CN1272401C - Adhesive, fireproof board with adhesive and its production process - Google Patents

Adhesive, fireproof board with adhesive and its production process Download PDF

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Publication number
CN1272401C
CN1272401C CN 02152849 CN02152849A CN1272401C CN 1272401 C CN1272401 C CN 1272401C CN 02152849 CN02152849 CN 02152849 CN 02152849 A CN02152849 A CN 02152849A CN 1272401 C CN1272401 C CN 1272401C
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China
Prior art keywords
weight parts
weight
dibutyl tin
plastic laminated
mica
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Expired - Fee Related
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CN 02152849
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CN1432618A (en
Inventor
陶世毅
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CHENGDU XINXIDIAN SCI-TECH Co Ltd
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CHENGDU XINXIDIAN SCI-TECH Co Ltd
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Priority to CN 02152849 priority Critical patent/CN1272401C/en
Publication of CN1432618A publication Critical patent/CN1432618A/en
Priority to PCT/CN2003/000980 priority patent/WO2004045847A1/en
Priority to AU2003284810A priority patent/AU2003284810A1/en
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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
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K21/00—Fireproofing materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B19/00—Layered products comprising a layer of natural mineral fibres or particles, e.g. asbestos, mica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
    • C04B37/008—Joining burned ceramic articles with other burned ceramic articles or other articles by heating by means of an interlayer consisting of an organic adhesive, e.g. phenol resin or pitch
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/206—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2315/00—Other materials containing non-metallic inorganic compounds not provided for in groups B32B2311/00 - B32B2313/04
    • B32B2315/02—Ceramics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2315/00—Other materials containing non-metallic inorganic compounds not provided for in groups B32B2311/00 - B32B2313/04
    • B32B2315/10—Mica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2607/00—Walls, panels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/32—Ceramic
    • C04B2237/34—Oxidic
    • C04B2237/341—Silica or silicates

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The present invention relates to an adhesive containing 100 to 150 weight shares of basic polymer, 5 to 20 weight shares of cross-linking agent, 0.1 to 150 weight shares of catalyst and 5 to 100 weight shares of stuffing. The adhesive can be used for adhering material having the disadvantages of small specific surface energy and difficult adhesion. The present invention also relates to a fireproof board formed by the method of adhering a mica board with various boards by the adhesive, and a preparation method for the fireproof board.

Description

A kind of PLASTIC LAMINATED and preparation technology thereof
Invention field
The present invention relates to a kind of PLASTIC LAMINATED, relate in particular to fire-proof board plate mica and the bonding formation of various sheet materials.
The invention still further relates to the preparation method of this PLASTIC LAMINATED.
Background technology
In the prior art, fields such as aerospace, building increase day by day for the demand of various sheet materials, and perforated plate is in light weight because of it, intensity is used widely greatly.Generally honeycomb core structures (honeycombcore) is combined with other various sheet materials and make the honeycomb three-ply-wood, make honeycomb core structures performance optimal performance.Honeycomb core structures has optimal physical strength and rigidity, and is best aerospace applications and bears the trunk material that static state, dynamic load are used.The bonding honeycomb three-ply-wood of making of the strong in addition glue of honeycomb core structures and panel (being generally Resins, epoxy) can guarantee that the mechanics load passes to honeycomb core structures by panel, makes the honeycomb three-ply-wood whole and have a high-strength bending stiffness as one.The honeycomb three-ply-wood not only is applied to aircraft industry at present, their multi-functional great potential make it Application Areas constantly to be increased, for example, the 3003 type perforated plates that on the wall of aircraft, train and automobile and dividing plate, use, the honeycomb three-ply-wood that on ceiling and floor, uses, and be used for surfboard, ski, billboard etc.At aerospace field, sheet material to fire-resistant, high temperature resistant, high-intensity require high, at present honeycomb core structures and carbon fiber board are combined to form the honeycomb three-ply-wood and are processed into single or hyperboloid (5052,5056 type honeycomb three-ply-wood), be widely used in positions such as aircraft wing, fuselage, nacelle, the missile launching wing.
The honeycomb core structures of using mainly contains following several types at present:
The aluminium honeycomb core structure can be used for high temperature, thermal conductivity height, fire-resistant, moisture-resistant, preservative property are strong, anti-mouldy, have the highest weight ratio of rigidity and the highest weight strength ratio;
The aromatic poly honeycomb core structures, have the highest weight ratio of rigidity and the highest weight strength ratio, can be used for high temperature, can high-temperature shaping, thermal insulation height, fire resistance be good;
Polypropylene honeycomb cored structure, but thermoformable recirculation use, thermal insulation and electrical insulating property is good, weight strength ratio is good, anticorrosive, top temperature is no more than 82.2 ℃;
The polycarbonate honeycomb core structures, thermal insulation and electrical insulating property are good, fire prevention, anticorrosive, anti-mouldy, top temperature are no more than 93 ℃.
Mica is a natural mineral raw, electric property with good uniqueness, comprise high insulation resistance, low dielectric loss, anti-corona, simultaneously mica has favorable mechanical performance and highly heat-resistant (reaching thousands of degrees centigrade), anti-moisture performance again, is applied to fields such as electronics, thermoelectricity, oil, chemical industry, building.Mica mainly originates from North America, India, Ukraine, China and other several countries.Natural mica comprises white mica (muscovite) and phlogopite (phlogopite) two classes, the trade(brand)name of white mica is called common mica (common mica), salt of wormwood mica (potash mica) or Russia's glass (moscovy glass) again, and chemical structural formula is K 2Al 4[Si 6Al 2O 20] (OH, F) 4The chemical structural formula of phlogopite is: K 2(Mg 2+), Fe 2+) 6[Si 6Al 2O 20] (OH, F) 4, its heat resistanceheat resistant strength ratio white mica is higher, but its physical strength will be lower than white mica.
Mica can be made into various mica productss, comprises mica paper, plate mica, mica tape, micanite pipe and mica powder etc.
Performance in view of the outstanding fire prevention of mica, heat-resisting, electrical isolation, plate mica combined with other sheet materials make composition board, but the fire-proof board of widespread use will be obtained, but the micaceous specific surface energy is very little, very difficult bonding with other base material, still there are not plate mica and the compounded product of other sheet material in the prior art at present.
Summary of the invention
Defective at prior art, the objective of the invention is to a kind of fire-proof board, existing sheet material is undertaken bonding by layer of adhesive layer and plate mica, make it have high temperature resistant, anti-naked light, incombustible performance, and have excellent electric insulating and light weight, physical strength height.Can be widely used in fields such as Aeronautics and Astronautics, boats and ships, building.
A further object of the present invention provides the manufacture method of this PLASTIC LAMINATED.
According to an aspect of the present invention, a kind of PLASTIC LAMINATED comprises an edge grain, at least one binder layer and at least one stratus motherboard.Edge grain can be any suitable material, and for example metal sheet, cardboard, plastic plate, wood plywood, resol foaming plate or honeycomb core structures etc. are preferably honeycomb core structures, can be as required at a side or the bilateral combined mica plate of edge grain.Plate mica can be commercially available white clouds motherboard or phlogopite plate, and thickness is 0.01mm～20mm, also can adopt the plate mica of specific thicknesses as required.
In PLASTIC LAMINATED of the present invention, the binder layer that is used for bonding edge grain and plate mica contains (weight part):
Base polymer 100～150
Linking agent 5～20
Catalyzer 0.1～2.5
Filler 5～100
Described base polymer is hydroxy-end capped line style polydiorganosiloxane and the multipolymer thereof suc as formula (I) structure,
HO(CH 3R 1SiO) nH，
(I)
Radicals R in the formula (I) 1And CH 3Be connected R respectively with Si 1Be selected from methyl (Me), phenyl (Ph) and CF 3CH 2CH 2, n=100～1000; Its viscosity is 5～20Pa.s;
Described linking agent is selected from one or more of tetraethoxy, the positive butyl ester of boric acid, tetrabutyl titanate, methyl tributanoximo silane, γ-An Bingjisanyiyangjiguiwan, methyltrimethoxy silane and two (two acyl acetonyls) diisopropoxy titanium.The catalyzer that uses in the tackiness agent of the present invention is used for causing or promotes base polymer and linking agent to carry out condensation reaction; Preferred catalyzer is selected from dibutyl tin laurate, tetraethoxysilane dibutyl tin, Sn (OCOC 8H 17) 2, aniline (PhNH 2) and dibutylamine (Bu 2NH) one or more.
The filler that uses in the binder layer of PLASTIC LAMINATED of the present invention comprises reinforced filling and reinforcing filler, and preferred reinforced filling is silicon-dioxide, carbon black or titanium dioxide, and preferred reinforcing filler is diatomite, silica powder, ferric oxide or water-ground limestone.
In actual use, above-mentioned tackiness agent can use with the single component structure, also can use with bicomponent structure, is about to base polymer and filler as component A, and with compositions such as linking agent and catalyzer as B component, component A and B component are mixed before bonding carrying out.
For improving the bond properties of binder layer, above-mentioned tackiness agent can further comprise thinner, thickening material and coupling agent in use.
According to a further aspect in the invention, provide the method for making PLASTIC LAMINATED of the present invention, comprise the steps:
1. batch mixing:
For one-package adhesive of the present invention, earlier sizing material (base polymer), filler etc. are mixed, carry out drying treatment after, add cross-linking system and mix, tubulation seals is standby.For two component adhesive of the present invention, then earlier A component and B component are mixed respectively, when coating with two components of A, B in proportion (as A: B=100: 3.5～4.0) uniform mixing.Mixing can be carried out in blender or in the original packing bucket.Few as consumption, can in clean and exsiccant cup or keg, mix, mix with artificial or mechanical stirring and all can.
2. sulfuration:
Generally in room temperature (23～25 ℃) sulfuration down, improve temperature and can accelerate vulcanization rate, but temperature surpasses 90 ℃, in order to avoid the viscosity increase of glue is too big, obstruction is applied to glue uniformly to be desired on the adherent material.Vulcanization rate is also relevant with humidity, is exposed in the air of high humidity to accelerate vulcanization rate.
3. the adjustment of denseness:
Be to adapt to processing requirement, in the time of need be to the sizing material thickening, can add some thickening materials, as lime carbonate, diatomite, silica powder etc.; When needs reduce compound viscosity, can add some consistencies low molecular weight silicone oil good or same structure type and make thinner.
4. surface treatment:
The specific surface energy of some base material is very little, is difficult to other base material bonding.Tackle that substrate surface degreases this moment and wait to clean and drying treatment, if rubber also needs with sand surperficial hacking.In order to improve the bond strength of tackiness agent, can on substrate surface, coat silane coupling agent to base material.Most of silane coupling agents are made up of the higher silane coupling agent of reactive behavior or the organic solvent diluting liquid of other organometallic compounds, can hydrolytic condensation resin shape active coating in damp atmosphere, it and substrate surface play bonding and action of coupling agents, thereby improve binding property.
5. bonding:
On plate mica, coat tackiness agent of the present invention equably, will place on the plate mica through the base material of above-mentioned processing at last and send into vulcanizing press, handle promptly getting PLASTIC LAMINATED of the present invention in 1-24 hour at the pressure of 0.1-0.5Mpa in 23-90 ℃ down.
In adhesion process, as required, sulfuration and step for adhering can be finished in same step operation.
That PLASTIC LAMINATED of the present invention has is high temperature resistant, anti-naked light, do not burn, do not produce the excellent properties of toxic gas, and has excellent electric insulating and characteristics in light weight, that physical strength is high.Can be widely used in the dividing plate in aerospace, boats and ships, the building industry.
Brief description of drawings
Fig. 1 is the heat energy flow curve of the composition board of the compound Nomex paper of honeycomb core;
Fig. 2 is the heat energy flow curve of PLASTIC LAMINATED of the present invention.
The embodiment of invention
The preparation of [embodiment 1] aluminium honeycomb/mica composite sheet
The aluminium honeycomb core that adopts among the present invention is from U.S. PLASCORE company, and thickness is 5-200mm, and plate mica is Yaan, Sichuan mica factory " refined cloud board " plate mica, and thickness is 0.01-20mm.The thickness of aluminium honeycomb core is 15mm in this example; The thickness 0.5mm of plate mica.Used chemical reagent is commercially available analytical reagent, tackiness agent consist of 100 parts of (weight parts of hydroxyl-terminated injecting two methyl siloxane, below identical), 20 parts of the aerosils that prestox ring tetrasilane is handled, 20 parts of 947 silicone resins, 0.4 part of boric acid, 5 parts of tetraethoxys, 3 parts of the positive butyl esters of boric acid, 2 parts of tetrabutyl titanates, 108 parts of dibutyl tin laurates, 3 parts of KH-560 (γ-glycidyl ether oxygen propyl trimethoxy silicane).With hydroxyl-terminated injecting two methyl siloxane, the aerosil that prestox ring tetrasilane is handled, 947 silicone resins, boric acid are mixing even in mill, and be standby as the A component earlier; Then that all the other component mixings are standby as the B component.During coating by the A component: B component=mixing after use at 100: 3.8.
Each component in tackiness agent consumption and act on as shown in table 1:
Table 1
Component Content (weight part) Effect
The positive butyl ester tetrabutyl titanate of the aerosil 947 organic siliconresin boric acid ethyl orthosilicate boric acid dibutyl tin laurate KH-560 that hydroxyl-terminated injecting two methyl siloxane prestox ring tetrasilane is processed 100 20 20 0.4 5 3 2 1.08 3 Base polymer reinforced filling base polymer catalyst crosslinking agent crosslinking agent cross-linking catalyst coupling agent
When making sheet material, the aluminium honeycomb core bonding plane earlier with the processing of primary coat liquid (primary coat liquid consist of 50 parts of tetraethoxys, 30 parts of Union carbide A-162s, 20 parts of KH-560,0.4 part of boric acid, 2 parts of methyl aceto acetates, 3 parts of three fluoroboric acid chromium, 118 parts of dehydrated alcohols reach mixed solution compositions such as PH conditioning agent-formic acid), and standby after drying.Simultaneously tackiness agent is coated on the plate mica equably, the about 0.5mm of coat-thickness places aluminium honeycomb core on the plate mica then and sends into 80-90 ℃ vulcanizing press, and sulfuration promptly got aluminium honeycomb/mica composite sheet in 2-3 hour under the pressure of 0.1Mpa.
The preparation of embodiment 2 aluminium razor clam nest/mica composition boards
The source of honeycomb core, plate mica is with embodiment 1.The thickness of aluminium honeycomb core is 15mm in this example, the thickness 0.5mm of plate mica.100 parts of the graft copolymers that consists of α, alpha, omega-dihydroxy polydimethyl siloxane and vinylbenzene, butyl acrylate of tackiness agent (weight part, below identical), 7 parts of methyl tributanoximo silanes, D 4Handle 5 parts of silica 1s, 3 parts of γ-An Bingjisanyiyangjiguiwans, 2.5 parts of tetraethoxysilane dibutyl tins.The configuration of tackiness agent can be carried out in equipment such as stirring tank or kneader.Earlier that sizing material, filler etc. are mixing even on cutting machine, and carry out drying treatment, and then the adding cross-linking system is mixing evenly, tubulation seals is standby.This tackiness agent is an one-package adhesive, and whole glue operating process will avoid contacting the moisture in the atmosphere, to guarantee the long storage use.
Each components contents of tackiness agent and effect are as shown in table 2:
Table 2
Component Content (weight part) Effect
The graft copolymer methyl tributanoximo silane D of α, alpha, omega-dihydroxy polydimethyl siloxane and vinylbenzene, butyl acrylate 4Handle silicon-dioxide γ-An Bingjisanyiyangjiguiwan tetraethoxysilane dibutyl tin 100 7 15 3 2.5 Base polymer linking agent reinforced filling cross-linking catalyst
When making sheet material, the aluminium honeycomb core bonding plane is handled (primary coat liquid is formed with embodiment 1) with primary coat liquid earlier, and then on plate mica, coat one-package adhesive equably, place aluminium honeycomb core on the plate mica at last and send into vulcanizing press, the pressure of 0.1Mpa in room temperature or 80-90 ℃ down sulfuration promptly got aluminium honeycomb/mica composite sheet in 1-2 hour.
The preparation of embodiment 3 aluminium honeycomb/mica composition board
The source of honeycomb core, plate mica is with embodiment 1.The thickness of aluminium honeycomb core is 15mm in this example, the thickness 0.5mm of plate mica.Tackiness agent consist of 100 parts of hydroxyl-terminated injecting two methyl siloxanes, 20 parts of 201 silicone oil (viscosity 0.5Pa.s), 7 parts of Union carbide A-162s, D 4Handle 20 parts of silicon-dioxide, 30 parts of calcium carbonate superfine powders, 0.2 part of dibutyl tin laurate.Earlier that sizing material, filler etc. are mixing even in mill, and carry out drying treatment, and then the adding cross-linking system is mixing evenly, tubulation seals is standby.This tackiness agent is an one-package adhesive, and whole glue operating process will avoid contacting the moisture in the atmosphere, to guarantee the long storage use.
Each component in tackiness agent consumption and act on as shown in table 3:
Table 3
Component Content (weight part) Effect
Hydroxyl-terminated injecting two methyl siloxane 201 silicone oil (viscosity 0.5Pa.s) MTES D4 processes silica calcium carbonate superfine powder dibutyl tin laurate 100 20 7 20 30 0.2 Base polymer thinner linking agent reinforced filling reinforcing filler catalyzer
When making sheet material, the aluminium honeycomb core bonding plane is handled (primary coat liquid is formed with embodiment 1) with primary coat liquid earlier, and then on plate mica, coat one-package adhesive equably, place aluminium honeycomb core on the plate mica at last and send into vulcanizing press, the pressure of 0.1Mpa in room temperature or 80-90 ℃ down sulfuration promptly got aluminium honeycomb/mica composite sheet in 1-2 hour.
The preparation of [embodiment 4] aluminium honeycomb/mica composition board
The source of honeycomb core, plate mica is with embodiment 1.The thickness of aluminium honeycomb core is 15mm in this example, the thickness 0.5mm of plate mica.Tackiness agent consist of 100 parts of hydroxyl-terminated injecting two methyl siloxanes, 30 parts of 201 silicone oil, 8 parts of methyltrimethoxy silanes, 10 parts of aerosils, 50 parts of calcium carbonate superfine powders, 0.1 part of two (two acyl acetonyls) diisopropoxy titanium, 0.5 part of dibutyl tin laurate, 0.8 part of stannous octoate, 5 parts of KH-550 (γ-An Bingjisanyiyangjiguiwan).Earlier that sizing material, filler etc. are mixing even in mill, and carry out drying treatment, and then the adding cross-linking system is mixing evenly, tubulation seals is standby.This tackiness agent is an one-package adhesive, and whole glue operating process will avoid contacting the moisture in the atmosphere, to guarantee the long storage use.
Each component in tackiness agent consumption and act on as shown in table 4:
Table 4
Component Content (weight part) Effect
Two (two acyl acetonyls) the diisopropoxy titanium dibutyl tin laurate stannous octoate KH-550 of hydroxyl-terminated injecting two methyl siloxane 201 silicone oil MTMS aerosil calcium carbonate superfine powders 100 30 8 10 50 0.1 0.5 0.8 5 Base polymer diluent crosslinking agent reinforced filling reinforcer cross-linking catalyst catalyst coupling agent
When making sheet material, the aluminium honeycomb core bonding plane is handled (primary coat liquid is formed with example 1) with primary coat liquid earlier, and then on plate mica, coat one-package adhesive equably, place aluminium honeycomb core on the plate mica at last and send into vulcanizing press, the pressure of 0.1Mpa in room temperature or 80-90 ℃ down sulfuration promptly got aluminium honeycomb/mica composite sheet in 1-2 hour.
The preparation of [embodiment 5] aramid fiber honeycomb/mica composite sheet
The source of honeycomb core, plate mica is with embodiment 1.The aramid fiber honeycomb core is made by fully aromatic polyamide paper (aramid fiber 1313, Fanglun l414).The thickness of aramid fiber honeycomb core is 15mm in this example, and the thickness of plate mica is 0.5mm.The composition of tackiness agent is identical with embodiment 1-4 with method for making.
When making sheet material, aramid fiber honeycomb core bonding plane is handled (primary coat liquid is formed with example 1) with primary coat liquid earlier, and then on plate mica coated with adhesive equably, place the aramid fiber honeycomb core on the plate mica at last and send into vulcanizing press, the pressure of 0.1Mpa in room temperature or 80-90 ℃ down sulfuration promptly got aramid fiber honeycomb/mica composite sheet in 1-2 hour.
The preparation of [embodiment 6] polypropylene honeycomb/mica composite sheet
The source of honeycomb core, plate mica is with embodiment 1.The thickness of polypropylene honeycomb core is 15mm in this example, and the thickness of plate mica is 0.5mm.The composition of tackiness agent is identical with embodiment 1-4 with method for making.
When making sheet material, polypropylene honeycomb core bonding plane is handled (primary coat liquid is formed with example 1) with primary coat liquid earlier, and then on plate mica coated with adhesive equably, place the polypropylene honeycomb core on the plate mica at last and send into vulcanizing press, vulcanize under room temperature at the pressure of 0.1Mpa and promptly got polypropylene honeycomb/mica composite sheet in 1-2 hour.
The preparation of [embodiment 7] polycarbonate honeycomb/mica composite sheet
The source of honeycomb core, plate mica is with embodiment 1.The polycarbonate honeycomb core thickness of Cai Yonging is 15mm in this example, and the thickness of plate mica is 0.5mm.The composition of tackiness agent is identical with embodiment 1-4 with method for making.
When making sheet material, polycarbonate honeycomb core bonding plane is handled (primary coat liquid is formed with embodiment 1) with primary coat liquid earlier, and then on plate mica coated with adhesive equably, place the polycarbonate honeycomb core on the plate mica at last and send into vulcanizing press, vulcanize under room temperature at the pressure of 0.1Mpa and promptly got polycarbonate honeycomb/mica composite sheet in 1-2 hour.
The preparation of [embodiment 8] hard phenol formaldehyde foam/mica composite sheet
The hard phenol formaldehyde foam that adopts among the present invention can be the hard phenolic foam board of little foaming, middle foaming or high foaming, and its thickness is 5-200mm.Hard phenolic foam board, plate mica are originated with embodiment 1.In this example, the hard phenolic foam board of employing is middle foaming plate, and thickness is 15mm, and the thickness of plate mica is 0.5mm.The composition of tackiness agent is identical with embodiment 1-4 with method for making.
When making sheet material, the bonding plane of hard phenolic foam board is handled (primary coat liquid is formed with embodiment 1) with primary coat liquid earlier, and then on plate mica coated with adhesive equably, place the hard phenolic foam board on the plate mica at last and send into vulcanizing press, the pressure of 0.1Mpa in room temperature or 80-90 ℃ down sulfuration promptly got hard phenol formaldehyde foam/mica composite sheet in 1-2 hour.
The resistance toheat test of [embodiment 9] honeycomb core/mica composite sheet
Composite sheet and the surperficial bonding Nomex of honeycomb core in contrast with honeycomb core of the present invention surface built up mica plate TMThe composition board of paper is carried out diathermanous performance relatively, and in the composition board one side burning that is used to test, the heat energy flow (every square metre kilowatt number) of test opposite side the results are shown in Figure 1 and Fig. 2, and ordinate zou is the test heat flux among the figure, and X-coordinate is combustion time.
By the test result among Fig. 1 and Fig. 2 as seen, the bonding Nomex in the honeycomb core of control group surface TMIts high flux of heat of the composition board of paper is 51.98KW/sq.m, and the time that arrives high flux of heat is 26 seconds, and the total heat that was passed in five minutes is 56.43KW-min-sq.m (kilowatt * minute * square metre).And its high flux of heat of honeycomb core mica composition board of the present invention is 38.69KW/sq.m, and the time that arrives high flux of heat is 215.5 seconds, and the total heat that was passed in five minutes is 13.15KW-min-sq.m (kilowatt * minute * square metre).Therefore, PLASTIC LAMINATED diathermancy of the present invention is extremely low.
When carrying out above-mentioned diathermancy test, also carried out the test that the burning back produces gas, the results are shown in Table 5:
Table 5 burning back smog toxicity test: the smog that in the time of 1.5 and 4 minutes, distributes
Test products HF HCl HCN SO 2-H 2S CO NO-NO 2
Honeycomb core+Nomax TMPaper honeycomb core mica composition board 50/50 0/0 50/500 140/138 100/150 2/3 50/100 0/0 3000/3500 170/295 50/100 2/8
By the result of last table as seen, PLASTIC LAMINATED of the present invention never produces toxic gas when burning, produce nontoxic gas hardly.
More than the detailed description of the specific embodiment of the invention is not limited the present invention, those skilled in the art can make various changes and distortion according to the present invention, only otherwise break away from the spirit and scope of the present invention, all should belong to the scope of the appended claim of the present invention.

Claims (23)

1, a kind of PLASTIC LAMINATED comprises an edge grain, at least one binder layer and at least one stratus motherboard; It is characterized in that
Wherein said binder layer comprises following component:
Base polymer 100～150 weight parts
Linking agent 5～20 weight parts
Catalyzer 0.1～2.5 weight part
Filler 5～100 weight parts
Described base polymer is hydroxy-end capped line style polydiorganosiloxane and the multipolymer thereof suc as formula (I) structure,
HO(CH 3R 1SiO) nH，
(I)
R 1Be selected from methyl, phenyl and CF 3CH 2CH 2, n=100～1000;
Described linking agent is selected from one or more of tetraethoxy, the positive butyl ester of boric acid, tetrabutyl titanate, methyl tributanoximo silane, γ-An Bingjisanyiyangjiguiwan, Union carbide A-162, methyltrimethoxy silane and two (two acyl acetonyls) diisopropoxy titanium;
Described catalyzer is selected from dibutyl tin laurate, tetraethoxysilane dibutyl tin, Sn (OCOC 8H 17) 2With one or more of aniline.
2, PLASTIC LAMINATED according to claim 1 is characterized in that described edge grain is selected from metal sheet, cardboard, plastic plate, wood plywood, resol foaming plate or honeycomb core.
3, PLASTIC LAMINATED according to claim 2 is characterized in that described edge grain is a honeycomb core.
4, PLASTIC LAMINATED according to claim 3 is characterized in that the both sides built up mica plate of described edge grain.
5, PLASTIC LAMINATED according to claim 1, wherein said filler comprises reinforced filling and reinforcing filler.
6, PLASTIC LAMINATED according to claim 5, wherein said reinforced filling are silicon-dioxide, carbon black or titanium dioxide.
7, PLASTIC LAMINATED according to claim 5, wherein said reinforcing filler are diatomite, silica powder, ferric oxide or water-ground limestone.
8, PLASTIC LAMINATED according to claim 1, wherein said binder layer comprises:
Hydroxyl-terminated injecting two methyl siloxane 100 weight parts
Aerosil 20 weight parts that prestox ring tetrasilane is handled
947 silicone resins, 20 weight parts
Boric acid 0.4 weight part
Tetraethoxy 5 weight parts
Positive butyl ester 3 weight parts of boric acid
Tetrabutyl titanate 2 weight parts
Dibutyl tin laurate 1.08 weight parts
γ-glycidyl ether oxygen propyl trimethoxy silicane 3 weight parts.
9, PLASTIC LAMINATED according to claim 1, wherein said binder layer comprises:
α, alpha, omega-dihydroxy polydimethyl siloxane and
Graft copolymer 100 weight parts of vinylbenzene, butyl acrylate
Methyl tributanoximo silane 7 weight parts
D 4Handle silica 15 weight parts
γ-An Bingjisanyiyangjiguiwan 3 weight parts
Tetraethoxysilane dibutyl tin 2.5 weight parts.
10, PLASTIC LAMINATED according to claim 1, wherein said tackiness agent comprises:
Hydroxyl-terminated injecting two methyl siloxane 100 weight parts
Viscosity is 201 silicone oil, 20 weight parts of 0.5Pa.s
Union carbide A-162 7 weight parts
D 4Handle silicon-dioxide 20 weight parts
Calcium carbonate superfine powder 30 weight parts
Dibutyl tin laurate 0.2 weight part.
11, PLASTIC LAMINATED according to claim 1, wherein said binder layer comprises:
Hydroxyl-terminated injecting two methyl siloxane 100 weight parts
201 silicone oil, 30 weight parts
Methyltrimethoxy silane 8 weight parts
Aerosil 10 weight parts
Calcium carbonate superfine powder 50 weight parts
Two (two acyl acetonyls) diisopropoxy titanium 0.1 weight part
Dibutyl tin laurate 0.5 weight part
Stannous octoate 0.8 weight part
γ-An Bingjisanyiyangjiguiwan 5 weight parts.
12, a kind of preparation method of PLASTIC LAMINATED comprises the steps:
A) batch mixing is with each component of tackiness agent uniform mixing in proportion;
B) sulfuration is vulcanized mixed tackiness agent at 23～90 ℃;
C) denseness of adjusting tackiness agent;
D) need adherent edge grain and plate mica are carried out surface treatment;
E) bonding;
Wherein said tackiness agent comprises:
Base polymer 100～150 weight parts
Linking agent 5～20 weight parts
Catalyzer 0.1～2.5 weight part
Filler 5～100 weight parts
Described base polymer is hydroxy-end capped line style polydiorganosiloxane and the multipolymer thereof suc as formula (I) structure,
HO(CH 3R 1SiO) nH，
(I)
R in the formula (I) 1Be selected from methyl, phenyl and CF 3CH 2CH 2, n=100～1000;
Described linking agent is selected from one or more of tetraethoxy, the positive butyl ester of boric acid, tetrabutyl titanate, methyl tributanoximo silane, γ-An Bingjisanyiyangjiguiwan, Union carbide A-162, methyltrimethoxy silane and two (two acyl acetonyls) diisopropoxy titanium;
Described catalyzer is selected from dibutyl tin laurate, tetraethoxysilane dibutyl tin, Sn (OCOC 8H 17) 2, aniline one or more.
13, method according to claim 12, wherein said tackiness agent comprises:
Hydroxyl-terminated injecting two methyl siloxane 100 weight parts
Aerosil 20 weight parts that prestox ring tetrasilane is handled
947 silicone resins, 20 weight parts
Boric acid 0.4 weight part
Tetraethoxy 5 weight parts
Positive butyl ester 3 weight parts of boric acid
Tetrabutyl titanate 2 weight parts
Dibutyl tin laurate 1.08 weight parts
γ-glycidyl ether oxygen propyl trimethoxy silicane 3 weight parts.
14, method according to claim 12, wherein said tackiness agent comprises:
α, alpha, omega-dihydroxy polydimethyl siloxane and
Graft copolymer 100 weight parts of vinylbenzene, butyl acrylate
Methyl tributanoximo silane 7 weight parts
D 4Handle silica 15 weight parts
γ-An Bingjisanyiyangjiguiwan 3 weight parts
Tetraethoxysilane dibutyl tin 2.5 weight parts.
15, method according to claim 12, wherein said tackiness agent comprises:
Hydroxyl-terminated injecting two methyl siloxane 100 weight parts
Viscosity is 201 silicone oil, 20 weight parts of 0.5Pa.s
Union carbide A-162 7 weight parts
D 4Handle silicon-dioxide 20 weight parts
Calcium carbonate superfine powder 30 weight parts
Dibutyl tin laurate 0.2 weight part.
16, method according to claim 12, wherein said binder layer comprises:
Hydroxyl-terminated injecting two methyl siloxane 100 weight parts
201 silicone oil, 30 weight parts
Methyltrimethoxy silane 8 weight parts
Aerosil 10 weight parts
Calcium carbonate superfine powder 50 weight parts
Two (two acyl acetonyls) diisopropoxy titanium 0.1 weight part
Dibutyl tin laurate 0.5 weight part
Stannous octoate 0.8 weight part
γ-An Bingjisanyiyangjiguiwan 5 weight parts.
17, preparation method according to claim 12, wherein batch mixing described in the step a) is for one-package adhesive, earlier sizing material, filler etc. mixed, carry out drying treatment after, add cross-linking system and mix, tubulation seals is standby; For two component adhesive, then earlier A component and B component are mixed respectively, with two components of A, B uniform mixing in proportion, described A component is base polymer and filler when coating, the B component comprises linking agent and catalyzer.
18, method according to claim 17, the ratio of A, B component is A: B=100 in the wherein said two-pack batch mixing: 3.5～100: 4.0.
19, method according to claim 12, wherein the denseness of the described adjusting tackiness agent of step c) comprises that adding thickening material as required increases denseness or add thinner reduction denseness; The described surface treatment of step d) comprises to be cleaned and dry, hacking processing substrate surface; Step e) further comprises bonding preceding step at substrate surface coating silane coupling agent.
20, method according to claim 19, wherein said silane coupling agent comprise the silane coupling agent of tool reactive behavior or the organic solvent diluting liquid of organometallic compound.
21, method according to claim 20, wherein said silane coupling agent comprises:
Tetraethoxy 50 weight parts
Union carbide A-162 30 weight parts
γ-glycidyl ether oxygen propyl trimethoxy silicane 20 weight parts
Boric acid 0.4 weight part
Methyl aceto acetate 2 weight parts
Three fluoroboric acid chromium, 3 weight parts
Dehydrated alcohol 118 weight parts
The PH conditioning agent.
22, method according to claim 12, the described pressurized adhesion that is bonded as of step e) wherein, its pressure is 0.1-0.5Mpa, be 1-24 hour clamping time.
23, method according to claim 22, the temperature of wherein said pressurized adhesion are≤90 ℃.
CN 02152849 2002-11-21 2002-11-21 Adhesive, fireproof board with adhesive and its production process Expired - Fee Related CN1272401C (en)

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CN 02152849 CN1272401C (en) 2002-11-21 2002-11-21 Adhesive, fireproof board with adhesive and its production process
PCT/CN2003/000980 WO2004045847A1 (en) 2002-11-21 2003-11-18 A new fire retarding board and manufacturing method thereof
AU2003284810A AU2003284810A1 (en) 2002-11-21 2003-11-18 A new fire retarding board and manufacturing method thereof

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