CN111993719A - Flame-retardant environment-friendly composite layer material and preparation method thereof - Google Patents

Flame-retardant environment-friendly composite layer material and preparation method thereof Download PDF

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Publication number
CN111993719A
CN111993719A CN202010820547.1A CN202010820547A CN111993719A CN 111993719 A CN111993719 A CN 111993719A CN 202010820547 A CN202010820547 A CN 202010820547A CN 111993719 A CN111993719 A CN 111993719A
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flame
retardant
environment
starch
water
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Chinese (zh)
Inventor
胡广全
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Hangzhou Keneng New Material Technology Co ltd
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Hangzhou Keneng New Material Technology Co ltd
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Priority to CN202010820547.1A priority Critical patent/CN111993719A/en
Priority to KR1020200143638A priority patent/KR102499883B1/en
Publication of CN111993719A publication Critical patent/CN111993719A/en
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/28—Processes for applying liquids or other fluent materials performed by transfer from the surfaces of elements carrying the liquid or other fluent material, e.g. brushes, pads, rollers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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    • B32B17/02—Layered products essentially comprising sheet glass, or glass, slag, or like fibres in the form of fibres or filaments
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    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/061—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of metal
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    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
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    • C08L33/04—Homopolymers or copolymers of esters
    • 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
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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
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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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/04—Polysiloxanes
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • C09K21/06—Organic materials
    • C09K21/10—Organic materials containing nitrogen
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
    • E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
    • E04B1/62—Insulation or other protection; Elements or use of specified material therefor
    • E04B1/92—Protection against other undesired influences or dangers
    • E04B1/94—Protection against other undesired influences or dangers against fire
    • E04B1/941—Building elements specially adapted therefor
    • E—FIXED CONSTRUCTIONS
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    • B32B2307/40—Properties of the layers or laminate having particular optical properties
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  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Structural Engineering (AREA)
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  • Life Sciences & Earth Sciences (AREA)
  • Fluid Mechanics (AREA)
  • Inorganic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Electromagnetism (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention discloses a flame-retardant environment-friendly composite layer material and a preparation method thereof. The flame-retardant environment-friendly composite layer material comprises an aluminum foil, a flame-retardant adhesive layer, an inorganic fiber layer, a flame-retardant adhesive layer and an aluminum foil which are sequentially arranged, wherein the coating amount of the flame-retardant adhesive layer is 10-25g/m2, and the thickness of the aluminum foil is 6-30 mu m, and the flame-retardant adhesive layer consists of the following components in percentage by weight: 25-32% of water-based environment-friendly resin; 18-25% of water-based acrylic resin; 15-25% of starch; 2 to 5 percent of nitrogen flame retardant; the balance of water. The flame-retardant environment-friendly composite layer material can be used for flame retardance and has the advantages of good installation operability and high stability of flame-retardant effect.

Description

Flame-retardant environment-friendly composite layer material and preparation method thereof
Technical Field
The invention relates to the field of functional decorative materials, in particular to a flame-retardant environment-friendly composite layer material and a preparation method thereof.
Background
With the improvement of the living standard of residents, the pursuit of the residents for the living quality is gradually strengthened. At present, the wall structure of a common building is formed by covering a layer of cement on the exterior of a bricked wall body, coating paint on the exterior or pasting a wall brick on the exterior, and scraping putty and paint on the interior of the wall. Like this kind of wall structure, can only satisfy effects such as basic support, isolation, do not possess some special requirements such as heat preservation, sound insulation and fire-retardant.
Chinese patent publication No. CN105297551A discloses a flame retardant wallpaper as an indoor wall decoration and finishing material and a preparation method thereof, wherein the preparation method of the flame retardant wallpaper comprises the steps of soaking a decoration veneer and a wallpaper base layer (base paper) in a flame retardant solution, and then performing ultrasonic impregnation treatment on the decoration veneer and the wallpaper base layer to obtain the flame retardant decoration veneer and the flame retardant base layer; and then the flame-retardant veneer is covered on the surface of the flame-retardant base layer.
In the above prior art, although the subject name is limited to the wallpaper, the layer material of the wallpaper includes the decorative veneer, the thickness of the decorative veneer is larger than that of the layer material, and the wallpaper includes the hard wood material, so that the installation operability is also poor; in addition, the decorative veneer and the wallpaper base layer need to be ultrasonically dipped in a flame retardant solution, the adhesion rate after dipping cannot be ensured to be stable, and the stability of the flame retardant effect can be influenced. In conclusion, the prior art has the defects of poor installation operability and low product stability.
Disclosure of Invention
Aiming at the defects in the prior art, the first purpose of the invention is to provide a flame-retardant environment-friendly composite layer material which has the advantages of good installation operability and high flame-retardant effect stability.
The second objective of the present invention is to provide a method for preparing a flame-retardant environment-friendly composite layer material, which has the advantages of obtaining a stable composite layer material with uniform and stable flame-retardant efficacy.
In order to achieve the first object, the invention provides the following technical scheme: the flame-retardant environment-friendly composite layer material comprises an aluminum foil, a flame-retardant adhesive layer, an inorganic fiber layer, a flame-retardant adhesive layer and an aluminum foil which are sequentially arranged, wherein the coating amount of the flame-retardant adhesive layer is 10-25g/m2The thickness of the aluminum foil is 6-30 mu m;
the flame-retardant adhesive layer comprises the following components in percentage by weight:
25-32% of water-based environment-friendly resin;
18-25% of water-based acrylic resin;
15-25% of starch;
2 to 5 percent of nitrogen flame retardant;
the balance of water.
By adopting the technical scheme, the aluminum foil is used for heat insulation, the inorganic fiber layer serves as a main framework to provide excellent mechanical performance, and the flame-retardant glue layer realizes the flame-retardant effect. The flame-retardant material is made into a composite material form, the layer does not need to be impregnated, the problem that the adhesion rate cannot be controlled is solved, and the uniform stability of the flame-retardant effect of the material is well improved; in addition, the composite layer material has good flexibility, is convenient to transport, carry, cut and install on the inner wall surface, and has better operability than the prior art during installation.
The aluminum foil is used as the outermost layer of the two sides of the composite layer material, can be recycled in a whole block, is a soft metal film, has good sealing performance, can prevent moisture, plays a role in heat insulation mainly through reflected light, delays the direct transmission of temperature to the wall surface, and prolongs the escape time. The main material of the inorganic fiber layer is the interwoven inorganic fiber, the inorganic fiber is produced by high-temperature melting and centrifuging ore and coke according to a certain proportion, has excellent hardness and strength and lower density, is arranged in the middle layer as a main framework in the composite layer material, and provides excellent mechanical strength for the composite layer material.
The flame-retardant glue in the flame-retardant glue layer plays a role in bonding each layer and retarding flame. The water-based environment-friendly resin and the water-based acrylic resin in the flame-retardant adhesive are adhesive main materials of the adhesive, the water-based environment-friendly resin and the water-based acrylic resin can form a coating which is soft, good in adhesive property and high in supporting strength, and a flame-retardant adhesive layer with excellent flexibility can be obtained after curing. The matching of the aluminum foil and the flame-retardant adhesive layer can improve the problems of easy breakage and poor flexibility of the aluminum foil, prolong the service life of the whole composite layer material, realize heat insulation and flame retardance and strive for time for escape; and the inorganic fiber layer is matched to improve the overall mechanical strength of the composite layer material, so that the composite layer material with good flexibility, good flame retardance and long service life is obtained.
The water-based environment-friendly resin and the water-based acrylic resin are water-soluble resins, so that the use of an organic solvent is avoided, and the safety and the environment friendliness of the material are improved. Inorganic fiber layer sets up between two-layer fire-retardant glue film, and fire-retardant glue can the cladding when the coating outside inorganic fiber, provides the guarantee for the maintenance of inorganic fiber layer form on the one hand, and on the other hand can protect inorganic fiber layer, ensures that inorganic fiber layer provides the intensity to the composite bed material and supports, has improved the structural stability of composite bed material when suffering high temperature greatly.
Mixing starch and water, heating and gelatinizing to form a pasty solution, wherein hydrogen bonds exist between starch molecules and water molecules at the moment, and the starch molecules and the water molecules are mutually adsorbed. On the one hand, starch after the gelatinization is mixed with waterborne environmental protection resin and waterborne acrylic resin, can seal the hydrone in fire-retardant glue film, and when indoor catching fire, the intensity of a fire is close to the composite layer material on the wall gradually, and when aluminium foil and fire-retardant glue film were gradually burnt, starch was heated and can become the form that flows again, and water realization cooling realizes fire-retardant effect simultaneously. On the other hand, the flame retardant can be uniformly dispersed in the starch pasting solution, so that the good dispersibility of the flame retardant in the flame-retardant adhesive is promoted, and the uniformity and the stability of the flame-retardant property of the flame-retardant adhesive layer are improved. In addition, when the starch is heated and becomes a flowing state again, besides the cooling of water molecules, a large amount of flame retardant gas generated by the decomposition of the flame retardant breaks through the starch coating, and meanwhile, the starch can also be carried to a high-temperature area, so that instant flame retardance is realized, the integral flame retardant effect is improved, and the flame retardant effect is further improved.
In addition, the starch is added, so that the overall fluidity of the flame-retardant adhesive can be reduced, the overall viscosity of the flame-retardant adhesive can be adjusted, and the adhesive can be conveniently applied. The starch and water form a pasting solution, so that the starch adhesive has adhesion, and the influence of the addition of the flame retardant and the water on the adhesion strength of the flame-retardant adhesive can be reduced while the water is kept.
After the nitrogen flame retardant is heated and decomposed, the temperature can be reduced, non-combustible gas is discharged, oxygen supply is blocked, flame retardance is realized, and the nitrogen flame retardant is environment-friendly.
After the composite layer material is installed on the inner wall surface, the indoor fire spreads towards the wall surface, and the flame can directly damage the wall surface by destroying the composite layer material. Due to the heat insulation effect of the aluminum foil on the outer surface, the inner layer and the wall surface of the composite layer material cannot be heated rapidly, and the discovery and escape time can be prolonged; when the fire breaks through the aluminum foil, the temperature is transmitted to the flame-retardant adhesive layer, the flame-retardant adhesive layer is gradually destroyed, the starch is exposed and is pasty, the flame retardant coated in the starch absorbs heat and decomposes to generate bubbles, once the starch is exposed, the starch coating is broken by gas to realize the isolation gas layer, the flame retardance is realized, the moisture release absorbed by the starch can also provide a cooling effect, the time for the flame to spread to the wall surface is prolonged, and sufficient time is provided for escaping. After flame broke through first each fire-retardant glue film, inorganic fiber layer, second fire-retardant glue film in addition, the aluminium foil that is close to the wall simultaneously can further the separation heat, avoids the temperature too fast to transmit to the wall, can prolong the possibility that the intensity of a fire stretchs to the wall greatly, ensures that the wall provides time and the condition of fleing to the support in house.
When the aluminum foil is used, an adhesive layer, such as non-woven fabric, is adhered to the outer layer of the aluminum foil, and then the non-woven fabric is adhered to the wall surface to complete installation.
Further, the flame-retardant glue layer comprises the following components in percentage by weight:
30% of water-based environment-friendly resin;
20% of water-based acrylic resin;
20% of starch;
3.5 percent of nitrogen flame retardant;
the balance of water.
By adopting the technical scheme, the obtained composite layer material has excellent flexibility, good operability during installation, uniform, stable and excellent flame retardant effect, and greatly prolongs the escape time.
Further, the starch is at least one of corn starch, potato starch, glutinous rice starch and sweet potato starch.
By adopting the technical scheme, the corn starch, the potato starch and the glutinous rice starch have excellent moisture absorption capacity and water retention capacity. Firstly, the viscosity of the whole flame-retardant adhesive can be adjusted, and the adhesive can be conveniently applied when the composite layer material is manufactured; secondly, the adhesive force can be provided for the interior of the flame retardant adhesive, and the structural strength of the flame retardant adhesive is prevented from being too low due to the addition of the nitrogen flame retardant and the starch; thirdly, water can be sealed in the flame-retardant adhesive layer, and the flame-retardant adhesive layer and the flame retardant can realize the effects of cooling and flame retardance; fourthly, the dispersibility of the flame retardant in the flame-retardant glue can be provided.
Further, the aqueous environment-friendly resin is aqueous polyurethane resin.
By adopting the technical scheme, the waterborne polyurethane resin has good water solubility, and can obtain a flame-retardant adhesive layer with excellent flexibility after being blended with the waterborne acrylic resin for use.
Further, the nitrogen flame retardant is prepared from the following components in parts by mass of 1: (0.1-0.3) melamine and 45-60% nitric acid solution.
By adopting the technical scheme, melamine can be formed by the reaction of melamine and acid, so that the nitrogen flame retardant consists of melamine salt and melamine in a certain proportion, on one hand, the alkaline environment is reduced, and on the other hand, the acid environment is provided, when starch is mixed with resin, the acid environment can promote the self-crosslinking and blending effects of the resin, the curing time is shortened, and the integral uniformity of the flame-retardant adhesive layer is improved.
Further, the thickness of the aluminum foil is 6-30 μm.
By adopting the technical scheme, the heat insulation performance and the whole thickness of the composite layer material are balanced by limiting the thickness of the aluminum foil.
Furthermore, the inorganic fiber layer adopts glass fiber, and the gram weight is 60-300g/m2。
By adopting the technical scheme, the material of each layer is matched to ensure the overall lightness of the composite layer material, and the composite layer material is convenient to produce, transport, install and use.
In order to achieve the second object, the invention provides the following technical scheme: the preparation method of the flame-retardant environment-friendly composite layer material is characterized by comprising the following steps of: uniformly coating a flame-retardant adhesive layer on the aluminum foil dark surface, covering an inorganic fiber layer on the flame-retardant adhesive, after hot pressing, continuously coating a flame-retardant adhesive layer on the inorganic fiber layer, and finally bonding the aluminum foil dark surface outside the flame-retardant adhesive; hot pressing the materials at 100-150 deg.C by hot press roller, and standing for more than 12 hr;
the glue gluing temperature of the flame retardant glue is 40-80 ℃;
the raw material flame-retardant adhesive of the flame-retardant adhesive layer is prepared by the following steps:
s1: mixing starch with half of water, heating to 55-70 ℃, stirring for 5-8min at a stirring speed of 30-80r/min to obtain a gelatinized starch solution, adding a flame retardant into the starch solution, and continuously stirring for 5-10min to obtain a first mixed solution;
s2: mixing half of water, the water-based environment-friendly resin and the water-based acrylic resin, heating to 60-80 ℃, stirring for 2-4h under the condition of 3-10r/min, and cooling to 55-70 ℃ for later use to obtain a second mixed solution;
s3: and adding the first mixed solution into the second mixed solution, and mixing for 10-30min under the stirring condition of 10-20r/min to obtain the flame-retardant adhesive.
By adopting the technical scheme, the starch and the water are mixed to form a pasty solution, the free water content is greatly reduced, and then the flame retardant is added and uniformly dispersed in the starch pasting solution. The flame retardant can promote the good dispersibility of the flame retardant in the flame retardant adhesive, and a large amount of flame retardant gas generated by the decomposition of the flame retardant can break through the coating of the starch when the starch is heated and becomes a flowing state again, and can carry the starch to adsorb water molecules to a high-temperature area, thereby realizing instant flame retardance and cooling.
In conclusion, the invention has the following beneficial effects:
1. according to the invention, the aluminum foil, the flame-retardant adhesive layer, the inorganic fiber layer, the flame-retardant adhesive layer and the aluminum foil are arranged in a layer structure, heat is insulated through the aluminum foil, the inorganic fiber layer serves as a main structure to provide excellent mechanical properties, and the flame-retardant adhesive layer realizes a flame-retardant effect; on one hand, the flame-retardant material is made into a composite material form, the layer does not need to be impregnated, the problem that the adhesion rate cannot be controlled is solved, and the uniform stability of the flame-retardant effect of the material is well improved; on the other hand, the composite layer material has good flexibility, is convenient to transport, carry, cut and install on the inner wall surface, and has better operability than the prior art during installation.
2. According to the invention, the water-based environment-friendly resin and the water-based acrylic resin are preferably adopted as the main bonding body of the flame-retardant adhesive, and the components used by matching the aluminum foil and the inorganic fiber can improve the problems of easy breakage and poor flexibility of the aluminum foil, so that the whole composite layer material has good flexibility and high mechanical strength.
3. In the invention, starch and the flame retardant are preferably used in a matching manner, so that the integral flame retardant effect is improved, and the flame retardant effect is further improved.
4. According to the invention, melamine and 45-60% nitric acid solution are preferably adopted to form the nitrogen flame retardant, so that on one hand, an alkaline environment is reduced, and on the other hand, an acidic environment is provided, when starch and resin are mixed, the acidic environment can promote the self-crosslinking and blending effects of the resin, the curing time is reduced, and the overall uniformity of the flame-retardant adhesive layer is improved.
Drawings
FIG. 1 is a schematic view of the layer structure of the composite layer material of the present invention.
Reference numerals: 1. aluminum foil; 2. a flame-retardant adhesive layer; 3. and an inorganic fiber layer.
Detailed Description
Examples 1 to 9: a flame-retardant environment-friendly composite layer material is shown in figure 1 and comprises an aluminum foil 1, a flame-retardant adhesive layer 2, an inorganic fiber layer 3, a flame-retardant adhesive layer 2 and the aluminum foil 1 which are sequentially arranged, wherein the bright surfaces of the two aluminum foils 1 face outwards. The components, specific compositions and corresponding masses of the flame retardant adhesives in examples 1-5 are shown in table 1.1, and the components, specific compositions and corresponding masses of the flame retardant adhesives in examples 4-9 are shown in table 1.2, and are prepared by the following steps:
layer material preparation: coating a flame-retardant adhesive layer on the dark surface of the aluminum foil by using a gluing roller, coating an inorganic fiber layer on the flame-retardant adhesive by using a conveying roller, continuously coating a flame-retardant adhesive layer on the inorganic fiber layer by using a gluing roller after passing through a hot-pressing roller at 50 ℃ (the pressure of the hot-pressing roller is 0.3Mpa, and the hot-pressing time is 0.5s), finally bonding the dark surface of the aluminum foil outside the flame-retardant adhesive by using a conveying roller, carrying out hot pressing on the material under the hot-pressing roller at 40-80 ℃ (the pressure of the hot-pressing roller is 0.3Mpa, and the hot-pressing time is 0.5s) by using a; the glue temperature of the flame retardant glue is 40 ℃.
Preparing flame-retardant glue for the flame-retardant glue layer:
s1: adding starch and half of water into a first stirring barrel, heating to 60 ℃, preserving heat, stirring for 7min at a stirring speed of 50r/min to obtain a gelatinized starch solution, adding a flame retardant into the starch solution, and continuously stirring for 10min to obtain a first mixed solution;
s2: adding half of water, the water-based environment-friendly resin and the water-based acrylic resin into a second stirring barrel, heating to 70 ℃, stirring for 3 hours under the condition of 5r/min, and cooling to 60 ℃ for later use to obtain a second mixed solution;
s3: and adding the first mixed solution into the second mixed solution, and mixing for 30min under the stirring condition of 10r/min to obtain the flame-retardant adhesive.
TABLE 1.1 examples 1-5 compositions and corresponding masses (kg)
Figure BDA0002634272560000061
TABLE 1.2 examples 6-9 compositions and corresponding masses (kg)
Figure BDA0002634272560000062
Figure BDA0002634272560000071
In the above examples, glass fibers were used for the inorganic fiber layer.
In example 1, the coating amount of the flame-retardant adhesive layer was 10g/m2The gram weight of the glass fiber is 60g/m2(ii) a The thickness of the aluminum foil was 30 μm.
In example 2, the coating amount of the flame-retardant adhesive layer was 25g/m2The gram weight of the glass fiber is 300g/m2(ii) a The aluminum foil has a thickness of 20 μm.
In example 4, the coating amount of the flame-retardant adhesive layer was 20g/m2The gram weight of the glass fiber is 200g/m2(ii) a The aluminum foil has a thickness of 20 μm.
In example 3 and examples 5-9, the coating amount of the flame-retardant glue layer is 15g/m2The gram weight of the glass fiber is 100g/m2(ii) a The thickness of the aluminum foil was 6 μm.
Example 10: a preparation method of a flame-retardant environment-friendly composite layer material comprises the following steps: layer material preparation: coating a flame-retardant adhesive layer on the dark side of the aluminum foil by using a sizing roller, wherein the coating amount is 10g/m2Coating inorganic fiber layer on the flame-retardant adhesive by a conveying roller, passing through a hot-pressing roller at 40 deg.C (the pressure of the hot-pressing roller is 0.4Mpa, and the hot-pressing time is 1s), and coating a flame-retardant adhesive layer on the inorganic fiber layer by a sizing roller with a coating amount of 10g/m2Finally, adhering the aluminum foil dark side outside the flame-retardant adhesive through a conveying roller, carrying out hot pressing on the materials at 40 ℃ by a hot pressing roller (the pressure of the hot pressing roller is 0.4Mpa, the hot pressing time is 1s), and finally standing for 24 h; the gluing temperature of the flame retardant adhesive is 70 ℃.
Preparing the flame-retardant adhesive of the flame-retardant adhesive layer:
s1: mixing starch with half of water, heating to 55 ℃, preserving heat, stirring for 8min at a stirring speed of 30r/min to obtain a gelatinized starch solution, adding a flame retardant into the starch solution, and continuously stirring for 8min to obtain a first mixed solution;
s2: mixing half of water, the water-based environment-friendly resin and the water-based acrylic resin, heating to 60 ℃, stirring for 4 hours under the condition of 10r/min, and cooling to 55 ℃ for later use to obtain a second mixed solution;
s3: and adding the first mixed solution into the second mixed solution, and mixing for 20min under the stirring condition of 15r/min to obtain the flame-retardant adhesive.
Example 11: a preparation method of a flame-retardant environment-friendly composite layer material comprises the following steps: layer material preparation: coating a flame-retardant adhesive layer on the dark side of the aluminum foil by using a sizing roller, wherein the coating amount is 10g/m2Coating inorganic fiber layer on the flame-retardant adhesive by a conveying roller, passing through a hot-pressing roller at 80 deg.C (the pressure of the hot-pressing roller is 0.45Mpa, and the hot-pressing time is 0.1s), and coating a flame-retardant adhesive layer on the inorganic fiber layer by a sizing roller with a coating amount of 10g/m2Finally, adhering the aluminum foil dark side outside the flame-retardant adhesive through a conveying roller, carrying out hot pressing on the materials at a hot pressing roller of 80 ℃ through a hot pressing roller (the pressure of the hot pressing roller is 0.45Mpa, the hot pressing time is 0.1s), and finally standing for 24 h; the glue temperature of the flame retardant glue is 80 ℃.
Preparing the flame-retardant adhesive of the flame-retardant adhesive layer:
s1: mixing starch with half of water, heating to 70 ℃, preserving heat, stirring for 5min at a stirring speed of 80r/min to obtain a gelatinized starch solution, adding a flame retardant into the starch solution, and continuously stirring for 5min to obtain a first mixed solution;
s2: mixing half of water, the water-based environment-friendly resin and the water-based acrylic resin, heating to 80 ℃, stirring for 2 hours under the condition of 3r/min, and cooling to 70 ℃ for later use to obtain a second mixed solution;
s3: and adding the first mixed solution into the second mixed solution, and mixing for 10min under the stirring condition of 20r/min to obtain the flame-retardant adhesive.
Comparative example 1: the flame-retardant environment-friendly composite layer material is different from the material in the embodiment 1 in that the material is composed of an aluminum foil, a flame-retardant adhesive layer and the aluminum foil, and the bright surface of the aluminum foil faces outwards.
Comparative example 2: the flame-retardant environment-friendly composite layer material is different from the material in the embodiment 1 in that the material is composed of aluminum foil, inorganic fibers and the aluminum foil, and the bright surface of the aluminum foil faces outwards.
Comparative examples 3 to 5: the difference between the flame-retardant environment-friendly composite layer material and the embodiment 1 is that the flame-retardant adhesive layer comprises the components, the specific composition and the quality shown in table 2.
TABLE 2 comparative examples 3-5 compositions and corresponding masses (kg)
Figure BDA0002634272560000081
Characterization experiment:
1. experiment of flame retardant Effect
Subject: examples 1-9 and comparative examples 1-5, for a total of 14 experimental groups.
The experimental method comprises the following steps: the flame retardant rating of the test specimens was determined according to the UL94 flame retardant rating test method and the limit oxygen index was determined.
And (3) testing the flame retardant grade: specification, quantity and pretreatment of experimental samples: each example and comparative example was prepared by cutting 10 replicates of 5inch by 0.5inch and dividing the 10 replicates equally into two groups. Before testing, a group of experimental samples are placed at 23 ℃ and 50% RH for 48 h; the other group was left at 70 ℃ for 7 days and then tested.
The test method comprises the following steps: the sample was placed perpendicular to the long axis and mounted. When the device is installed, the lower end of the test sample is 3/8inch away from the top of the combustion tube, a blue flame with the height of 3/4 is placed at the center of the lower end of the test sample, and the test sample is combusted for 10 s. If the test sample drips, the liquid drips onto a layer of non-surgically treated cotton underneath the sample, which is placed 12 inches below the sample. The ratings were made according to the rating requirements specified in the UL94 flame rating test method.
And (3) oxygen index determination: an oxygen index tester was prepared according to GB2406.2-2009 and placed in a fume hood for use, the fume hood being opened after each test and closed for the next test. The experimental sample specification was 140mm 52mm, and 15 parallel samples were set for each example and comparative example. And (3) testing environment: 25 ℃ and 55% RH.
The experimental results are as follows: the results of the flame retardant effect tests are reported in table 3.
TABLE 3 flame retardant effectiveness test results
Figure BDA0002634272560000091
And (3) data analysis: as can be seen from the data above, the examples all achieved a V0 flame rating, comparative example 1 also achieved a V0 rating, and the remaining comparative examples failed to achieve a V0 rating.
Comparing all the examples, the preferable main body resin, starch selection and the dosage and selection of the nitrogen flame retardant are combined in the examples 7-9, on the basis of aluminum foil heat insulation, the inorganic fiber layer provides a main support structure for supporting, and the flame retardant adhesive layer realizes the main flame retardant effect; the heat insulation of the aluminum foil delays the overall temperature rise rate of the composite layer material, the starch in the flame-retardant adhesive is matched with the main body resin, the overall flexibility of the flame-retardant adhesive layer can be improved, meanwhile, the starch coats the flame retardant, the starch is converted into paste again when the fire is close to the starch, the flame retardant and water molecules play a role in cooling and isolating the air layer in a high-temperature fire area, and flame retardance is realized. In comparative example 6 and comparative examples 7 to 9, the selection of flame retardant directly affects the flame retardant effect.
In comparative example 1, no inorganic fiber layer was provided, and the flame retardant effect was not greatly affected. The comparative example 2 is not provided with a flame-retardant adhesive layer, and the flame-retardant effect is poor. In the comparative example 3, the main resin in the flame-retardant adhesive layer is only aqueous epoxy resin, starch is not used, and a trace amount of flame retardant is used; in comparative example 4, no starch was used and the flame retardant amount was out of the preferred range; in comparative example 5, both starch and flame retardant were used in excess, and neither of them achieved a good flame retardant effect. The direct influence of the matching of the starch and the flame retardant and the use amount of the starch, the flame retardant and the main resin on the flame retardant effect is shown.
1. Flexibility test
Subject: examples 1-9 and comparative examples 1-5, for a total of 14 experimental groups.
The experimental method comprises the following steps: the experimental sample is cut into a spline of 10cm by 5cm, two ends of the spline are fixed on two clamps with the distance of 6cm on a horizontal plane, one clamp is a fixed clamp, the other clamp is a movable clamp, the movable clamp can horizontally move towards and away from the fixed clamp, the movable clamp is driven by a cylinder, the frequency of the cylinder is 60 times/min, the output distance of the cylinder is 4cm, and after the operation is continued for 30min, the state of the outer surface of the aluminum foil is observed, whether the aluminum foil is damaged or not and the aluminum foil fades.
The experimental results are as follows: the flexibility test results are reported in table 4.
Table 4 records of flexibility test results
Figure BDA0002634272560000101
And (3) data analysis: as can be seen from the data shown above, examples and comparative examples 3 to 5 all exhibited very good flexibility, and comparative examples 1 to 2 exhibited poor flexibility.
In the embodiment, the flexibility of the aluminum foil can be greatly improved by matching the flame retardant adhesive with the aluminum foil, so that in comparative example 2, which does not contain the flame retardant layer, the flexible adhesive layer is easily damaged and discolored. The flame retardant was provided in comparative example 1, but since the main frame having no inorganic fiber layer was supported, it was not supported at the time of bending, and was easily bent, and breakage occurred.
Comparative example 1 has a good flame retardant effect, but it has poor flexibility and is inconvenient to transport, produce, store and install, and is not adopted.
The present embodiment is only for explaining the present invention, and it is not limited to the present invention, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present invention.

Claims (8)

1. The flame-retardant environment-friendly composite layer material is characterized by comprising an aluminum foil (1), a flame-retardant adhesive layer (2) and an inorganic fiber layer (A)3) The flame-retardant adhesive layer (2) and the aluminum foil (1), wherein the coating amount of the flame-retardant adhesive layer (2) is 10-25g/m2The thickness of the aluminum foil is 6-30 mu m;
the flame-retardant adhesive layer (2) is composed of the following components in percentage by weight:
25-32% of water-based environment-friendly resin;
18-25% of water-based acrylic resin;
15-25% of starch;
2 to 5 percent of nitrogen flame retardant;
the balance of water.
2. The flame-retardant environment-friendly composite layer material as claimed in claim 1, wherein the flame-retardant adhesive layer (2) is composed of the following components in percentage by weight:
30% of water-based environment-friendly resin;
20% of water-based acrylic resin;
20% of starch;
3.5 percent of nitrogen flame retardant;
the balance of water.
3. The flame-retardant environment-friendly composite layer material as claimed in claim 1 or 2, wherein the starch is at least one of corn starch, potato starch, glutinous rice starch and sweet potato starch.
4. The flame-retardant environment-friendly composite layer material as claimed in claim 1 or 2, wherein the aqueous environment-friendly resin is an aqueous polyurethane resin.
5. The flame-retardant environment-friendly composite layer material as claimed in claim 1 or 2, wherein the nitrogen-based flame retardant is prepared from the following components in parts by mass of 1: (0.2-0.5) melamine and 45-60% nitric acid solution.
6. A fire-retardant environment-friendly composite layer material according to claim 1 or 2, characterized in that the thickness of the aluminum foil (1) is 6-30 μm.
7. The flame-retardant environment-friendly composite layer material as claimed in claim 1 or 2, wherein the inorganic fiber layer (3) is made of glass fiber and has a gram weight of 60-300g/m2。
8. The preparation method of the flame-retardant environment-friendly composite layer material as claimed in claims 1 to 7, characterized by comprising the following steps: uniformly coating a flame-retardant adhesive layer (2) on the dark surface of the aluminum foil (1), then coating an inorganic fiber layer (3) on the flame-retardant adhesive, after hot pressing, continuously coating a flame-retardant adhesive layer (2) on the inorganic fiber layer (3), and finally bonding the dark surface of the aluminum foil (1) outside the flame-retardant adhesive layer (2); hot pressing the materials at 100-150 deg.C by hot press roller, and standing for more than 12 hr;
the glue gluing temperature of the flame retardant glue is 40-80 ℃;
the raw material flame-retardant adhesive of the flame-retardant adhesive layer is prepared by the following steps:
s1: mixing starch with half of water, heating to 55-70 ℃, stirring for 5-8min at a stirring speed of 30-80r/min to obtain a gelatinized starch solution, adding a flame retardant into the starch solution, and continuously stirring for 5-10min to obtain a first mixed solution;
s2: mixing half of water, the water-based environment-friendly resin and the water-based acrylic resin, heating to 60-80 ℃, stirring for 2-4h under the condition of 3-10r/min, and cooling to 55-70 ℃ for later use to obtain a second mixed solution;
s3: and adding the first mixed solution into the second mixed solution, and mixing for 10-30min under the stirring condition of 10-20r/min to obtain the flame-retardant adhesive.
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