CN1637108A - Flame resistant sealing material - Google Patents
Flame resistant sealing material Download PDFInfo
- Publication number
- CN1637108A CN1637108A CNA2004101003111A CN200410100311A CN1637108A CN 1637108 A CN1637108 A CN 1637108A CN A2004101003111 A CNA2004101003111 A CN A2004101003111A CN 200410100311 A CN200410100311 A CN 200410100311A CN 1637108 A CN1637108 A CN 1637108A
- Authority
- CN
- China
- Prior art keywords
- sealing material
- elastic sheet
- flame
- flame resistant
- resistant sealing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/82—Post-polymerisation treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
- C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
- C08G18/0847—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers
- C08G18/0852—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers the solvents being organic
- C08G18/0857—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers the solvents being organic the solvent being a polyol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/016—Flame-proofing or flame-retarding additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
- C08K3/12—Hydrides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Manufacturing & Machinery (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Sealing Material Composition (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention provides a flame-retardant sealing material which has an elastic sheet obtained by forming a mixture of a main material formed of polyol and isocyanate, an auxiliary material including foam stabilizer and metal hydroxide, and a gas for foaming. In the flame-retardant sheet material is characterized by the followings: 25-50 pts.wt. of a metal hydroxide is mixed with 100 pts.wt. of the polyol using the material reactive with the isocyanate as the diluting solvent of the auxiliary material; having the flame retardancy attaining the HBF standard prescribed by UL 94; and exhibiting 25% compression load of <=0.03 MPa. The invention is capable of providing a flame-retardant sealing material with excellent flame-retardancy and excellent sealing property, which is used under a severe environment such as a high-temperature atmosphere and suitably applicable to high heat-buildup electronic components, precision devices, and the like.
Description
Technical field
The present invention relates to a kind of flame resistant sealing material.Be specifically, relate to and a kind ofly have good sealing property and flame retardant resistance, and the flame resistant sealing material that is adapted in the rigorous environment such as high-temperature atmosphere or in high electronics of exothermicity or precision instrument, uses.
Background technology
On the electronics of indicating meter of mobile phone, TV, computer and so on, be provided with as input and output portions such as liquid crystal display part, microphone portion, the portions of raising one's voice.These input and output portions are arranged at the position to outside opening of electrical equipment basket.Therefore, under the situation of for example liquid crystal display part, between the periphery of liquid crystal display part and basket, be provided with and be used to the sealing material that light backlight leaks and basket rocks that prevents that liquid-crystal display from using.In recent years, multifunction and lightweight along with the mobile phone being the various electrical equipment of representative have also proposed little and thin requirement to such sealing material.As the starting material of this sealing material, the urethane foam with good flexibility and soft is owing to approaching and can giving full play to the sealing material effect, so be widely used.In addition, because the deterioration (the so-called mistake strained) of material or the generation of gas seldom appear in urethane foam, therefore be suitable for being arranged in the purposes of the intravital sealing material of electrical equipment basket.
As implied above, the sealing material that is made of urethane foam has the superperformance as sealing material.But described sealing material has high specific surface area owing to formed by organism, form thin laminar simultaneously, therefore, under the situation that is assembled into electrical equipment or electronics basket, the heat that sends in the time of might be by these equipment works and be in the condition of high temperature.Therefore, sealing material also needs to have high flame retardant resistance.At this point, extensively adopt following technology at present, promptly, general halogenated flame retardant, (b) organophosphorus based compound, (c) ANTIMONY TRIOXIDE SB 203 99.8 PCT, (d) metal hydroxidess such as (a) organbromine compound, organochlorine compound of in the raw material of sealing material, containing, a kind of or two or more Deng in the fire retardant, thus flame retardant resistance improved.
Yet, under the situation of the fire retardant of stating in the use (a)～(d), have following problem.
(a) the halogen based compound is owing to can produce the halogenide big to the load of environment when burning, and it is unfavorable therefore using as fire retardant.
(b) when using the organophosphorus based compound as fire retardant, might produce the problem of the strength deterioration of urethane foam, perhaps can cause the detrimentally affect of the formation reaction that hinders urethane foam.
(c) ANTIMONY TRIOXIDE SB 203 99.8 PCT is confirmed to be and can causes foregoing carrying capacity of environment, therefore is not suitable for using.
(d) when using metal hydroxidess such as aluminium hydroxide or magnesium hydroxide, can not bring the problem of foregoing relevant carrying capacity of environment as fire retardant.But on the other hand,, need in the raw material of urethane foam, mix a large amount of metal hydroxidess in order to satisfy for example flame-retardancy standards of UL94 (packing material and the sound-proof material of light current power locomotive system) regulation.At this moment, as sealing material useful rerum natura, the rerum naturas such as soft that for example in urethane foam, should be embodied originally probably be compromised.
Here, UL94 is that U.S. UNDERWRITERS LABORATORIES INC. society formulates and approved safety standards about electric installation.The flame retardant resistance of UL94 regulation is estimated in the following manner, promptly, in the experimental installation shown in Fig. 5 (a) and (b) 40, the updraft of Bunsen burner or Trirrill lamp 44 is touched mounting on the test film on the wire netting 42 41, and by estimating burning extent and the combustion time of measuring this test film 41.In this UL94, with as Fig. 5 (a), (b) horizontal burning test shown in (Horizontal Burning Foamed MaterialTest) comes under the situation of HBF standard of flame retardant resistance of evaluation test sheet 41, when an end of the length direction of the rectangle test film 41 that updraft is touched 150mm * 50mm, judge whether to satisfy (i) and be no more than the 40mm/ branch to the combustionvelocity of the position of the 100mm of being separated by along test film 41 length directions from being contacted with the up-draft position, and ii) test film 41 and is estimated thus by disappeared before arriving the 125mm mark in these two conditions either party of the flame after lighting or aura.In addition, described 125mm mark is arranged at from being contacted with the up-draft position along the be separated by position of 125mm of the length direction of test film 41.
Summary of the invention
In order to overcome above problem and to reach desired purpose, the invention provides a kind of flame resistant sealing material, wherein have elastic sheet 12, this elastic sheet 12 utilizes to mix the main raw material that is made of polyvalent alcohol and isocyanic ester, comprise the auxiliary material of surfactant and metal hydroxides 16 and make mixture that bubble forms with gas and forms and obtain.And then, this flame resistant sealing material is characterised in that: the metal hydroxides 16 that is mixed with 25～50 weight parts in the described polyvalent alcohol of 100 weight parts, and can use with solvent as the dilution of auxiliary material with the material of described isocyanate reaction, and, when the flame retardant resistance of stipulating among the UL94 of sealing material satisfied the HBF standard, 25% compression load was below 0.03MPa.
Flame resistant sealing material of the present invention has good sealing property and flame retardant resistance, and is suitable for using under rigorous environment such as high-temperature atmosphere, perhaps uses in high electronics of exothermicity or precision instrument.
Description of drawings
Fig. 1 is that expression part is cut the flame resistant sealing material of suitable embodiment of the present invention and the stereographic map represented.
Fig. 2 is a stereographic map of representing not possess the flame resistant sealing material of base material film.
Fig. 3 is the process picture sheet of manufacture method of the flame resistant sealing material of expression embodiment.
Fig. 4 is the figure of an example of the manufacturing installation of the expression flame resistant sealing material of making embodiment.
Fig. 5 (a) is the stereographic map of the integral body of the expression experimental installation of implementing the flame retardant test stipulated among the UL94, and Fig. 5 (b) is the enlarged view around the test film of the same experimental installation of expression.
Among the figure: 10-flame resistant sealing material, 12-elastic sheet, 16-metal hydroxides.
Embodiment
Below, the suitable embodiment of the flame resistant sealing material that present invention will be described in detail with reference to the accompanying.The inventor has drawn following opinion by the further investigation to flame resistant sealing material.That is, in the urethane foam, heated volatile and become the inflammable gas composition, and to reduce the content of the unreacted monomer of flame retardant resistance and low molecule oligopolymer thus very little.Therefore, urethane foam is suitable as the raw material use of sealing material.In addition,, then can avoid using amine catalyst, and can suppress the inevitably volatilization of surfactant in the manufacturing of foams as the high lower-molecular substance of volatility if adopt mechanical foaming (mechanical froth) method.Thus obtained flame resistant sealing material has not only reduced the combined amount of metal hydroxides, also has sufficient flame retardant resistance and stopping property.
In addition, in the present invention, as the flame retardant resistance and the stopping property of the feature rerum natura of flame resistant sealing material, respectively by the HBF standard of stipulating among the above-mentioned UL94 and 25% compression load (below, be called 25%CLD (Compression Load Deflection)) defined.In addition, be to estimate about flame retardant resistance according to whether satisfying the HBF standard, about stopping property then be according to as the 25%CLD of the index of expression flexibility whether at 0.03Mpa to estimate down.
As shown in Figure 1, flame resistant sealing material 10 is made of following two-part structure, the i.e. elastic sheet 12 that constitutes by the foams that possess various rerum naturas such as resiliency, stopping property, flexibility and shape servo-actuated, and be layered on the one side of this elastic sheet 12 and be used to improve the base material film 14 of the structural strength of flame resistant sealing material 10.Described elastic sheet 12 can be by known mechanical foaming manufactured.More particularly, by mixing the main raw material that constitutes by polyvalent alcohol and isocyanic ester, comprising surfactant and as the auxiliary material of the metal hydroxides 16 of fire retardant with make bubble gas, and be modulated into foams raw material M, afterwards, M is shaped to laminar with this foams raw material.The inside homodisperse of elastic sheet 12 has metal hydroxides 16 (with reference to Fig. 1).About the more detailed description of mechanical foaming method, be documented in the special public clear 53-8735 communique.Main points wherein are as follows: so-called mechanical foaming method is meant, imports in aqueous material behind the gas by with mechanical system it being mixed the method that obtains foams.
As the physics value of the elastic sheet 12 that obtains by above method,,, require (1) 25%CLD below 0.03MPa as the index of flexibility in order to estimate stopping property.The load of the necessity when 25%CLD represents to implement the physical property compression, the i.e. hardness of the elastic sheet 12 when the physical property compression that applies 25%.In addition, about another physics value of elastic sheet 12, as the index of estimating stopping property and flame retardant resistance both sides, preferred (2) density is 240～500kg/m
3As other physics values of elastic sheet 12, preferred (3) thickness is 0.3～3.0mm.
Here, if 25%CLD surpasses 0.03MPa, then the flexibility of elastic sheet 12 will descend, thereby can not bring into play sufficient stopping property.If the not enough 240kg/m of density
3, then the bubble in the elastic sheet 12 will be in sparse state, cause and air between contact area increase, thereby be difficult to satisfy the HBF standard of UL94 regulation.In contrast, if density surpasses 500kg/m
3, then 25%CLD also increases simultaneously, so the stopping property of elastic sheet 12 can reduce.If the not enough 0.3mm of thickness then not only is difficult to give full play to the stopping property of elastic sheet 12, but also owing to improve for the up-draft ignition quality, so the HBF standard of UL94 regulation is difficult to be satisfied.If opposite thickness surpasses 3.0mm,, be difficult to be assembled into being provided with in the limited small sized product in space of mobile phone and so on then because thickness is blocked up.
In addition, about to elastic sheet 12 desired above-mentioned physics values in addition,, need to satisfy the HBF standard of (4) UL94 regulation as the index of estimating flame retardant resistance.The flame retardant resistance of elastic sheet 12 can improve in the following manner, promptly, for foams raw material M hybrid regulatory certainty ratio as the metal hydroxides 16 of fire retardant the time, with using with solvent as the dilution of auxiliary material of polyvalent alcohol and so on the material of described isocyanate reaction, and the dispersion liquid of thus obtained surfactant mixed, improve flame retardant resistance with this.
In the manufacturing of elastic sheet 12, identical when making common urethane foam as previously mentioned, use the main raw material that constitutes by polyvalent alcohol and isocyanic ester and comprise surfactant and the auxiliary material of metal hydroxides 16.In addition this moment, can use at least a auxiliary material that is selected from whipping agent, linking agent, softening agent and the catalyzer as required.Here, the content of polyvalent alcohol in the elastic sheet 12 and isocyanic ester is preferably set to respectively about 20～45 weight % and 25～35 weight %.In addition, set by following scope respectively, that is, and preferred 2～3 weight % of the content of the surfactant in the elastic sheet 12 (comprising the dilution solvent), preferred 8～15 weight % of content of linking agent, preferred 3～5 weight % of content of catalyzer.In addition, in the manufacturing of this elastic sheet 12, be used in the mechanical foaming method non-active gas and so on make the combined amount of bubble with gas, preferably, contain about 50～200 volume % with respect to the cumulative volume 100 of making the whole raw materials the bubble usefulness gas except that this.
As metal hydroxides 16, can use can dissociate intramolecular hydroxyl by heating and (OH) generate the metal hydroxides of water as aluminium hydroxide or magnesium hydroxide and so on.The combined amount of metal hydroxides 16 is 25～50 weight parts with respect to polyvalent alcohol 100 weight parts preferably, more preferably contains 30～35 weight parts.If these combined amount less than 25 weight parts then can't be brought into play the flame retardant resistance of expectation, and in contrast, if surpass 50 weight parts, then flame resistant sealing material 10 may hardening or is embodied fragility and reduce stopping property.
The median size of metal hydroxides 16 is preferably 10～100 μ m, more preferably 20～60 mu m ranges.If the median size deficiency of metal hydroxides 16 10 μ m, then because the viscosity of foams raw material M can improve or the water ratio of foams raw material M uprises, cause the foamable reaction between water and the isocyanic ester, therefore be difficult to by the suitable elastic sheet 12 of mechanical foaming manufactured.If the median size of opposite metal hydroxides 16 surpasses 100 μ m, then because when metal hydroxides 16 is mixed into foams raw material M, be easy to generate the precipitation of metal hydroxides 16, the inside that therefore is difficult in elastic sheet 12 is dispersed metal compound 16 suitably.If use has produced the sedimentary foams raw material M of metal hydroxides 16 and make flame resistant sealing material 10, then can occur producing according to the also different condition of poor of the different flame retardant resistances at position.In addition, though also can finish the manufacturing of flame resistant sealing material 10 before the precipitation that produces described metal hydroxides 16, manufacturing time can be restricted in this case, therefore might bring obstruction to the ideal manufacturing.
Can be suitable for known silicone-based surfactant as surfactant.This surfactant is absolutely necessary in the manufacturing based on the urethane foam of mechanical foaming method, but owing to be lower-molecular substance and burning easily, therefore also becomes simultaneously a reason of the flame retardant resistance that reduces elastic sheet 12.In addition, owing to the very high viscosity that has of silicone-based surfactant itself, therefore must in diluting, re-use after the dilution earlier with solvent.As the solvent that is used to dilute surfactant, can use polyvalent alcohol and so on can with the material of described isocyanate reaction.
When utilization is dispersed in the conduct dilution with the manufacturing of the surfactant in the polyvalent alcohol of solvent elastic sheet 12, react as the polyvalent alcohol of diluting solvent and isocyanic ester as the main raw material of elastic sheet 12, generate polyurethane molecular, and surfactant enters in this polyurethane molecular.Its result, in the elastic sheet 12 that obtains, the volatilization of surfactant is prevented from, thereby has weakened the reason that flame retardant resistance descends.The amount of the solvent during the dilution surfactant is preferably set to the amount that the content that makes surfactant reaches 30～70 weight % scopes.If described surfactant contain quantity not sufficient 30 weight %, the frothing function when then making elastic sheet 12 will descend.On the contrary, if the content of surfactant surpasses 70 weight %, then the viscosity of the dispersion liquid of surfactant will improve, thereby the operability when making is descended.
In addition, general solvent as dilution silicone-based surfactant can use well as the low-viscosity aqueous low-boiling point material of having at normal temperatures of alkylbenzene and so on.But these low-boiling point materials volatilize easily, and the danger that therefore damages the goods flame retardant resistance becomes bigger.About such low-boiling point material, be not only dilution and use solvent, also be fit to be used in and synthesize as diversified materials such as the monomer of the polyvalent alcohol of main raw material or antioxidants.In addition, satisfy a condition of HBF standard as the flame retardant resistance of stipulating among the UL94, but the content that is dissolvable in water material in the acetone (below, be called dissolved material) in the regulation elastic sheet 12.In the present invention, the content of the dissolved material in the elastic sheet 12 is preferably below 5.0 weight %.If the inventor has also confirmed the content of dissolved material and has surpassed 5.0 weight %, even the correlated condition of the combined amount of then above-mentioned metal hydroxides 16 and relevant above-mentioned surfactant all is satisfied, the flame retardant resistance of stipulating among the UL194 can not satisfy the HBF standard.
The content of this dissolved material, be when measuring with acetone extract elastic sheet 12 percentage extraction,, the acetone extract rate obtains by measuring.In the embodiment of back, will provide an example of the concrete measuring method of acetone extract rate.In addition, under the situation of the low-boiling point material that uses alkylbenzene and so on as the solvent that dilutes surfactant, therefore this low-boiling point material makes solvent significantly change to the transitivity problem of the parts transfer of basket that touches elastic sheet 12 and so on owing to exist with the form outside the molecular structure that is free on urethane in the inside of elastic sheet 12 probably.Thereby, by the solvent as the dilution surfactant use as polyvalent alcohol and so on can with as described in the material of isocyanate reaction, be expected significantly to suppress above-mentioned transitivity problem.
(example of manufacture method)
The following describes the example of suitable manufacturing installation of the flame resistant sealing material 10 of present embodiment, and use this manufacturing installation to make an example of the method for flame resistant sealing material 10.The manufacture method of flame resistant sealing material 10 as shown in Figure 3, is made of raw material preparation process S1, raw material supplying and forming process S2, heating process S3, final operation S4.This flame resistant sealing material 10 is made by manufacturing installation shown in Figure 4 30.
In this manufacturing installation 30,, possess and mix main raw material, various auxiliary material and make the mixing portion 31 of bubble with gas in order to obtain to be used to implement the foams raw material M of the urethane foam of mechanical foaming method.In addition, in this manufacturing installation 30, also possess by the donor rollers 32a and the goods that use drive source not shown in the figures to transport and reclaim the roller mechanism 32 that roller 32b constitutes as the base material film that transports media 14 of foams raw material M.On base material film 14, supply with foams raw material M by nozzle 34.At the downstream side of this nozzle 34, be provided with the products thickness controlling organization 36 that is used for foams M is configured as the laminar knife coater and so on of specific thickness, and, be provided with tunnel heating 38 at the downstream side of products thickness controlling organization 36.In addition, here be foams raw material M is reacted and to solidify, but also can react in required shaping die or on the release paper and solidify.
Mixing portion 31 possess have as the polyvalent alcohol of the polyvalent alcohol of main raw material with container 31a, have as the isocyanic ester of the isocyanic ester of main raw material with container 31b, have as the surfactant of the surfactant of auxiliary material with container 31c and there is metal hydroxides container 31d as the metal hydroxides 16 of auxiliary material.In addition as required, the container that has surfactant and metal hydroxides 16 auxiliary material in addition can also be set.In addition, mixing portion 31 also possesses to be filled with and makes bubble with gas containers 31e and mixing machine 31f.Raw material in each container 31a～31e is supplied to mixing machine 31f, and mixes in this mixing machine 31f under controlled state.
Among the raw material preparation process S1 that in mixing portion 31, implements, prepare main raw material, auxiliary material and make bubble and use gas, use mixing machine 31f that they are mixed afterwards, thereby be modulated into foams raw material M by known method in the past.
In raw material supplying and forming process S2, after nozzle 34 was ejected into base material film 14, this foams raw material M was shaped by products thickness controlling organization 36 with by the state of mounting on base material film 14 at foams raw material M.Products thickness controlling organization 36, be ejected to foams raw material M on the base material film 14 be configured as specific thickness (0.3～3.0mm) laminar.
In heating process S3, be configured as the duplexer of laminar foams raw material M and base material film 14, in tunnel heating 38, be heated.Tunnel heating 38 by under in check condition the foams raw material M that is configured as specific thickness being heated, is reacted foams raw material M and is solidified into flame resistant sealing material 10.
In final operation S4,, afterwards, implement final inspection to flame resistant sealing material 10 at the flame resistant sealing material 10 that obtains to form strip through each operation S1～S3.At this moment, can constitute the die-cut operation of the shape of end article to flame resistant sealing material 10 as required.Finish final inspection flame resistant sealing material 10 afterwards and be winding on the goods recovery roller 32b, become the state that to freight.In this manufacture method,, therefore be expected significantly to reduce manufacturing cost owing to the strip that flame resistant sealing material 10 can be fabricated to more than the 5m.
(embodiment)
Represented to use manufacturing installation shown in Figure 4 30 below, in table 1 (embodiment 1～8) and table 2 (comparative example 1～8), make after the flame resistant sealing material experimental example of estimating for the various rerum naturas of the flame resistant sealing material that is obtained under the condition of record.
Metal catalyst (the stannous octoate that mixes 0.1 weight part to 100 weight part polyether glycols (molecular-weight average 3000, hydroxyl value 43.0), ス Na ス オ Network ト エ one ト) and silicone-based surfactant of 3 weight parts (contain dilution use solvent) and metal hydroxides 16 (combined amount is with reference to table 1 and table 2), acquisition mixture.Then, by flow mixings nitrogen (making bubble gas) from 0.1NL/ to this mixture that divide with and isocyanate index be set to 0.9～1.1 isocyanic ester (natural MDI, NCO content: 31%), and cut fragrant plant, thereby acquisition foams raw material M.Make this foams raw material M through nozzle 34, be ejected on the base material film 14 (PET system) with specific thickness.In addition this moment, base material film 14 is supplied with from donor rollers 32a continuously to be applied the tensile state by roller mechanism 32.In addition, described foams raw material M becomes the amount of the numerical value that table 1 and table 2 put down in writing with the density of the elastic sheet 12 after making, and supplies with from nozzle 34, and be shaped with products thickness controlling organization 36, make the thickness of the elastic sheet 12 after the manufacturing reach the numerical value that table 1 and table 2 are put down in writing.In addition, by in tunnel heating 38, carrying out heating 1～3 minute under 150 ℃～200 ℃, react and solidify being layered in foams raw material M on the base material film 14.Its result has obtained the flame resistant sealing material of stacked flexible thin slice 12 on base material film 14.At last, reclaim roller 32b, reclaim the flame resistant sealing material that obtains with goods.
The metal hydroxides 16 and the surfactant that use are as follows.
Metal hydroxides: the aluminium hydroxide (trade(brand)name of clear and electrician's system: Ha イ ジ ラ イ ト H-21 (median size 25 μ m))
Surfactant:
(A) Osi Specialties system, trade(brand)name: L-5617 (using in the polyvalent alcohol of solvent as dilution, containing the commodity of polydimethylsiloxane and polyoxyethylene glycol with the ratio of 50 weight %)
(B) Osi Specialties system, trade(brand)name: L-5614 (using in the alkylbenzene of solvent as dilution, containing the commodity of polydimethylsiloxane and polyoxyethylene glycol with the ratio of 50 weight %)
From the flame resistant sealing material of the embodiment 1～8 that makes based on table 1 and table 2 and comparative example 1～8, peel off base material film 14, only obtain elastic sheet 12.From the elastic sheet 12 that obtains, the test film that has obtained the round shape test film of the rectangle test film 41 that is used for specific thickness * 150mm * 50mm that flame retardant resistance estimates of 1g, specific thickness * φ 50mm that 25%CLD measures usefulness respectively and be used to measure the content of dissolved material.For these test films, the acetone extract rate (%) of having measured expression 25%CLD (MPa) respectively and having represented the content of dissolved material.In addition, use experimental installation 40 as shown in Figure 5, the flame retardant resistance of stipulating among the UL94 is estimated.When estimating this flame retardant resistance, under the situation that satisfies the HBF standard, be designated as zero, ungratified situation is next is designated as *, and be documented in the table respectively.In addition,, whether the present invention is suitable as flame resistant sealing material, has carried out comprehensive evaluation according to these results.When carrying out the above-mentioned comprehensive evaluation that whether is fit to, under situation about being fit to, be designated as zero, the situation that is not suitable for is next is designated as *, and be documented in respectively in the comprehensive evaluation hurdle in the table.In addition, whether elastic sheet 12 is contained alkylbenzene detect, and be documented in the table.Measuring method and condition determination are as follows.
(measuring method and condition)
Density: measure based on JIS K 6401.That is, take the square test film of 50mm * 50mm, and usage degree disc type thickness gauge and electronic scales, the weight and volume of determination test sheet.And, according to calculating formula: density (kg/m
3Volume (the m of the weight of)=test film (kg)/test film
3), calculated the density of elastic sheet 12.
25%CLD: use compression testing machine, the compression speed so that 1mm/ divides is compressed to 25% of original thickness with test film, measures load this moment.And, the area (cm of load (the N)/test film when compressing according to calculating formula: 25%CLD (MPa)=25%
2), calculated 25%CLD.
Flame retardant resistance: use the experimental installation 40 shown in Fig. 5 (a) and (b), and according to the HBF standard of stipulating among the UL94, the flame retardant resistance of evaluation test sheet 41.
The amount of dissolved substances in the acetone (acetone extract rate): be contained on the soxhlet's extractor by test film (here being 1g) with elastic sheet 12, and in this extractor, acetone is carried out 3 hours reflux, thereby extraction is dissolved in the material in the acetone, then, dry this extract, and measure dry weight.And, calculate the percentage extraction of acetone according to following calculating formula, that is:
Test film weight (g) * 100 before the dry weight (g) of acetone extract rate (%)=extract/the be contained in soxhlet's extractor.
Whether contain alkylbenzene: use gas chromatograph quality analysis apparatus (GC-MS; Shimadzu Seisakusho Ltd.'s system, trade(brand)name: QP-5000), above-mentioned extract is carried out spectroscopic analysis, and estimate thus.
(result)
The result is shown in the following table.Can confirm according to table 1 and table 2: be set in the benzene scope of invention by each physics value, can obtain to have the flame-retardant materials of flame retardant resistance and stopping property elastic sheet 12.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| Elastic sheet thickness (mm) | ??0.3 | ??0.4 | ??0.5 | ??← | ??← | ??1.0 | ??1.5 | ??3.0 |
| Density (kg/m 3) | ??360 | ??360 | ??240 | ??320 | ??500 | ??360 | ??320 | ??240 |
| The surfactant kind | ??A | ??← | ??← | ??← | ??← | ??← | ??← | ??← |
| The combined amount of metal hydroxides (weight part) | ??30 | ??← | ??← | ??← | ??← | ??← | ??20 | ??30 |
| The result | ||||||||
| 25％CLD(MPa) | ??0.012 | ??0.012 | ??0.007 | ??0.011 | ?0.030 | ??0.012 | ??0.011 | ??0.007 |
| Flame retardant resistance (zero, *) | ??○ | ??← | ??← | ??← | ??← | ??← | ??← | ??← |
| Acetone extract rate (%) | ??4.5 | ??4.7 | ??4.0 | ??5.0 | ??4.1 | ??4.7 | ??4.5 | ??4.0 |
| Whether contain alkylbenzene | Do not have | ??← | ??← | ??← | ??← | ??← | ??← | ??← |
| Comprehensive evaluation | ??○ | ??← | ??← | ??← | ??← | ??← | ??← | ??← |
In this table, so-called 25%CLD represents 25% compression load.
In this table, the kind of surfactant is A:L-5617, B:L-5614.
Table 2
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | |
| Elastic sheet thickness (mm) | ??0.3 | ??0.5 | ??← | ??← | ??← | ??← | ??1.5 | ??0.5 |
| Density (kg/m 3) | ??400 | ??200 | ??550 | ??400 | ??320 | ??400 | ??320 | ??400 |
| The surfactant kind | ??A | ??← | ??← | ??← | ??← | ??B | ??← | ??A |
| The combined amount of metal hydroxides (weight part) | ??30 | ??← | ??← | ??20 | ??50 | ??30 | ??20 | ??30 |
| The result | ||||||||
| 25％CLD(MPa) | ??0.015 | ??0.005 | ??0.035 | ??0.015 | ??0.040 | ??0.015 | ??0.011 | ??0.011 |
| Flame retardant resistance (zero, *) | ??× | ??× | ??○ | ??× | ??○ | ??× | ??← | ??← |
| Acetone extract rate (%) | ??4.2 | ??4.4 | ??4.5 | ??4.1 | ??4.5 | ??4.4 | ??4.5 | ??7.5 |
| Whether contain alkylbenzene | Do not have | ??← | ??← | ??← | ??← | Have | ??← | Do not have |
| Comprehensive evaluation | ??× | ??← | ??← | ??← | ??← | ??← | ??← | ??← |
In this table, so-called 25%CLD represents 25% compression load.
In this table, the kind of surfactant is A:L-5617, B:L-5614.
Claims (5)
1. flame resistant sealing material, has elastic sheet (12), this elastic sheet (12) forms and obtains mixing the main raw material be made up of polyvalent alcohol and isocyanic ester, contain the auxiliary material of surfactant and metal hydroxides (16) and making mixture that bubble forms with gas, it is characterized in that:
Be mixed with the metal hydroxides (16) of 25～50 weight parts with respect to the described polyvalent alcohol of 100 weight parts, and can use with solvent as the dilution of auxiliary material with the material of described isocyanate reaction, and flame retardant resistance sealing material, that stipulate among the UL94 satisfies the HBF standard, and 25% compression load is below 0.03MPa simultaneously.
2. flame resistant sealing material as claimed in claim 1 is characterized in that: contain the following material that is dissolvable in water acetone of 5.0 weight % in the described elastic sheet (12).
3. flame resistant sealing material as claimed in claim 1 is characterized in that: the median size of described metal hydroxides (16) is set to the scope of 10～100 μ m.
4. flame resistant sealing material as claimed in claim 1 is characterized in that: the thickness of described elastic sheet (12) is set to 0.3～3.0mm scope.
5. as any one described flame resistant sealing material in the claim 1～4, it is characterized in that: the density of described elastic sheet (12) is set to 240～500kg/m
3Scope.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003413831A JP4544853B2 (en) | 2003-12-11 | 2003-12-11 | Method for producing flame retardant sealing material |
| JP2003413831 | 2003-12-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1637108A true CN1637108A (en) | 2005-07-13 |
| CN100393805C CN100393805C (en) | 2008-06-11 |
Family
ID=34733851
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004101003111A Active CN100393805C (en) | 2003-12-11 | 2004-12-09 | Flame resistant sealing material |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP4544853B2 (en) |
| KR (1) | KR101133148B1 (en) |
| CN (1) | CN100393805C (en) |
| HK (1) | HK1074456A1 (en) |
| TW (1) | TWI363079B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101850639A (en) * | 2009-03-24 | 2010-10-06 | 井上株式会社 | Polyurethane foam laminate, manufacturing method thereof, and gasket |
| CN101017965B (en) * | 2007-02-14 | 2011-07-06 | 上海市电力公司 | A blocking technology of SF6 gas insulation power device leakage |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5660975B2 (en) * | 2011-05-27 | 2015-01-28 | 株式会社イノアックコーポレーション | Sealing material and manufacturing method thereof |
| PL3677610T3 (en) * | 2019-01-07 | 2022-01-31 | Evonik Operations Gmbh | Preparation of polyurethane foam |
| CN116218202A (en) * | 2023-02-03 | 2023-06-06 | 广东安拓普聚合物科技有限公司 | Sealing ring material and preparation method thereof |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA999400A (en) * | 1972-04-28 | 1976-11-02 | General Tire And Rubber Company (The) | Flame retardant flexible polyurethane foams |
| JPS60139445A (en) * | 1983-12-27 | 1985-07-24 | 株式会社イノアックコーポレーション | Flame-retardant polyurethane foam for flame lamination |
| US4876291A (en) * | 1988-08-24 | 1989-10-24 | J.M. Huber Corporation | Mineral filler fire retardant composition and method |
| DE3902238A1 (en) * | 1989-01-26 | 1990-08-02 | Jones Parker & Co Ltd | Foamable potting compound with adjustable, preferably longer processing time |
| JPH06240135A (en) * | 1993-01-07 | 1994-08-30 | Bayer Ag | Highly flame-retardant polyamide molding composition |
| DK0791613T3 (en) * | 1996-02-14 | 1999-11-01 | Sika Ag | Flame retardant polyurethane systems |
| JPH09249728A (en) * | 1996-03-19 | 1997-09-22 | Inoac Corp | Flame-retardant polyurethane foam |
| JPH11140150A (en) * | 1997-11-13 | 1999-05-25 | Chisso Corp | Composition for low-smoking flame-retardant polyisocyanurate foam and low-smoking flame-retardantfoam prepared therefrom |
| JPH11291375A (en) * | 1998-04-10 | 1999-10-26 | Achilles Corp | Fixed form elastic foamed sealing material and manufacture thereof |
| DE19921472A1 (en) * | 1999-05-08 | 2000-11-16 | Sued Chemie Ag | Flame retardant polymer composition |
| JP2002226545A (en) | 2001-01-31 | 2002-08-14 | Sanyo Chem Ind Ltd | Polymer polyol composition and method for producing polyurethane resin |
| JP2003221425A (en) | 2002-01-31 | 2003-08-05 | Sanyo Chem Ind Ltd | Method for producing polyurethane foam |
-
2003
- 2003-12-11 JP JP2003413831A patent/JP4544853B2/en not_active Expired - Lifetime
-
2004
- 2004-12-02 TW TW093137114A patent/TWI363079B/en not_active IP Right Cessation
- 2004-12-09 CN CNB2004101003111A patent/CN100393805C/en active Active
- 2004-12-10 KR KR1020040104154A patent/KR101133148B1/en active IP Right Grant
-
2005
- 2005-09-28 HK HK05108548A patent/HK1074456A1/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101017965B (en) * | 2007-02-14 | 2011-07-06 | 上海市电力公司 | A blocking technology of SF6 gas insulation power device leakage |
| CN101850639A (en) * | 2009-03-24 | 2010-10-06 | 井上株式会社 | Polyurethane foam laminate, manufacturing method thereof, and gasket |
| CN101850639B (en) * | 2009-03-24 | 2014-10-01 | 井上株式会社 | Polyurethane foam laminate, manufacturing method thereof, and gasket |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100393805C (en) | 2008-06-11 |
| KR20050058220A (en) | 2005-06-16 |
| TWI363079B (en) | 2012-05-01 |
| JP2005171102A (en) | 2005-06-30 |
| TW200519163A (en) | 2005-06-16 |
| HK1074456A1 (en) | 2005-11-11 |
| KR101133148B1 (en) | 2012-04-06 |
| JP4544853B2 (en) | 2010-09-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101950156B1 (en) | Phenol resin foam body and method for producing same | |
| CN109880585B (en) | Liquid silicone rubber selectively bonding plastic base materials and preparation method thereof | |
| KR19990067895A (en) | Flexible cellular material, composition and process for its preparation | |
| RU2714081C2 (en) | Method of producing article from foamed polyurethane | |
| TWI383030B (en) | Silicone-free adhesive composition without aromatic solvent and adhesive tape, sheet or label | |
| CN103998528B (en) | Thermal conductivity moisture-curable resin combination | |
| KR100585531B1 (en) | Hard polyurethane foam composition and insulation for keeping coolness using it | |
| CN1637108A (en) | Flame resistant sealing material | |
| CN114478626B (en) | Difunctional modified flame-retardant isocyanate compound and synthesis method thereof | |
| KR20120005406A (en) | Method for manufacturing cured product of thermosetting resin composition and cured product obtained thereby | |
| JP6316592B2 (en) | Addition-curing silicone rubber composition used for light transmission from a light source in a lighting fixture | |
| TW200415148A (en) | Vapor pressure depressant and use thereof | |
| JP6126944B2 (en) | Polyurethane foam waterproofing material | |
| CN105368068A (en) | High-temperature-resistant, high-breakdown-voltage and filler-free organic silicone rubber for sleeve | |
| JP3902143B2 (en) | Polyol composition for rigid polyurethane foam and method for producing rigid polyurethane foam | |
| JP4263028B2 (en) | Polyol composition for rigid polyurethane foam and method for producing rigid polyurethane foam | |
| EP4206271A1 (en) | Resin composition | |
| CN109880058B (en) | Preparation method of molecular chain soft segment flame-retardant polyurethane foam | |
| TW201430063A (en) | Thermosetting silicone rubber composition | |
| JP5086575B2 (en) | Polyol composition and method for producing rigid polyurethane foam | |
| EP2686373B1 (en) | Reactive flame retardants blends for flexible polyurethane foams | |
| EP4353764A1 (en) | Polyurethane foam and manufacturing method therefor | |
| CN116376509B (en) | Flame-retardant silicone fireproof sealant and preparation method thereof | |
| JP7363787B2 (en) | Resin compositions, heat storage materials, and articles | |
| CN1659219A (en) | Compositions of pentafluoropropane, pentafluorobutane and water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: DE Ref document number: 1074456 Country of ref document: HK |
|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: GR Ref document number: 1074456 Country of ref document: HK |