive and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J189/00—Adhesives based on proteins; Adhesives based on derivatives thereof
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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
- B27D1/08—Manufacture of shaped articles; Presses specially designed therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B27—WORKING OR PRESERVING WOOD OR SIMILAR MATERIAL; NAILING OR STAPLING MACHINES IN GENERAL
- B27M—WORKING OF WOOD NOT PROVIDED FOR IN SUBCLASSES B27B - B27L; MANUFACTURE OF SPECIFIC WOODEN ARTICLES
- B27M3/00—Manufacture or reconditioning of specific semi-finished or finished articles
- B27M3/04—Manufacture or reconditioning of specific semi-finished or finished articles of flooring elements, e.g. parqueting blocks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- 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
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- 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
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- 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
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention aims to provide a modified soybean formaldehyde-free flame retardant adhesive, which comprises the following components: 100 parts of crosslinking modifier, 50-100 parts of water, 100-200 parts of defatted soybean powder, 50-150 parts of activated modified flame retardant, 5-7 parts of aqueous tackifier and 0.1-0.2 part of assistant; wherein, the activated modified flame retardant consists of the following components: 20-40 parts of ammonium polyphosphate APP, 10-20 parts of melamine phosphate MP, 2-3.5 parts of a coupling agent, 4-7 parts of a dispersing agent and 50-80 parts of aluminum hydroxide or magnesium hydroxide.
Description
Technical Field
The invention relates to the technical field of production and processing of solid wood composite floors, in particular to a modified soybean formaldehyde-free flame retardant adhesive and a preparation method thereof.
Background
The wood floor is a common ground decoration material, and the main varieties comprise a laminate wood floor, a solid wood composite floor, a solid wood floor and a impregnated paper laminated board veneer multi-layer solid wood composite floor. Compared with other floor decorative materials such as carpets, stones, tiles and plastic floors, the wood floor has the characteristics of natural and beautiful texture, light weight, easy processing, good heat preservation, capability of adjusting indoor temperature and humidity, elasticity, capability of buffering impact and the like, and is popular with people because the wood floor gives people a feeling of returning to nature. The solid wood composite floor occupies a dominant position in a wood floor product group and is widely applied to floor material decoration of indoor public places such as cinemas, markets and the like, but the solid wood composite floor is a flammable material, so that the flammability of the solid wood composite floor is reduced by flame retardant treatment after processing, and the safety of the solid wood composite floor in use is further improved.
With the development of science and technology and the continuous improvement of the requirements of people on living quality, the requirements of people on home decoration are also improved day by day, and the indexes of formaldehyde emission, flame retardant effect and the like become one of the main standards for selecting floors. For example, in the current existing research, patent with application number CN201811111237.1 discloses an aldehyde-free flame retardant floor and a preparation method thereof, the aldehyde-free flame retardant floor is prepared by processing weeds and crop straws through a series of process steps; in patent application No. CN201610747070.2, a method for producing a full eucalyptus solid wood composite floor by using a flame-retardant composite urea-formaldehyde resin is disclosed; the patent with the application number of CN201811421996.8 discloses a low TVOC flame-retardant solid wood composite floor and a processing technology thereof, and no literature report that the solid wood composite floor is produced by taking flame-retardant modified soybean adhesive as glue solution exists, and the relevance is not great.
At present, the flame retardant on the market has uneven quality and high price with good flame retardant effect, otherwise, the flame retardant effect cannot meet the requirement if the flame retardant is cheap, and if the flame retardant is directly compounded with soybean glue, the problems of quick glue drying, no molding during cold pressing, unqualified wet strength and impregnation stripping of finished products and the like exist. The solid wood composite floor is trial-manufactured by adopting the formaldehyde-free flame retardant adhesive disclosed in the patent with the application number of CN201910843380.8, and the detection result shows that the flame retardant grade and the formaldehyde release amount are both qualified, but the II-class bonding strength is only 0.3-0.4 MPa, and the impregnation stripping is unqualified, so that the solid wood composite floor is not suitable for the solid wood composite floor.
Disclosure of Invention
In order to solve the technical problems and overcome the defects in the prior art, the invention aims to provide a modified soybean formaldehyde-free flame retardant adhesive, which comprises the following components:
100 parts of crosslinking modifier, 50-100 parts of water, 100-200 parts of defatted soybean powder, 50-150 parts of activated modified flame retardant, 5-7 parts of aqueous tackifier and 0.1-0.2 part of assistant;
wherein, the activated modified flame retardant consists of the following components: 20-40 parts of ammonium polyphosphate APP, 10-20 parts of melamine phosphate MP, 2-3.5 parts of a coupling agent, 4-7 parts of a dispersing agent and 50-80 parts of aluminum hydroxide or magnesium hydroxide.
Preferably, the ammonium polyphosphate APP is type II, the polymerization degree is more than 2000, the manufacturer is Craine, and the flame retardant of the type Craine has excellent flame retardant effect, but the use cost is high, so from the aspect of production cost, the ammonium polyphosphate APP is compounded with aluminum hydroxide or magnesium hydroxide, and the like, so that the cost is reduced, and the ammonium polyphosphate APP has good flame retardant performance.
Preferably, the melamine phosphate MP has the N content of more than or equal to 36.0 percent and the P content of more than or equal to 12.0 percent, higher nitrogen and phosphorus content can have better flame retardant effect but higher cost, and the flame retardant compounded by the MP and the APP, the aluminum hydroxide or the magnesium hydroxide is adopted, so that the flame retardant effect is obviously improved compared with that when the MP is not added.
Preferably, the coupling agent is one or a mixture of more of silane coupling agent, titanate, aluminate, sodium dodecyl benzene sulfonate, dibutyl phthalate, dioctyl phthalate and the like, and the coupling agent is added for activating and modifying the flame retardant, so that the soybean glue added with the flame retardant has good strength, otherwise, the strength of the soybean glue is reduced due to the addition of the flame retardant.
Preferably, the dispersant is one or more of sodium silicate, sodium tripolyphosphate, sodium pyrophosphate, sodium dodecyl sulfate, sodium hexametaphosphate and the like. The addition of the dispersing agent can uniformly mix the coupling agent with the flame retardant and can also uniformly disperse the modified flame retardant in the adhesive.
Preferably, the mesh number of the aluminum hydroxide and the magnesium hydroxide is more than or equal to 2000 meshes, and the aluminum hydroxide and the magnesium hydroxide are used as low-cost inorganic flame retardants, so that the flame retardant not only can be flame-retardant, but also can effectively prevent fuming, dripping and toxic gas, and after the aluminum hydroxide and the magnesium hydroxide are compounded with APP and MP, the system cost is reduced, and the flame retardant property is obviously improved.
Preferably, the crosslinking modifier is one or two of modified polyamide resin, epoxy resin, polyisocyanate and hydroxymethyl acrylamide. In some embodiments of the invention, the crosslinking modifier is a modified polyamide resin having a solids content of 24 to 26%, a viscosity of 60 to 100 mPas, and a pH of 3.0 to 3.5.
Preferably, the defatted soybean flour contains protein more than or equal to 50%, fat less than or equal to 1.0%, carbohydrate 25-30% and ash 4-5%.
Preferably, the auxiliary agent is one of glycerol, propylene glycol, butanediol, hexanediol, polyethylene glycol, polysorbate, polypropylene glycol and sorbitol, and the purpose is to improve the water retention performance of the glue.
Preferably, the aqueous tackifier in the second step is a mixture of rosin ester and non-rosin resin, the solid content is 57%, and the viscosity is 300mPa & s, the addition of the aqueous tackifier can greatly improve the viscosity of the glue, effectively improve the poor initial viscosity of the glue caused by the addition of the activated modified flame retardant, and solve the problems of no molding and board scattering after cold pressing due to the poor initial viscosity.
Preferably, the material of the flame-retardant base material layer in the third step is a eucalyptus veneer, and the thickness of the base material layer is 1.0-3.0 mm; the surface plate is made of beech, birch, oak and the like, and the thickness of the surface plate is 0.6-3 mm; the back plate is made of beech and has a thickness of 0.6-3 mm.
The invention also aims to provide a preparation method of the modified soybean formaldehyde-free flame retardant adhesive, which is characterized by comprising the following steps:
firstly, preparing an activated modified flame retardant:
sequentially adding ammonium polyphosphate APP, melamine phosphate MP, a coupling agent and a dispersing agent into a high-speed mixer, stirring for 10-20 min, adding aluminum hydroxide or magnesium hydroxide, and stirring for 10-20 min to be uniform to obtain an activated modified flame retardant;
secondly, preparing the modified soybean formaldehyde-free flame retardant adhesive:
and (2) sequentially adding a crosslinking modifier, water, defatted soybean flour, an activated modified flame retardant, a water-based tackifier and an auxiliary agent into a reaction kettle, and stirring at 55-110 ℃ for 1.5-3 hours until the mixture is uniform, thus obtaining the modified soybean formaldehyde-free flame retardant adhesive.
The invention also aims to provide a preparation method of the modified soybean formaldehyde-free flame retardant adhesive, which comprises the following steps:
firstly, preparing an activated modified flame retardant
Sequentially adding 20-40 parts of ammonium polyphosphate APP, 10-20 parts of melamine phosphate MP, 2-3.5 parts of coupling agent and 4-7 parts of dispersing agent into a high-speed mixer, stirring for 10-20 min, adding 50-80 parts of aluminum hydroxide or magnesium hydroxide, and stirring for 10-20 min to be uniform to obtain an activated modified flame retardant;
secondly, preparing the modified soybean formaldehyde-free flame retardant adhesive
And (2) sequentially adding 100 parts of crosslinking modifier, 50-100 parts of water, 100-200 parts of defatted soybean flour, 50-150 parts of activated modified flame retardant, 5-7 parts of waterborne tackifier and 0.1-0.2 part of auxiliary agent into a reaction kettle, and stirring at 55-110 ℃ for 1.5-3 hours until the mixture is uniform, thus obtaining the modified soybean formaldehyde-free flame retardant adhesive.
The invention further aims to provide an activated modified flame retardant, which comprises 20-40 parts of ammonium polyphosphate APP, 10-20 parts of melamine phosphate MP, 2-3.5 parts of a coupling agent, 4-7 parts of a dispersing agent and 50-80 parts of aluminum hydroxide or magnesium hydroxide.
The invention also aims to provide a formaldehyde-free flame-retardant solid wood composite floor and a preparation method thereof, wherein the formaldehyde-free flame-retardant solid wood composite floor comprises a paint coating layer, a surface plate, a flame-retardant adhesive layer, a flame-retardant multilayer substrate layer, a flame-retardant adhesive layer and a back plate, wherein the flame-retardant multilayer substrate layer is formed by assembling eucalyptus single plates and flame-retardant adhesive according to a plywood substrate for the solid wood composite floor; the preparation method comprises the following steps:
firstly, preparing an activated modified flame retardant
Sequentially adding 20-40 parts of ammonium polyphosphate APP, 10-20 parts of melamine phosphate MP, 2-3.5 parts of coupling agent and 4-7 parts of dispersing agent into a high-speed mixer, stirring for 10-20 min, adding 50-80 parts of aluminum hydroxide or magnesium hydroxide, and stirring for 10-20 min to be uniform to obtain an activated modified flame retardant;
secondly, preparing the modified soybean formaldehyde-free flame retardant adhesive
Sequentially adding 100 parts of crosslinking modifier, 50-100 parts of water, 100-200 parts of defatted soybean flour, 50-150 parts of activated modified flame retardant, 5-7 parts of aqueous tackifier and 0.1-0.2 part of auxiliary agent into a reaction kettle, and stirring at 55-110 ℃ for 1.5-3 hours until the mixture is uniform, thereby preparing the modified soybean formaldehyde-free flame retardant adhesive;
thirdly, preparing the aldehyde-free flame-retardant solid wood composite floor
1) Coating the modified soybean formaldehyde-free flame retardant adhesive prepared in the second step on the surface of the eucalyptus veneer, assembling the modified soybean formaldehyde-free flame retardant adhesive into a multi-layer plywood for the solid wood composite floor in a criss-cross mode, and preparing a flame retardant multi-layer base material layer after cold pressing and hot pressing;
2) and (3) after the flame-retardant multilayer substrate layer is balanced, coating the modified soybean formaldehyde-free flame-retardant adhesive prepared in the second step, adhering a surface plate on the upper surface and adhering a bottom plate on the lower surface, assembling, and performing cold pressing, hot pressing, health preserving, slicing, sanding, grooving, painting and other processes to prepare the formaldehyde-free flame-retardant solid wood composite floor.
As further described in the scheme, the coating weight of the modified formaldehyde-free flame retardant adhesive in the step three is 200-300 g/m2The cold pressing time is 1h under the process conditions, and the unit pressure is 7-1.1 kg/cm2The hot pressing temperature is 125 ℃, (50-55 +25) s/mm, and the unit pressure is 7-1.1 kg/cm2And (5) preparing. In the long-term practice process, a writer finds that after the activated modified flame retardant is added into the soybean gum according to the proportion, the strength of the soybean gum is not affected, the solid content of the soybean gum can be increased, the solid content of the commercially available soybean gum is less than 35%, the solid content of the formaldehyde-free flame retardant of the modified soybean provided by the invention is up to 48-52%, so that the hot pressing efficiency of a floor is greatly increased, and the floor is increased from (70+30) s/mm to (50-50 +25) s/mm.
In the embodiment of the invention, the flame retardant rating is B1-C when the addition amount of the activated modified flame retardant is 25%, the flame retardant rating is B1-B when the addition amount of the activated modified flame retardant is 35%, in some embodiments, the addition amount of the activated modified flame retardant is 25% + the flame retardant rating is B1-B when the UV flame retardant paint is used, and the formaldehyde emission is 0.01mg/m3Formaldehyde released by wood, cold press forming, dipping and peeling, II-type bonding strength and paint film surface propertyAll the products are qualified; as shown above, the invention provides an activated modified flame retardant for solid wood composite floors, the APP, MP and aluminum hydroxide or magnesium hydroxide are compounded, the cost is lower than that of a commercially available flame retardant, the flame retardant effect is good, and the flame retardant grade reaches B1-C-B1-B grade when the addition amount is 25-35%; the inventor of the invention also finds that when the coupling agent and the dispersing agent are not added, the dipping and stripping are unqualified, and the class II bonding strength is only 0.5MPa, but the embodiment of the invention creatively activates and modifies the flame retardant by adding the coupling agent and the dispersing agent, so that the soybean glue added with the flame retardant has good strength; further, when the water-based tackifier is not added, the problems of no forming and board scattering after cold pressing exist due to poor initial viscosity, but the embodiment of the invention selects to add the water-based tackifier, so that the viscosity of the glue is greatly improved, and the problems of no forming and board scattering after cold pressing, which are caused by poor initial viscosity due to the addition of the activated modified flame retardant, are solved; furthermore, when the soybean formaldehyde-free flame retardant adhesive is directly compounded by adopting the commercially available soybean gum (the solid content is less than 35%) and the commercially available flame retardant APP to replace the modified soybean formaldehyde-free flame retardant adhesive, the soybean formaldehyde-free flame retardant adhesive is cold-pressed, is not formed and scattered, is unqualified in dipping and peeling, and has the bonding strength of class II of only 0.4MPa, but the embodiment of the invention activates and modifies the flame retardant and adds the water-based tackifier, so that the physical and chemical performance indexes of the prepared floor are qualified, and the flame retardant grade reaches B1-C; furthermore, the inventors of the present invention have also found that when commercially available soybean gum (solids content < 35%) is used instead of the modified soybean aldehyde-free flame retardant gum, the flame retardant rating is only B2-E, whereas when the embodiment of the present invention uses the modified soybean aldehyde-free flame retardant gum, the flame retardant rating is B1-C. The floor provided by the invention has the characteristics of no aldehyde, environmental friendliness, excellent flame retardant property, and good surface property and mechanical strength. The formaldehyde-free flame-retardant solid wood composite floor prepared by the invention has qualified physical and chemical performance indexes and 0.01mg/m of formaldehyde release amount3(formaldehyde released by the wood) and the highest flame retardant grade can reach B1-B. In conclusion, the beneficial effects of the invention are as follows:
1. the invention provides an activated modified flame retardant for solid wood composite floors, which is prepared by compounding APP, MP and aluminum hydroxide or magnesium hydroxide, and has lower cost and good flame retardant effect compared with commercially available flame retardants, and the flame retardant grade reaches B1-C-B1-B grade when the addition amount is 25-35%.
2. According to the invention, the activated modified flame retardant is added into the soybean glue, and the added flame retardant components enable the floor to have a flame retardant function, so that the safety performance of the floor is greatly improved, and the flame retardant grade is not less than B1-C.
3. The invention provides a modified soybean formaldehyde-free flame-retardant adhesive for solid wood composite floors, which can improve the hot-pressing efficiency of floors greatly when used for preparing floors, can be improved from (70+30) s/mm to (50-50 +25) s/mm, and the formaldehyde emission of the prepared formaldehyde-free flame-retardant solid wood composite floors is 0.01mg/m3(formaldehyde released by the wood) and the highest flame retardant grade can reach B1-B.
Drawings
Fig. 1 is a structural section view of a water-formaldehyde-free flame-retardant solid wood composite floor provided by the invention: 1-paint coating layer, 2-surface plate, 3-flame-retardant multilayer base material layer and 4-bottom plate.
Detailed Description
The parts in the invention are parts by weight.
The specific embodiment of the invention is as follows:
example 1
Firstly, preparing an activated modified flame retardant
Sequentially adding 30 parts of ammonium polyphosphate APP, 15 parts of melamine phosphate MP, 3 parts of sodium dodecyl benzene sulfonate and 5 parts of sodium silicate into a high-speed mixer, stirring for 15min, adding 65 parts of aluminum hydroxide, and stirring for 20min to be uniform to obtain the activated modified flame retardant;
secondly, preparing the modified soybean formaldehyde-free flame retardant adhesive
Sequentially adding 100 parts of modified polyamide resin, 70 parts of water, 140 parts of defatted soybean flour, 80 parts of activated modified flame retardant, 6 parts of waterborne tackifier 880G and 0.15 part of polyethylene glycol into a reaction kettle, and stirring for 2 hours at 80-85 ℃ until the mixture is uniform to obtain the modified soybean formaldehyde-free flame retardant adhesive;
thirdly, preparing the aldehyde-free flame-retardant solid wood composite floor
1) Coating the surface of the eucalyptus veneer with the thickness of 2.2mm with the modified soybean formaldehyde-free flame retardant adhesive prepared in the second step, wherein the coating weight is 220g/m2The multilayer plywood for the solid wood composite floor is assembled into a vertically and horizontally staggered blank according to each layer, and is made into a flame-retardant multilayer substrate layer after cold pressing and hot pressing, wherein the process conditions are that the cold pressing time is 1 hour, and the unit pressure is 9kg/cm2The hot pressing temperature is 125 ℃, the (52+25) s/mm and the unit pressure is 9kg/cm2；
2) After the flame-retardant multilayer substrate layer is balanced, the modified soybean aldehyde-free flame-retardant adhesive prepared in the second step is coated, an oak surface plate with the thickness of 1.2mm is bonded on the upper surface, a beech bottom plate with the thickness of 1.7mm is bonded on the lower surface, and after assembly, the aldehyde-free flame-retardant solid wood composite floor is prepared through the working procedures of cold pressing, hot pressing, health preserving, slicing, sanding, grooving, painting and the like;
the aldehyde-free flame-retardant solid wood composite floor comprises a paint coating layer, a surface plate, a flame-retardant adhesive layer, a flame-retardant multilayer substrate layer, a flame-retardant adhesive layer and a back plate.
Example 2
The production process of step three in example 1 was not changed, and the changed parts were as follows:
firstly, preparing an activated modified flame retardant
Sequentially adding 35 parts of ammonium polyphosphate APP, 15 parts of melamine phosphate MP, 2.5 parts of sodium dodecyl benzene sulfonate and 6 parts of sodium silicate into a high-speed mixer, stirring for 15min, adding 75 parts of aluminum hydroxide, and stirring for 20min till uniformity to obtain the activated modified flame retardant;
secondly, preparing the modified soybean formaldehyde-free flame retardant adhesive
And sequentially adding 100 parts of modified polyamide resin, 65 parts of water, 130 parts of defatted soybean flour, 110 parts of activated modified flame retardant, 7 parts of water-based tackifier 880G and 0.15 part of polyethylene glycol into a reaction kettle, and stirring for 2 hours at the temperature of 80-85 ℃ until the mixture is uniform, thereby obtaining the modified soybean formaldehyde-free flame retardant adhesive.
Example 3
The first and second production processes in example 1 were not changed, and the changed parts were as follows:
thirdly, preparing the aldehyde-free flame-retardant solid wood composite floor
1) Coating the surface of the eucalyptus veneer with the thickness of 2.2mm with the modified soybean formaldehyde-free flame retardant adhesive prepared in the second step, wherein the coating weight is 250g/m2The multilayer plywood for the solid wood composite floor is assembled into a vertically and horizontally staggered blank according to each layer, and is made into a flame-retardant multilayer substrate layer after cold pressing and hot pressing, wherein the process conditions are that the cold pressing time is 1 hour, and the unit pressure is 9kg/cm2The hot pressing temperature is 125 ℃, the (52+25) s/mm and the unit pressure is 9kg/cm2；
2) And after the flame-retardant multilayer substrate layer is balanced, coating the modified soybean aldehyde-free flame-retardant adhesive prepared in the second step, adhering an oak surface plate with the thickness of 1.2mm on the upper surface and adhering a beech bottom plate with the thickness of 1.7mm on the lower surface, assembling, and performing cold pressing, hot pressing, health preserving, slicing, sanding, grooving, UV flame-retardant paint and other processes to prepare the aldehyde-free flame-retardant solid wood composite floor, wherein the UV flame-retardant paint is A185721705 in model number.
Comparative example 1
The second and third production processes in example 1 were not changed, and the changed parts were as follows:
firstly, preparing an activated modified flame retardant
And sequentially adding 30 parts of ammonium polyphosphate APP, 15 parts of melamine phosphate MP and 65 parts of aluminum hydroxide into a high-speed mixer, and stirring for 20min to be uniform to obtain the activated modified flame retardant.
Comparative example 2
The first and third production processes in example 1 were not changed, and the changed parts were as follows:
secondly, preparing the modified soybean formaldehyde-free flame retardant adhesive
And (2) sequentially adding 100 parts of modified polyamide resin, 70 parts of water, 140 parts of defatted soybean flour, 80 parts of activated modified flame retardant and 0.15 part of polyethylene glycol into a reaction kettle, and stirring for 2 hours at 80-85 ℃ until the mixture is uniform, thus obtaining the modified soybean formaldehyde-free flame retardant adhesive.
Comparative example 3
100 parts of commercially available soybean gum (solid content is less than 35%) and 25 parts of commercially available flame retardant APP are directly compounded into the formaldehyde-free flame retardant glue to replace the modified formaldehyde-free flame retardant glue, and the formaldehyde-free flame retardant solid wood composite floor is prepared according to the third step of the embodiment.
Comparative example 4
The formaldehyde-free solid wood composite floor is prepared by adopting commercially available soybean gum (the solid content is less than 35%) to replace modified soybean formaldehyde-free flame retardant glue according to the third step of the embodiment, and only the hot pressing process conditions are changed into that the hot pressing temperature is 125 ℃, the (70+30) s/mm and the unit pressure is 9kg/cm2。
The physical and chemical properties of the floors obtained in the examples and the comparative examples are detected according to the detection method in GB/T17657-2013, and the flame retardant properties are detected by the national center for quality supervision and inspection of fireproof building materials, with the results shown in Table 1 below.
TABLE 1
Wherein the surface properties of the paint film comprise paint film hardness, paint film adhesion and surface scratch resistance.
As can be seen from the data in examples 1, 2 and 3, the flame retardant rating of B1-C was achieved when 25% of the addition amount of the activated modified flame retardant was used in example 1, the flame retardant rating of B1-B was achieved when 35% of the addition amount of the activated modified flame retardant was used in example 2, the flame retardant rating of B1-B was achieved when 25% of the addition amount of the activated modified flame retardant was used in example 3 and UV flame retardant paint was used in example 3, and the formaldehyde emission was 0.01mg/m3Formaldehyde released by the wood is used, and the cold press molding, the dipping stripping, the II-type bonding strength and the paint film surface performance are all qualified;
as can be seen from the data in the example 1 and the comparative example 1, when the coupling agent and the dispersing agent are not added, the phenomena that the dipping and stripping are unqualified and the class II bonding strength is only 0.5MPa are shown, while the soybean glue added with the flame retardant has good strength in the example 1 because the coupling agent and the dispersing agent are added to carry out activation modification on the flame retardant; as can be seen from the data of example 1 and comparative example 2, the cold press had problems of non-forming and plate scattering due to poor initial adhesion when no aqueous tackifier was added, while example 1 had problems of non-forming and plate scattering due to the addition of the aqueous tackifierThe viscosity of the glue is greatly improved, and the problems of no molding and board scattering after cold pressing caused by poor viscosity due to the addition of the activated modified flame retardant are solved; as can be seen from the data in the example 1 and the comparative example 3, when the soybean formaldehyde-free flame retardant adhesive is directly compounded by adopting the commercially available soybean gum (the solid content is less than 35%) and the commercially available flame retardant APP to replace the modified soybean formaldehyde-free flame retardant adhesive, the soybean formaldehyde-free flame retardant adhesive is cold-pressed, unformed and scattered, unqualified in dipping and peeling, and the bonding strength of II class is only 0.4MPa, while the example 1 is characterized in that the flame retardant is activated and modified and the water-based tackifier is added, so that the physical and chemical performance indexes of the prepared floor are qualified, and the flame retardant grade reaches B1-C; as can be seen from the data in example 1 and comparative example 4, when commercially available soybean gum (solid content < 35%) is used instead of the modified soybean formaldehyde-free flame retardant adhesive, the flame retardant rating is only B2-E, while in example 1, when the modified soybean formaldehyde-free flame retardant adhesive is used, the flame retardant rating reaches B1-C. The floor disclosed by the invention has the characteristics of no aldehyde, environmental friendliness, excellent flame retardant property, and good surface property and mechanical strength. The formaldehyde-free flame-retardant solid wood composite floor prepared by the invention has qualified physical and chemical performance indexes and 0.01mg/m of formaldehyde release amount3(formaldehyde released by the wood) and the highest flame retardant grade can reach B1-B.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. The modified soybean formaldehyde-free flame retardant adhesive is characterized by comprising the following components:
100 parts of crosslinking modifier, 50-100 parts of water, 100-200 parts of defatted soybean powder, 50-150 parts of activated modified flame retardant, 5-7 parts of aqueous tackifier and 0.1-0.2 part of assistant;
wherein, the activated modified flame retardant consists of the following components: 20-40 parts of ammonium polyphosphate APP, 10-20 parts of melamine phosphate MP, 2-3.5 parts of a coupling agent, 4-7 parts of a dispersing agent and 50-80 parts of aluminum hydroxide or magnesium hydroxide;
the aqueous tackifier is a mixture of rosin resin and non-rosin resin, and has the solid content of 57% and the viscosity of 300mPa & s.
2. The modified soybean formaldehyde-free flame retardant glue of claim 1, wherein the ammonium polyphosphate APP is type II and has a polymerization degree of more than 2000.
3. The modified soybean formaldehyde-free flame retardant adhesive as claimed in claim 1, wherein the coupling agent is one or a mixture of silane coupling agent, titanate and aluminate.
4. The modified soybean formaldehyde-free flame retardant gum according to claim 1, wherein the dispersant is one or more of sodium silicate, sodium tripolyphosphate, sodium pyrophosphate, sodium dodecyl sulfate and sodium hexametaphosphate.
5. The modified soybean formaldehyde-free flame retardant adhesive as claimed in claim 1, wherein the mesh number of the aluminum hydroxide and the magnesium hydroxide is not less than 2000 meshes.
6. The modified soybean formaldehyde-free flame retardant gum of claim 1, wherein the crosslinking modifier is one or two of modified polyamide resin, epoxy resin, polyisocyanate and methylol acrylamide.
7. The modified soybean aldehyde-free flame retardant adhesive as claimed in claim 1, wherein the defatted soybean flour contains protein more than or equal to 50%, fat less than or equal to 1.0%, carbohydrate 25-30% and ash 4-5%.
8. The modified soybean formaldehyde-free flame retardant gum of claim 1, wherein the adjuvant is one of glycerol, propylene glycol, butylene glycol, hexylene glycol, polyethylene glycol, polysorbate, polypropylene glycol, sorbitol.
9. The preparation method of the modified soybean formaldehyde-free flame retardant adhesive as claimed in any one of claims 1 to 8, characterized by comprising the following steps:
firstly, preparing an activated modified flame retardant:
sequentially adding ammonium polyphosphate APP, melamine phosphate MP, a coupling agent and a dispersing agent into a high-speed mixer, stirring for 10-20 min, adding aluminum hydroxide or magnesium hydroxide, and stirring for 10-20 min to be uniform to obtain an activated modified flame retardant;
secondly, preparing the modified soybean formaldehyde-free flame retardant adhesive:
and (2) sequentially adding a crosslinking modifier, water, defatted soybean flour, an activated modified flame retardant, a water-based tackifier and an auxiliary agent into a reaction kettle, and stirring at 55-110 ℃ for 1.5-3 hours until the mixture is uniform, thus obtaining the modified soybean formaldehyde-free flame retardant adhesive.
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| CN112455028A (en) * | 2020-11-12 | 2021-03-09 | 浙江云峰莫干山地板有限公司 | Low-VOCs-release water-based paint resin film-faced solid wood composite floor and preparation method thereof |
| CN115256564B (en) * | 2022-08-05 | 2023-06-16 | 惠州市龙凌木业有限公司 | Manufacturing method of formaldehyde-free flame-retardant plywood |
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| CN102558914A (en) * | 2011-12-30 | 2012-07-11 | 大连亚泰科技新材料有限公司 | Surface activation modification technology for environment-friendly magnesium hydroxide flame retardant special for insulating materials |
| CN106313199A (en) * | 2016-08-15 | 2017-01-11 | 宁波中科朝露新材料有限公司 | Non-formaldehyde adhesive particle board and preparation method thereof |
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| CN102558914A (en) * | 2011-12-30 | 2012-07-11 | 大连亚泰科技新材料有限公司 | Surface activation modification technology for environment-friendly magnesium hydroxide flame retardant special for insulating materials |
| CN106313199A (en) * | 2016-08-15 | 2017-01-11 | 宁波中科朝露新材料有限公司 | Non-formaldehyde adhesive particle board and preparation method thereof |
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