CN100398590C - Expandable composition for filling use, expandable member for filling use and expanded article for filling use - Google Patents
Expandable composition for filling use, expandable member for filling use and expanded article for filling use Download PDFInfo
- Publication number
- CN100398590C CN100398590C CNB2004800094376A CN200480009437A CN100398590C CN 100398590 C CN100398590 C CN 100398590C CN B2004800094376 A CNB2004800094376 A CN B2004800094376A CN 200480009437 A CN200480009437 A CN 200480009437A CN 100398590 C CN100398590 C CN 100398590C
- Authority
- CN
- China
- Prior art keywords
- filling
- foam
- composition
- foaming
- whipping agent
- 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.)
- Expired - Fee Related
Links
Images
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Filling foam composition capable of providing excellent rustproof and also suppressing reduction of a foam ratio of the filling foam composition even when reusing unwanted parts thereof and inferior goods thereof a foam filling member using the same filling foam composition; and a filling foam produced by foaming the filling foam composition. The filling foam composition is prepared by mixing foamable polymer, a foaming agent, and a basic oxide in such a mixing ratio that a ratio of the basic oxide can be in the range of 0.05-70 parts by weight per 100 parts by weight of foaming agent. The mounting member for the filling foam composition to be mounted in an internal space of a hollow member is produced by mounting a mounting member on the filling foam composition obtained. The filling foam is formed by fitting the foam filling member in the internal space of the hollow member and, then, foaming the filling foam composition by the application of heat.
Description
Technical field
The present invention relates to fill the filling foam that use between the various members and the internal space of hollow member, and be used to form filling-foam member and the filling-foam composition of this filling with foam.
Background technology
Know that now the hollow member that forms for the closed section that prevents automobile support etc. is delivered to the noise of engine vibration or antitriptic wind sound etc. in the compartment, foam can be filled as packing material.
As this foam, used the foam of the polymkeric substance that forms by various resins and rubber, for example, in the internal space of hollow member, the preceding preplasticizing parison of foaming is set, afterwards, heating during through the hollow member baking vanish, cause the foaming of preplasticizing parison and crosslinked, thereby form foam, the internal space is seamlessly filled by these foaies in the internal space of hollow member.
For example, the Japanese Patent spy opens in the 2002-79955 communique and discloses, at least use the gap fill material that forms by polymkeric substance, whipping agent and linking agent and keep this gap fill material to make the resin system gap fill material anchor clamps of its internal space that is configured in the filled object thing.
In addition, disclose in the Japanese patent laid-open 10-95869 communique, will be for 100 weight part alkadiene synthetic rubber compositions, the crosslinked foam that the reinforcement car body that 50～200 weight part mineral-type packing materials, 1～50 weight part thermolysis type whipping agent and 2～10 weight part organo-peroxides are mixed and made into is used.
Form the preplasticizing parison of foam, be after each composition mixes, and corresponding to the shape of hollow member, is shaped by injection molding forming or pressure forming etc., nonuseable parts such as the runner of injection molding forming and pressure-formed burr can occur.In addition, the situation that is not inconsistent the formation substandard products because of size is arranged.
Then, with this nonuseable part and substandard products through burning or landfill disposal.
But, this preplasticizing parison (gap fill material, strengthen car body with crosslinked foam etc.), because the heating during foaming, whipping agent decomposes and generates acid, afterwards, the acid of generation contacts with the internal surface of the hollow member that foam is filled, and the situation generation of getting rusty is arranged.
Therefore, the Japanese Patent spy opens the gap fill material anchor clamps of putting down in writing in the 2002-79955 communique and is provided with the base station that keeps gap fill material, from outstanding saddle support of base station and the non-return sheet that extends in the end of this saddle support, at internal space configuration base station, can keep gap fill material by this base station, on the other hand, because the non-return sheet is connected in hollow member, internal space in hollow member, the internal surface of void filler and hollow member is separated with arranged spaced, that is to say, taked gap fill material not with antirust processing before the countermeasure that directly contacts of the internal surface of hollow member.
But the internal space as hollow member is narrow and small, just can not fully guarantee the interval of gap fill material and internal surface, still has gap fill material directly to contact with internal surface, the situation that internal surface is got rusty.
In addition, if with nonuseable part and substandard products recycling, then the utilization ratio height has price advantage.But, when these nonuseable parts and substandard products recycling, remove mixed raw material hot resume, therefore when hybrid shaping, produce hot resume again, when using this recycled materials, compare with using starting material, its after foaming the time, the low problem of frothing percentage is arranged.
That is, the heating of whipping agent during by hybrid shaping, its part is decomposed and is generated acid, when mixing organo-peroxide, this organo-peroxide is not to decomposite radical, but decomposites electronics, therefore, the result can not carry out crosslinked when foaming, the problem that existence can not fully be foamed.
The objective of the invention is, even provide rust-preventing characteristic good and use once again nonuseable part and substandard products, frothing percentage also reduce less filling-foam with composition, use this filling-foam with the filling-foam member of composition and make the filling foam of this filling-foam with composition foaming gained.
The announcement of invention
Filling-foam composition of the present invention is characterized in that, contains expandable polymer, whipping agent and basic oxide, and for the above-mentioned whipping agent of 100 weight parts, above-mentioned basic oxide use level is 0.05～70 weight part.
In addition, filling-foam composition of the present invention is preferably and contains organo-peroxide.
In addition, filling-foam of the present invention better contains the sulfonyl hydrazide compound or/and azo-compound with the above-mentioned whipping agent in the composition.
In addition, filling-foam of the present invention is preferably 4 with the above-mentioned sulfonyl hydrazide compound in the composition, 4 '-oxygen two (benzol sulfohydrazide), and above-mentioned azo-compound is preferably Cellmic C 121.
In addition, filling-foam member of the present invention is characterized in that, has above-mentioned filling-foam with composition be loaded on the installation component of above-mentioned filling-foam with the internal space of the be installed in hollow member of composition.
In addition, filling foaming body of the present invention is characterized in that, is resulting with the composition foaming by above-mentioned filling-foam.
Filling-foam composition of the present invention, even because the heating in when foaming, whipping agent is decomposed to form acid, and this acid also can be neutralized by basic oxide.Therefore can prevent to get rusty at the internal surface of hollow member.
In addition, when filling-foam is used composition hybrid shaping, generate acid even whipping agent partly decomposes, this acid also can be neutralized by basic oxide.Even therefore use nonuseable part or the substandard products of the filling-foam of once-forming once again,, also can obtain sufficient frothing percentage because the radical that organo-peroxide resolves into minimizing is less with composition.
As a result, can low-costly be shaped with composition and filling-foam member by filling-foam of the present invention obtains, even rust-preventing characteristic is good and use nonuseable part and substandard products once again, frothing percentage also reduce less filling with foam.
The simple declaration of accompanying drawing
Fig. 1 is, uses filling-foam of the present invention with composition, filling-foam member and fill and use foam, with the process picture sheet of an embodiment of the method for the internal space filling of automobile support.(a) be to be manufactured on filling-foam with the filling-foam member of adorning installation component in the composition, and it is arranged on operation in the support.(b) be depicted as by heating and make filling-foam with composition foaming, crosslinked and solidify, thereby to fill the operation with the internal space of foam filling bracket.
The best mode that carries out an invention
Filling-foam of the present invention contains expandable polymer, whipping agent and basic oxide with composition.
Expandable polymer of the present invention does not have specific restriction, can use known expandable polymer.As expandable polymer, can enumerate the resin of ethylene-vinyl acetate copolymer, polyethylene, polypropylene, polyester, polyvinyl butyral acetal, polyvinyl chloride, polymeric amide, polyketone etc., for example, the rubber of styrene-butadiene rubber(SBR) (SBR), polybutadiene rubber (BR) etc.Be preferably the use ethylene-vinyl acetate copolymer.Use ethylene-vinyl acetate copolymer, frothing percentage is increased.These expandable polymer can suit to select to use more than a kind or 2 kinds.
Whipping agent of the present invention so long as make the material of expandable polymer foaming, does not have specific restriction, can exemplify sulfonyl hydrazide compound and azo-compound.
Among the present invention, as the sulfonyl hydrazide compound, so long as intramolecularly has 1-SO at least
2-NHNH
2The compound of base, no specific restriction.Can exemplify as, 4,4 '-oxygen two (benzol sulfohydrazide), p-toluene sulfonyl hydrazide, 2,4-toluene disulfonic acid amide, p, p-two (benzol sulfohydrazide) ether, benzene-1,3-disulfonyl hydrazide, benzol sulfohydrazide etc.From the angle of foaminess and security, be preferably 4,4 '-oxygen two (benzol sulfohydrazide).
Among the present invention, as azo-compound, so long as intramolecularly has the compound of 1-N=N-base at least, no specific restriction.Can exemplify azodicarbonamide, barium azodicarboxylate, Diisopropyl azodicarboxylate.Angle from foaminess is preferably Cellmic C 121.
Above-mentioned whipping agent can suit to select to use more than a kind or 2 kinds.
In addition, as the whipping agent beyond sulfonyl hydrazide compound and the azo-compound, known have a N, the N-nitroso compound of N '-dinitrosopentamethylene tetramine etc., perhaps mineral-type whipping agent such as yellow soda ash, even thermal expansion micro-balloon.
But,, have desire control to use N, the requirement of N '-dinitrosopentamethylene tetramine from the viewpoint that sudden change takes place.In addition, sodium bicarbonate decomposes the back and generates carbon dioxide, because carbonic acid gas is good for the expandable polymer impregnability, so it is to have difficulties in the high foaming rate foaming.In addition, for expandable polymer, necessary heavy addition thermal expansion micro-balloon, but heavy addition cause viscosity to rise owing to enclose the shell of gas, have difficulties with the high foaming rate foaming.
In addition, this whipping agent, for example above-mentioned inorganic foaming agent, N-nitroso compound or, other known whipping agents such as fluothane, hydrazine class compound, Urea,amino-compounds, triazole class compounds for example, all can share with sulfonyl hydrazide compound or azo-compound according to purpose and purposes.
The use level of whipping agent does not have specific restriction, for 100 weight part expandable polymer, is 10～30 weight parts for example, is preferably 15～25 weight parts.If the use level of whipping agent is measured less than this, be the then essential big shape in internal space of filling hollow member, the problem of operation reduction in installation exercise etc. is then arranged.In addition, if the use level of whipping agent then can not obtain and the corresponding frothing percentage of use level greater than this amount, and the problem that produces cost disadvantage is arranged.
Basic oxide of the present invention if for can in and the basic oxide of the acid that decompose to generate of whipping agent, no specific restriction can be given an example as calcium oxide (CaO), magnesium oxide (MgO), iron protoxide (FeO), ferric oxide (Fe
2O
3) etc.These basic oxide can suit to select to use more than a kind or 2 kinds.
The use level of basic oxide, no specific restriction for example, for the whipping agent of 100 weight parts, is 0.05～70 weight part, is preferably 0.1～50 weight part.Basic oxide with respect to the use level of whipping agent if less than this amount, then the neutralization of being decomposed the acid that generates by whipping agent is reduced, in addition, basic oxide with respect to the use level of whipping agent if greater than this amount, can make the decomposition temperature excessive descent of whipping agent, foaming and crosslinked time are misfitted, cause frothing percentage to descend on the contrary.
In addition, same with basic oxide of the present invention, the material of the acid that generates by whipping agent as neutralizing, can exemplify as amine etc., but be to use amine, simultaneously at neutral, the decomposition temperature of whipping agent is excessively reduced, cause foaming and crosslinked time to misfit, frothing percentage is reduced.
In addition, in order to improve frothing percentage, filling-foam of the present invention is preferably with composition and contains organo-peroxide.
Organo-peroxide among the present invention, it is the linking agent that makes expandable polymer crosslinked, so long as can generate free radical by thermal degradation, generate free radical and can make the crosslinked free radical generating agent of expandable polymer, no specific restriction, can exemplify as, dicumyl peroxide, 1,1-di-t-butyl peroxide-3,3,5-trimethyl-cyclohexane, 2,5-dimethyl-2,5-di-t-butyl peroxide hexane, 2,5-dimethyl-2,5-di-t-butyl peroxide hexin, 1,3-two (t-butyl peroxy sec.-propyl) benzene, t-butyl peroxy ketone, t-butyl-oxybenzoate etc.These organo-peroxides can suit to select to use more than a kind or 2 kinds.
The combined amount of organo-peroxide, no specific restriction for example, for the expandable polymer of 100 weight parts, is 0.1～10 weight part, is preferably 0.5～5 weight part.If the combined amount of organo-peroxide is less than this amount, and the then crosslinked viscosity that causes rises and reduces, and might cause brokenly bubble by air pressure when foaming.In addition, if the use level of organo-peroxide is greater than this amount, and then excessively formation is crosslinked, and the air pressure the when tunicle of expandable polymer can suppress to foam is difficult to foam with high foaming rate.
In addition, filling-foam composition of the present invention, for example, can suit to contain packing material, frothing aid, other linking agents, crosslinking accelerator, processing aid, stablizer, softening agent, antiaging agent, antioxidant, pigment, tinting material, anti-Fungicide, fire-retardant base etc., known additive.
As packing material, no specific restriction, can exemplify as, lime carbonate, aluminium hydroxide, magnesiumcarbonate, magnesium hydroxide, calcium oxide, silicic acid and salt thereof, mica, clay, talcum powder, mica powder, bentonite, silicon-dioxide, porose granulated glass sphere, glass balloon (glass balloon), siliceous balloon (silex balloon), aluminum oxide, pure aluminium silicate, aluminium powder, carbon black, acetylene black, zinc oxide etc.These packing materials can suit to select to use more than a kind or 2 kinds.In addition, the use level of packing material can be according to purpose and the suitable selection of purposes.Be mixed with packing material, can improve stiffening effect.
As frothing aid, can exemplify as, urea compound, salicylic acid compounds, benzoic acid derivative etc.These frothing aids can suit to select to use more than a kind or 2 kinds.In addition, the use level of frothing aid can be according to purpose and the suitable selection of purposes.
As other linking agent, can exemplify as, sulphur, sulfide, selenium, magnesium oxide, yellow lead oxide, zinc oxide, p-quininie dioxime and p, ammonium salt classes such as resenes such as nitroso compound class, alkylphenol formaldehyde resin and melamine formaldehyde condensates, ammonium benzoate such as p '-oximes such as dibenzoyl quininie dioxime, p-dinitroso benzyne.These linking agents can suit to select to use more than a kind or 2 kinds.In addition, the use level of other linking agents can be according to purpose and the suitable selection of purposes.
As crosslinking accelerator, can exemplify as dithiocarbamic acid class, thiazoles, guanidine class, sulfenamide, thiurams, xanthan acids, aldehyde ammonia class, aldehyde amines, Thiourea etc.These crosslinking accelerators can suit to select to use more than a kind or 2 kinds.In addition, the use level of crosslinking accelerator can be according to purpose and the suitable selection of purposes.
As processing aid, can exemplify as, lubricants such as stearic acid or its ester class.These processing aids can suit to select to use more than a kind or 2 kinds, and in addition, the use level of processing aid can be according to purpose and the suitable selection of purposes.
Filling-foam composition of the present invention is that above-mentioned each composition is mixed by above-mentioned use level, and no specific restriction for example, can use mixing roll, adding pressure type kneading machine, forcing machine etc. in that whipping agent is decomposed under the less temperature, mixes, as mixing thing preparation.
In addition, during this preparation, the flow tester viscosity of the mixing thing of gained (120 ℃, 40Kg bears a heavy burden) is 0.5 * 10
4～1.5 * 10
4Pas is preferably and is mixed with 0.8 * 10
4～1.2 * 10
4Pas.The viscosity of mixing thing can make mixing thing foam with appropriate volume frothing percentage (aftermentioned) in this scope.
Can be with by the mixing thing of this modulator approach gained, shape is shaped and makes pre-moulding thing in accordance with regulations.
The shaping of mixing thing; no specific restriction; for example can be with mixing thing through the tablets press granulating; this particle decomposes under the less temperature condition whipping agent; be configured as the regulation shape through injection molding forming or extrusion molding etc., perhaps also can be the regulation shape through direct forming such as polishing machine shaping or pressure formings.
To so prepare the filling-foam composition of the present invention of gained,, make it foaming, crosslinked and curing, can form filling foam of the present invention by under suitable condition, heating.
The filling foam of the present invention of gained like this, its density (volume (g/cm of the weight of foam (g)/foam
3)), be for example 0.125～0.05g/cm
3, be preferably 0.10～0.06g/cm
3, in addition, the frothing percentage during foaming (volume frothing percentage) is preferably more than 8 times, more preferably 10～15 times.So in this way frothing percentage even the hollow member internal space is complicated shape, uses to fill and also it seamlessly can be filled with foam.
In addition, like this filling foam of the present invention of gained, the frothing percentage when recirculation is as described later for example compared with raw-material frothing percentage, is preferably more than 65% more preferably 80～110%.65% when above, even use nonuseable part or the substandard products that occur in the manufacturing engineering once again, can prevent that also gained from filling the downgrade with foam.
Like this filling foam of the present invention of gained for various members, can be given various effects such as reinforcement, antidetonation, sound insulation, dustproof, heat insulation, buffering, waterproof.Therefore, fill it between the various members or the internal space of hollow member.For example, applicable packing material as various mechanicalss such as reinforcement material, packing, sound-proof material, dust-proof material, lagging material, cushioning material, water-proof materials.
In addition, between various members or the filling of the internal space of hollow member, no specific limited, for example between the member that is filled to purpose with the space or in the internal space of hollow member, the filling-foam composition is set, afterwards the filling-foam that is provided with is heated with composition, by make its foaming, crosslinked, solidify to form to fill and use foam.Use this filling to get final product with between the foam noggin piece or the internal space of hollow member.
More particularly, for example, when filling the internal space of hollow member, at first, be manufactured on filling-foam with the filling-foam member of adorning installation component in the composition, the installation component of this filling-foam member is installed in the internal space of hollow member after, as make it foaming through heating, form to fill and use foam, can fill with foam by this internal space of hollow member is filled.
As this hollow member, can exemplify support as automobile, make the filling-foam member by filling-foam of the present invention with composition, and after it is installed in the internal space of support, as make it foaming, use foam by filling, support is strengthened fully, can effectively prevent simultaneously the vibrations or the noise of engine, perhaps, antitriptic wind sound etc. are delivered in the compartment.
Below,, illustrate and use these to fill the method for the internal space of automobile supports with composition, filling-foam member and filling a embodiment as filling-foam of the present invention with foam.
This method, at first shown in Fig. 1 (a), the filling-foam that is configured as the regulation shape is arranged in the support 2 with composition 1, filling-foam is provided with in support 2 with composition 1, for example, installation component 3 is installed in filling-foam with in the composition 1, makes filling-foam member P, the internal surface that again installation component 3 of this filling-foam member P is installed in support 2 gets final product.The installation of installation component 3 in filling-foam usefulness composition 1, for example, removing can be with installation component 3, and the filling-foam that is installed in shaping also can be shaped as inserts with mixing thing with in the composition 1 when filling-foam is shaped with composition 1.In addition, the installation of installation component 3 on the internal surface of support 2, for example, internal surface at support 2 forms the tying ditch, installation component 3 inserted make its tying, perhaps installation component 3 is made of sucker or magnetite etc., fixes by sorption or with magnetic force, even installation component 3 is made of metal sheet, can be through welded and installed.
In addition, this installation by installing material 3, makes filling-foam be separated with arranged spaced with the inner peripheral surface of composition 1 and support 2, i.e. the countermeasure that the inner peripheral surface of the support 2 before employing makes filling-foam with composition 1 and antirust processing does not directly contact.
In addition, this support 2, the interior lath 4 and the outer lath 5 that slightly are spill by section constitute, at first, filling-foam be arranged in the interior lath 4 with composition 1, afterwards, with the two end portions butt joint of interior lath 4 and outer lath 5, through being welded to connect the formation closed section.In addition, such support 2 specifically can make fore-stock, side stand or after poppet as vehicle body.
Afterwards, in this method, after the internal surface of support 2 is implemented antirust processing, shown in Fig. 1 (b), for example, through after baking vanish the time the heating (for example 110～190 ℃) of drying line operation, make filling-foam with composition 1 foaming, crosslinked and solidify, form and fill, with foam 6 internal space of support 2 is seamlessly filled by this filling with foam 6.
In addition, can be corresponding to the shape of support 2 etc., selects suitable filling-foam with the shape of composition 1, position, collocation method are set and dispose quantity etc.
The filling-foam composition of the present invention of gained like this, containing corresponding to whipping agent 100 weight parts is the basic oxide of 0.05～70 weight part, even the therefore heating when foaming, it is sour that whipping agent decomposes generation, this acid also can be neutralized by basic oxide.Thereby even the internal space of support 2 is narrow and small, filling-foam directly contacts with the internal surface of composition 1 with support 2, in the time of can not implementing sufficient antirust processing to this contact part, can prevent that also this contact part from getting rusty.
More specifically, with 4,4 '-oxygen two (benzol sulfohydrazide) and Cellmic C 121 are as whipping agent, and dicumyl peroxide is as organo-peroxide, and calcium oxide is the example explanation as basic oxide.At first, 4, thermolysis takes place in the heating when foaming of 4 '-oxygen two (benzol sulfohydrazide) and Cellmic C 121 shown in (1) and (2), emit gas (N
2Gas, CO gas) time, decompose residues 4 generated respectively, 4 '-oxygen two (benzene sulfinic acid) and cyanic acid.
Thereby the internal space of support 2 is when narrow and small, and filling-foam directly contacts with the internal surface of composition 1 with support 2, and this contact part is not if implement antirust processing, and the acid of generation can make the internal surface of support 2 get rusty.
Therefore,, be furnished with the calcium oxide of significant quantity as this filling-foam composition, shown in (3) and (4), in can distinguishing and 4,4 '-oxygen two (benzene sulfinic acid) and cyanic acid, thus can prevent that support 2 from getting rusty.
CaO+H
2O→Ca(OH)
2+2H
+R
-
→CaR
2+2H
2O (3)
(in the formula, R
-Expression 4, the ion of 4 '-oxygen two (benzene sulfinic acid))
CaO+H
2O→Ca(OH)
2+2HOCN
→Ca(OCN)
2+2H
2O (4)
In addition, when nonuseable part and substandard products recirculation, the heating when heating when being shaped because of starting material are mixing and the mixing shaping of recycled materials are heated, respectively suc as formula (1) and (2), gas (N is emitted in the decomposition of whipping agent portion of hot
2Gas, CO gas) time, decompose residues 4 generated respectively, 4 '-oxygen two (benzene sulfinic acid) and cyanic acid.
By 4, the acid (proton) that 4 '-oxygen two (benzene sulfinic acid) and cyanic acid produce, as act on dicumyl peroxide, as the formula (5), dicumyl peroxide does not decompose the generation free radical and decomposes the generation ion.
Like this, after foaming the time, can make to promote crosslinked free radical to generate number to reduce the problem that having can not be crosslinked smoothly, can not fully foam.
Therefore, as if this filling-foam composition, contain the calcium oxide of significant quantity, shown in (3) and (4), can neutralize by 4, the acid (proton) that 4 '-oxygen two (benzene sulfinic acid) and cyanic acid produce, thereby can prevent effectively that the decomposition of dicumyl peroxide from generating ion.
CaO+H
2O→Ca(OH)
2+2H
+R
-
→CaR
2+2H
2O (3)
(in the formula, R-represents 4, the ion of 4 '-oxygen two (benzene sulfinic acid))
CaO+H
2O→Ca(OH)
2+2HOCN
→Ca(OCN)
2+2H
2O (4)
Therefore, filling-foam composition of the present invention after mixing thing preparation, through injection molding forming or extrusion molding or calendering shaping or pressure forming, when being configured as the regulation shape, can reducing organo-peroxide as described above and decompose the generation ion.Thereby, even the nonuseable part that forms when this mixing thing is shaped, burr of the runner of injection molding forming and extrusion molding etc. for example, even the substandard products that generate when being shaped, be shaped once more and make pre-moulding thing, after foaming the time, can reduce the minimizing that organo-peroxide decompose to generate free radical, obtain sufficient frothing percentage.
As a result, filling-foam of the present invention is with composition and filling-foam member, and rust-preventing characteristic is good, even and use nonuseable part and substandard products once again, frothing percentage also can be reduced few filling foaming body and be shaped at low cost.
Embodiment
Below, will enumerate embodiment and be described in more detail the present invention, but the present invention is not limited to this.
The manufacturing of embodiment 1～4 and comparative example 1～2
Each filling-foam composition of embodiment 1～4 and comparative example 1～2 according to cooperating prescription shown in the table 1, with each composition of expandable polymer, whipping agent, organo-peroxide and basic oxide, is used mixing roll, at 110 ℃ of temperature, rotating speed 20min
-1After mixing, exert pressure 110 ℃ hot pressing was shaped in 1 minute, and becoming thickness is the laminar of 3mm.It is square to be cut into 30mm, obtains starting material.This starting material mounting 160 ℃ of heating 20 minutes, makes it foaming on the steel plate of handling through zinc phosphate.
Then, with gained foam and steel plate, 40 ℃ of temperature, humidity 92%RH preserved down after 7 days, took out steel plate and removed foam, had the part of foam, visual inspection steel plate to have or not to device and got rusty.It the results are shown in table 1.
In addition, the volume frothing percentage in the table 1 is to be tried to achieve by the density calculation after the preceding density/foaming of, volume frothing percentage=foaming.
Table 1
* 1EVA: ethene-vinyl acetate interpolymer
(vinyl acetate content is 19 weight % for Mitsui Du Pont Polychemical's system, EVAFLEX EV460, MFR2.5)
* 2OBSH:4,4 '-oxybis-benzenesulfonyl hydrazide
(Yonghe County changes into industrial's system, and NEOTHLENE HM806P, OBSH content are 80 weight %, and EPDM content is 20 weight %)
* 3ADCA: Cellmic C 121
(Yonghe County changes into system, VINYFOR AC#LQ)
* 4DCP: dicumyl peroxide
(Nof Corp.'s system, PERCUMYL D-40MBK, dicumyl peroxide content are 40 weight %, the content of silicon-dioxide+EPDM is 60 weight %)
* 5 urea compounds
(Yonghe County changes into system CELLPASTE K5)
As shown in Table 1, being mixed with corresponding to 100 weight part whipping agents is the embodiment 1～4 of 0.05～70 weight part basic oxide, can prevent steel plate corrosion.
The manufacturing of embodiment 5～8 and comparative example 3～5
Each filling-foam composition of embodiment 5～8 and comparative example 3～5, according to cooperating prescription shown in the table 2, with each composition of expandable polymer, whipping agent, organo-peroxide, basic oxide and amine (only for comparative example 5), with single shaft forcing machine (spiral footpath 40mm φ, L/D=20, compression ratio 2.6, nozzle form 3 φ) at 110 ℃ of temperature, rotating speed 20min
-1After extruding once, exert pressure 110 ℃ hot pressing was shaped in 1 minute, and becoming thickness is the laminar of 5mm.With it as starting material.160 ℃ of heating 20 minutes, make it foaming, measure the volume frothing percentage.The results are shown in table 2.
Then, after starting material were extruded once more under these conditions, exert pressure once more 110 ℃ hot pressing was shaped down in 1 minute, and becoming thickness is the laminar of 5mm.It as recycled materials, 160 ℃ of heating 20 minutes, is made it foaming, measure the volume frothing percentage.The results are shown in table 2.
In addition, the volume frothing percentage in the table 2 is to be tried to achieve by the density calculation after the preceding density/foaming of, volume frothing percentage=foaming.
Table 2
* 6EVA: ethene-vinyl acetate interpolymer
(Mitsui Du Pont Polychemical's system, EVAFLEX EV460, MFR2.5, vinyl acetate content are 19 weight %)
* 7OBSH:4,4 '-oxybis-benzenesulfonyl hydrazide
(Yonghe County changes into industrial's system, and NEOTHLENE HM806P, OBSH content are 80 weight %, and EPDM content is 20 weight %)
* 8DCP: dicumyl peroxide
(Nof Corp.'s system, PERCUMYL D-40MBK, dicumyl peroxide content are 40 weight %, the content of silicon-dioxide+EPDM is 60 weight %)
As shown in Table 2, being mixed with corresponding to 100 weight part whipping agents is the embodiment 5～8 of 0.05～70 weight part basic oxide, even use recycled materials, also can obtain high volume frothing percentage.
In addition, above-mentioned explanation provides the present invention illustrative embodiment, but only is illustration, is not the explanation that limits.The variation of the present invention that the practitioner of this technical field understands all is included in the scope of claim described later.
The possibility that industry is utilized
As more than, filling-foam of the present invention is with composition, filling-foam member and fill and be filled in foaming body Between the various members or the inner space of hollow member, for example be applicable to reinforcement material, packing, acoustic material, The packing material of the various industrial products such as dust-proof material, heat-barrier material, padded coaming, waterproof material.
Claims (6)
1. filling-foam composition, it is characterized in that, contain expandable polymer, whipping agent and basic oxide, the use level of above-mentioned basic oxide is 0.05～70 weight part with respect to the above-mentioned whipping agent of 100 weight parts, and above-mentioned basic oxide are selected from CaO, MgO, FeO or Fe
2O
3At least a.
2. filling-foam composition as claimed in claim 1, its feature also are, also contain organo-peroxide.
3. filling-foam composition as claimed in claim 1, its feature are that also above-mentioned whipping agent contains the sulfonyl hydrazide compound or/and azo-compound.
4. filling-foam composition as claimed in claim 3, its feature are that also above-mentioned sulfonyl hydrazide compound is 4,4 '-oxygen two (benzol sulfohydrazide), and above-mentioned azo-compound is a Cellmic C 121.
5. the filling-foam member is characterized in that, possesses in the claim 1～4 each described filling-foam with composition and adorning in the installation component of above-mentioned filling-foam with the internal space of the be installed in hollow member of composition.
6. fill and use foam, it is characterized in that, make with the composition foaming by each described filling-foam in the claim 1～4.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003309668 | 2003-09-02 | ||
| JP309668/2003 | 2003-09-02 | ||
| JP247247/2004 | 2004-08-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1771283A CN1771283A (en) | 2006-05-10 |
| CN100398590C true CN100398590C (en) | 2008-07-02 |
Family
ID=36751922
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800094376A Expired - Fee Related CN100398590C (en) | 2003-09-02 | 2004-09-01 | Expandable composition for filling use, expandable member for filling use and expanded article for filling use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100398590C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4966727B2 (en) * | 2007-04-24 | 2012-07-04 | 日東電工株式会社 | Filling foam composition, filled foam member and filling foam |
| JP4263767B2 (en) * | 2007-09-20 | 2009-05-13 | 日東電工株式会社 | Foam composition for filling, filled foam member, and foam for filling |
| JP5508090B2 (en) * | 2010-03-30 | 2014-05-28 | 日東電工株式会社 | Foam composition for filling, filled foam member, and foam for filling |
| JP5412542B2 (en) * | 2012-03-21 | 2014-02-12 | 日東電工株式会社 | Foamable sealing material, foamable sealing member, sealing foam, and space sealing method |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59225156A (en) * | 1983-06-07 | 1984-12-18 | Nippon Carbide Ind Co Ltd | Method for controlling decomposition temperature of azodicarbonamide, and foaming agent composition |
| CN86106392A (en) * | 1986-09-22 | 1987-05-06 | 哈尔滨市松江塑料化学技术研究所 | The ethene foaming product manufacture method of the high foam expansion of high-pressure polyethylene |
| CN1032943A (en) * | 1988-06-30 | 1989-05-17 | 哈尔滨市泡沫塑料制品厂 | A kind of polyethylene foams |
| JPH1095869A (en) * | 1996-09-25 | 1998-04-14 | Nissan Motor Co Ltd | Crosslinked foam for reinforcing car body and method for reinforcing car body therewith |
| JP2000085618A (en) * | 1998-09-18 | 2000-03-28 | Nissan Motor Co Ltd | Rigidity improving method for foam filler and box-type member |
| JP2001226663A (en) * | 2000-02-15 | 2001-08-21 | Hitachi Kasei Polymer Co Ltd | Thermosetting foamable sealing material |
| JP2004168856A (en) * | 2002-11-19 | 2004-06-17 | Nitto Denko Corp | Composition for foaming for filling use, foaming member for filling, and foamed body for filling |
-
2004
- 2004-09-01 CN CNB2004800094376A patent/CN100398590C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59225156A (en) * | 1983-06-07 | 1984-12-18 | Nippon Carbide Ind Co Ltd | Method for controlling decomposition temperature of azodicarbonamide, and foaming agent composition |
| CN86106392A (en) * | 1986-09-22 | 1987-05-06 | 哈尔滨市松江塑料化学技术研究所 | The ethene foaming product manufacture method of the high foam expansion of high-pressure polyethylene |
| CN1032943A (en) * | 1988-06-30 | 1989-05-17 | 哈尔滨市泡沫塑料制品厂 | A kind of polyethylene foams |
| JPH1095869A (en) * | 1996-09-25 | 1998-04-14 | Nissan Motor Co Ltd | Crosslinked foam for reinforcing car body and method for reinforcing car body therewith |
| JP2000085618A (en) * | 1998-09-18 | 2000-03-28 | Nissan Motor Co Ltd | Rigidity improving method for foam filler and box-type member |
| JP2001226663A (en) * | 2000-02-15 | 2001-08-21 | Hitachi Kasei Polymer Co Ltd | Thermosetting foamable sealing material |
| JP2004168856A (en) * | 2002-11-19 | 2004-06-17 | Nitto Denko Corp | Composition for foaming for filling use, foaming member for filling, and foamed body for filling |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1771283A (en) | 2006-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7989515B2 (en) | Filling foam composition, foam filling member, and filling foam | |
| EP1683827B1 (en) | Open-cell foam of ethylene-propylene-diene rubber | |
| US5045570A (en) | Endothermic blowing agents for surface migration of components in foamed products, compositions and applications | |
| Quinn | Chemical blowing agents: providing production, economic and physical improvements to a wide range of polymers | |
| US20070276054A1 (en) | Composition for foam filling, foam filling member, and foam for filling | |
| CN100398590C (en) | Expandable composition for filling use, expandable member for filling use and expanded article for filling use | |
| CN102731815B (en) | Filling foam composition, foam filling member, and filling foam | |
| US5317044A (en) | Endothermic blowing agents for surface migration of components in foamed products, compositions and applications | |
| US7855250B2 (en) | Filling foam composition, foam filling member, and filling foam | |
| CN103030867A (en) | Foaming composition for filling and sealing, foaming member for filling and sealing, foam for filling and sealing | |
| JP2004026990A (en) | Foamable composition, foamed member for hollow member, and filling foam | |
| JP3465507B2 (en) | Foamable rubber composition for filling structure | |
| CN103030866A (en) | Foaming composition for filling and sealing, foaming member for filling and sealing, foam for filling and sealing, and filling method using the same | |
| JP3565815B2 (en) | Conductive cross-linked polyethylene foam and method for producing the same | |
| US5306736A (en) | Endothermic blowing agents for surface migration of components in foamed products, compositions and applications | |
| WO2008101685A1 (en) | Injection mouldable foamable ethylene propylene diene copolymer rubber formulations | |
| JPH0853567A (en) | Rubber composition for foam-molding | |
| USRE35368E (en) | Endothermic blowing agents for surface migration of components in foamed products, compositions and applications | |
| JPH09208932A (en) | Expandable rubber composition for packing structure and foam for packing structure | |
| JPH0395238A (en) | Foam | |
| JP2004352748A (en) | Conductive crosslinked polyethylene foam and its manufacturing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080702 Termination date: 20180901 |