CN101880462A - Silicon rubber sponge, its manufacture and image forming roller thereof - Google Patents
Silicon rubber sponge, its manufacture and image forming roller thereof Download PDFInfo
- Publication number
- CN101880462A CN101880462A CN2010101355296A CN201010135529A CN101880462A CN 101880462 A CN101880462 A CN 101880462A CN 2010101355296 A CN2010101355296 A CN 2010101355296A CN 201010135529 A CN201010135529 A CN 201010135529A CN 101880462 A CN101880462 A CN 101880462A
- Authority
- CN
- China
- Prior art keywords
- sponge
- peroxide
- rate
- dunking
- composition
- 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
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fixing For Electrophotography (AREA)
- Rolls And Other Rotary Bodies (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
To provide a silicone sponge having a high continuous cell rate, capable of being produced by a normal temperature hot air vulcanization without considering the regulation of the cross-linking speed of the rubber and a delicate balance of a foaming gas rate, excellent in productivity, capable of forming a uniform and fine cell structure and having less toxicity. This silicone rubber sponge composition having the high continuous cell rate contains (A) 100 pts. mass organopolysiloxane expressed by the following averaged compositional formula (I): R<SP>1</SP><SB>a</SB>SiO<SB>4-(a/2)</SB>[wherein, R<SP>1</SP>s are each the same or different kind un-substituted or substituted monovalent hydrocarbon group; and (a) is 1.95-2.04 positive number] , (B) 0.5-50 pt. mass blowing agent generating gas at >=90[deg.]C temperature zone and (C) an effective amount for curing the component (A) of a non-acyl-based organic peroxide having >=150[deg.]C half-life temperature at 1 min.
Description
The application be that on 09 08th, 2005, application number are 200510098145.0 the applying date, denomination of invention divides an application for the patent application of " high continued dunking rate silicon rubber foam, its method for making and with its fixing roller ".
Technical field
The present invention relates to be used in building packing ring, various sponge sheet, suction is that the office machine led is with the sponge roller, particularly be used in the high continued dunking rate silicon rubber silicon rubber sponge of toning agent fusion fixing roller, feed roll, toner transport roller and cleaning roller etc. with image processing systems such as sponge, heat shield, industrial roller, duplicating machine, facsimile recorder, printers.
Background technology
The polysiloxane sponge has the distinctive physical property of silicon rubber, has character such as excellent thermotolerance, winter hardiness, electrical insulating property, flame retardant resistance, compression set.This silicon rubber foam is combination heat-curable silicone rubber compositions and solidifying agent, whipping agent basically, by foamable, be solidified to form the material of sponge, but the foaminess excellence, have homogeneous and fine pore structure this moment, and not damage the distinctive physical property of silicon rubber be very important.
In addition, as the method for shaping, be to carry out mostly making it to solidify in the normal pressure hot gas of continuous molding, foaming.Make the sponge of homogeneous and fine pore structure during for the moulding in such normal pressure hot gas, owing to must suppress with the state of rill in the inside of rubber and stay in the gas that produces when whipping agent decomposes, therefore, in common occasion, for before whipping agent decomposes, the repressed firmly blow(ing) pressure of rubber combination has tackify, solidified necessity.
Therefore, when the moulding sponge,, be generally following order as the reaction sequence in rubber.
1) by solidifying agent to the tackify (curing) as the organopolysiloxane of base polymer, the surface cure of rubber.
2) decomposition by whipping agent produces gas, forms the sponge hole.
3) as the completely solidified of the organopolysiloxane of base polymer.
In fact,, adjust addition-crosslinked catalytic amount and control reaction, or the decomposition temperature of the decomposition temperature of selecting organo-peroxide and whipping agent decomposition temperature identical or that be lower than whipping agent is set above-mentioned reaction sequence in order to react according to above-mentioned order.
Like this, common sponge composite is owing to be to make with the method for living blow(ing) pressure by crosslinked compacting, and therefore, the sponge hole is normally independently steeped and connected the bubble rate usually is below 10% or 10%, and becomes the state that air is closed in the inside, sponge hole.Like this, if heating sponge hole becomes the sponge forming composition of independent bubbles, the air that is closed in the inside is according to the boyle-Charles law thermal expansion, be full of the spatial sponge of the such sealing of gasket materials, pneumatic cushioning composition grow, sponge hardness are uprised, or in the roll material of photographic fixing sponge roller etc., owing to making sponge, thermal expansion directly becomes big, thereby changed photographic fixing pressure, perhaps opposite, the sponge roller is when the refrigerative state, and the setting between warming mill and the support roll broadens at interval, and roller is shaky and unstable becomes the generation of different sound source.Particularly, as photographic fixing sponge roller purposes, from the viewpoint of power saving, hope is at stand-by state, photographic fixing sponge roller increases the machine of the state colder than common fixing temperature, thereby is not subjected to the influence of Heating temperature, and makes the sponge footpath become certain high sponge of company's bubble rate easily.
The foaming system of conduct and and organic azo-compound crosslinked with the organo-peroxide of non-acyl group class has been proposed in patent documentation 1; used 1; two (t-butyl peroxy carboxyl) hexane (the peroxy esters classes of 6-; 163 ℃) and AIBN (Diisopropyl azodicarboxylate) as the sponge of whipping agent; but this patent is by using the organo-peroxide of surface cure excellence; obtain the technology of good sponge; described organo-peroxide is to make the organo-peroxide of common non-acyl group class because the crosslinked obstruction that is caused by carbon and out of use electro-conductive material can normal pressure hot gas add the organo-peroxide of the surface cure excellence of sulphur; the hole of sponge is independently to steep; in addition; particularly; it is not to improve the technology that sponge connects the bubble rate, does not connect the record of bubble rate.
Though put down in writing the silicon rubber sponge composite with the crystal water foaming of the inorganic salts with crystal water in patent documentation 2, record does not connect the alveolitoid sponge.
[patent documentation 1] spy opens flat 5-43802 communique
[patent documentation 2] spy opens flat 5-156061 communique
Summary of the invention
[problem that invention will solve]
The present invention makes in order to overcome the problems referred to above, and the high continued dunking rate polysiloxane sponge composite that easily provides a kind of toxicity few is provided its purpose.This sponge can not considered the control of rate of crosslinking of rubber or the trickle balance of foamed gas speed, make by HAV, and the productivity excellence, have homogeneous and fine pore structure, and do not select whipping agent just can carry out sponge and be shaped, when particularly using sodium bicarbonate class whipping agent.
[solving the method for problem]
Present inventors are through the result of deep research, it is high continued dunking rate silica-gel sponge more than 15% or 15% that a kind of bubble rate that connects is provided, wherein, as the means of reaching above-mentioned purpose, be that sponge composite foams by making, curing obtains, described sponge composite contains: (A) with a following average group accepted way of doing sth (I)
R
1 aSiO
4-a/2????????????????(I)
(R
11 valency alkyl for the non-replacement or the replacement of identical or different kind; a is 1.95～2.04 positive number) expression, have the organopolysiloxane of 2 alkenyls in a part at least: 100 mass parts, (B) produce the whipping agent of gas in the temperature province more than 90 ℃ or 90 ℃: 0.5～50 mass parts and (C) 1 minute half life temperature be non-acyl group class organo-peroxide more than 150 ℃ or 150 ℃: the significant quantity that can solidify (A) composition.
In addition, it is the manufacture method of the high continued dunking rate silica-gel sponge more than 15% or 15% that the present invention also provides a kind of even bubble rate, and wherein, this manufacture method contains above-mentioned sponge composite is added sulphur (HAV) foaming, solidified operation by normal pressure hot gas.
In addition, the present invention also provides a kind of fixing roller and has been provided with the electro photography image processing system that possesses this fixing roller, it is characterized in that, has at least 1 layer the layer that contains this high continued dunking rate silicon rubber foam.As such fixing roller, can enumerate, for example, the bonding fixing roller that connects the toning agent fusion photographic fixing purposes of the multilayered structure fixing roller structure of steeping the multilayer fixing roller more than 2 layers or 2 layers of sponge and top layer somatotype materials such as fixing roller individual layer or PFA tube or having had compound solid rubber and sponge glue-line and toning agent release layer.
Sponge composite of the present invention is that non-acyl group class organo-peroxide more than 150 ℃ or 150 ℃ carries out normal pressure hot gas and adds sulphur by using 1 minute half life temperature; impossible high continued dunking rate before can obtaining; that is, connect bubble rate 15% or 15% above, if desired can obtain more than 20% or 20%, can also obtain 30～100% silicon rubber foam.In addition, as (B) composition,, can obtain the more sponge of high continued dunking rate if use sodium bicarbonate class whipping agent.In addition, will can make that (A) composition is crosslinked by thermolysis, the organic blowing agent of tackify is as nucleator and usefulness, and can connect and steep the miniaturization of sponge hole, homogenization.Other effect describes in the following description.
[preferred plan that carries out an invention]
Below, explain the present invention.
-(A) composition-
(A) organopolysiloxane of composition is a following average group accepted way of doing sth (I)
R
1 aSiO
4-a/2????????????(I)
(R
1Be 1 valency alkyl of the non-replacement or the replacement of identical or different kind, a is 1.95～2.04 positive number) organopolysiloxane of expression.
In an average group accepted way of doing sth (I), as R
1Can enumerate aralkyl such as aryl such as alkenyls such as cycloalkyl such as alkyl such as methyl, ethyl, propyl group, butyl, hexyl, dodecyl, cyclohexyl, vinyl, allyl group, butenyl, hexenyl, phenyl, tolyl, β-hydrocinnamyl or select to be combined in part or all chloromethyl that replaces with halogen atom, cyano group etc., trifluoro propyl, cyanoethyl etc., the identical or different preferred carbonatomss 1～12 of the hydrogen atom on these groups, be more preferably 1 valency alkyl of the non-replacement or the replacement of carbonatoms 1～8.Particularly, preferable methyl, vinyl, phenyl, trifluoro propyl, special 80 moles of % of preferable methyl or 80 moles of above, special more 95 moles of % of preferable methyl of % or 95 moles are more than the %.In addition, a is 1.95～2.04 positive number, though this organopolysiloxane is essentially the straight chain shape, the silica-gel sponge after not damaging curing the scope of caoutchouc elasticity in, also can branch.Though this organopolysiloxane can become molecule chain end by TMS, dimethyl vinyl, the end capped material of dimethyl hydroxyl silylation, but in the present invention, this organopolysiloxane, it is necessary having 2 alkenyls in molecule at least, particularly, preferred R
1In 0.001～5 mole of %, preferred especially 0.01～0.5 mole of % be alkenyl, particularly vinyl.
This kind organopolysiloxane is can be by the hydrolytic condensation more than a kind or 2 kinds or 2 kinds of the organo-halogen-silane that will select usually, or by using alkalescence or an acidic catalyst to carry out the material that ring-opening polymerization obtains cyclic polysiloxanes (3 aggressiveness of siloxanes or 4 aggressiveness etc.), this material is essentially the straight chain shape, but also can a part of branch.In addition, also can be the different mixture more than 2 kinds or 2 kinds of molecular structure.In addition, the viscosity of this organopolysiloxane is 100mm 25 ℃ viscosity preferably
2/ s or 100mm
2More than/the s, be more preferably 100000～10000000mm
2/ s.The polymerization degree is more than 100 or 100, and more than preferred especially 3000 or 3000, its upper limit is preferred 100000, is more preferably 10000.
-(B) composition-
In the present invention, as (B) composition, use more than 90 ℃ or 90 ℃, preferred 100～180 ℃ temperature province produces the whipping agent of gas.So long as can access the material of gas by thermolysis (or evaporation), then there is no particular limitation, can use as to the immiscible rubber of polysiloxane with known organic blowing agent of whipping agent or inorganic foaming agent.
As organic blowing agent, can enumerate, for example, N, N '-dimethyl-N, N '-dinitroso pentamethylene tetramine, N, N '-dinitroso-nitroso compounds such as pentamethylene tetramine; Azodicarbonamide, Diisopropyl azodicarboxylate, azo cyclohexanenitrile, azo diaminobenzene, 2,2 '-azo is two-2-methylbutyronitrile, 2,2 '-azo two-2,4-methyl pentane nitrile, 1, organic azo-compounds such as 1 '-azo two (1-acetoxyl-1-diphenylphosphino ethane), azodicarbonamides, azoformic acid chromium; Benzol sulfohydrazide, toluene sulfonyl hydrazide, P, P '-oxo two (benzol sulfohydrazide), sulfobenzides-3,3 '-disulfonyl hydrazide, 4, sulfonyl hydrazide compounds such as 4 '-oxo two (benzol sulfohydrazide), p-toluene sulfonyl hydrazide; Azide calcium, 4, triazo-compounds such as 4-phenylbenzene disulfonyl trinitride, p-toluene sulfonyt azide thing etc.Wherein, preference as, Diisopropyl azodicarboxylate or 2,2 '-azo is two-2-methylbutyronitrile, 2,2 '-azo two-2,4-methyl pentane nitrile, 1,1 '-azo two (1-acetoxyl-1-diphenylphosphino ethane), 1,1 '-azo two (hexanaphthene-1-methyl carboxylic acids ester), 1,1 '-azo two (hexanaphthenes-1-nitrile), 2,2 '-azo two [N-(2-propenyl)-2-methyl propanamide] wait the azo class organic blowing agent that does not have the solidified sulphur compound, phosphoric acid salt of obstruction silicon rubber, strong amine etc. at intramolecularly.
In addition, as inorganic foaming agent, particularly, can enumerate sodium bicarbonate (Xiao Su reaches), yellow soda ash, bicarbonate of ammonia, volatile salt, ammonium nitrite etc.Preferred sodium bicarbonate.These preferably do not contain crystal water.Sodium bicarbonate is different with other volatile salt class or inorganic foaming agents such as ammonium nitrite, triazo-compound, owing to decompose and not produce strong acid or alkali, no stink, and the organo-peroxide that does not cause the use polysiloxane is crosslinked or the addition-crosslinked crosslinked obstruction of platinum class catalyzer, therefore have in order to obtain sponge, advantage that can heavy addition, in addition, also do not have toxicity, be particularly suitable in the present invention using.
With the sodium bicarbonate class whipping agent of sodium bicarbonate as host, compare with other whipping agent, particularly can the high sponge of the company's of acquisition bubble rate.We know that the decomposition behavior of sodium bicarbonate is slowly to decompose from 120 ℃ of front and back, mainly are 150 ℃ of decomposition, and the temperature range that produces gas is very wide.Therefore, can think,, foam, take place so-called gas leakage, the sponge that the company's of obtaining bubble rate is high in the front and back of crosslinking temperature scope if use the organo-peroxide of pyrolytic decomposition type to make sodium bicarbonate class blowing agent H AV solidify, foam.The combination of the organo-peroxide of dioxane base class and sodium bicarbonate whipping agent can the company's of obtaining bubble rate surpass 50% sponge.Sodium bicarbonate class whipping agent, as long as the host of whipping agent is sodium bicarbonate, just not special the appointment is arbitrarily for particle diameter or goods purity, to the hydrophobization processing of sodium bicarbonate etc., but wish that purity is 50～100%, median size is 50 μ m or below the 50 μ m.In addition, the nucleation of the sponge of whipping agent is handled or the interpolation of nucleator, and the inorganic foaming agent etc. that adds a spot of acid or add trace as decomposition accelerating agent all is arbitrarily.
As the addition of the whipping agent of (B) composition, the organopolysiloxane of per 100 mass parts (A) composition is generally 0.5～50 mass parts, preferred 1.0～20 mass parts.If less than 0.5 mass parts, produce that gas is insufficient to be difficult to become the sponge state, the bubble rate does not improve yet, if surpass 50 mass parts, then physics adds difficulty sometimes, in addition, when the sponge moulding, become many, cause hole heterogeneity or sponge to be isolated internally owing to produce gas.
-(C) composition-
It is the material that uses for (A) composition is solidified that the organo-peroxide of (C) of the present invention composition adds the sulphur agent, uses the non-acyl class organo-peroxide of 1 minute half life temperature more than 150 ℃ or 150 ℃.Particularly, wish for peroxyester, ketal peroxide, dialkyl peroxide, hydroperoxide such when normal pressure adds sulphur (HAV), because oxygen hinders the organo-peroxide that causes the crosslinked obstruction of rubber surface (being difficult to into piece).
When HAV adds the common independent bubbles sponge of sulphur; owing to foamed gas need be enclosed in the rubber the inside; therefore; in the organo-peroxide that uses; be necessary to select the diacyl class superoxide (peroxidation 2 that is subjected to the crosslinked obstruction of oxygen little; 4-dichloro-benzoyl, peroxidation are to toluyl, peroxidation o-methyl-benzene formyl etc.) or in peroxyesters; special antioxygen hinders 1 of strong organo-peroxide, two (t-butyl peroxy phosphinylidyne) hexanes of 6-or do not have the addition-crosslinked of the crosslinked obstruction of oxygen.Therefore, usually, when normal pressure hot gas adds sulphur, do not use separately, in addition, when using separately, can not obtain sponge hole homogeneous and have the sponge of high foamability because oxygen hinders the dialkyl peroxide class of rubber surface not crosslinked (not becoming foam).
In the present invention,, uprise, so preferably owing to make sponge connect the bubble rate if organo-peroxide is chosen in the material that decomposes than under the higher temperature of the decomposition temperature of the whipping agent of (B) composition.If give one example, when using sodium bicarbonate class whipping agent, for having set much at one or slow material than 150 ℃ of main decomposition temperatures, because the top layer (epidermal area) of silicon rubber is not too crosslinked, have the carbon dioxide that the decomposition by the whipping agent of sodium bicarbonate class produces and break through the sponge hole, escape into the effect of sponge outside easily.
The concrete example of organo-peroxide is listed below, and 1 minute half life temperature of each compound is shown in the bracket.Be fit to use uncle's hexyl peroxy isopropyl base monocarbonate (peroxyesters, 155 ℃), 2,5-dimethyl-2,5-di-t-butyl hexane peroxide (dioxane base class, 180 ℃), 2,5-dimethyl-2,5-di-tert-butyl peroxide hexin (dioxane base class, 194 ℃), ditertiary butyl peroxide (dioxane base class, 186 ℃), dicumyl peroxide (dioxane base class, 175 ℃), cumenyl tert-butyl peroxide (dioxane base class, 173 ℃), hydrogen peroxide be right
Alkane (hydroperoxide type, 200 ℃) etc., but wherein from stability of organo-peroxide etc., particularly preferably utilize the dialkyl peroxide class of 1 minute half life temperature more than 170 ℃ or 170 ℃.These organo-peroxides both can a kind use separately, and the mixture that also can be used as more than 2 kinds or 2 kinds uses.
If above-mentioned cross-linking system does not then become to connect and steeps owing to there is not the passage of foamed gas, therefore, suitable is not compressed moulding, but normal pressure hot gas adds sulphur.Add in the sulphur at normal pressure hot gas, also comprise the powder curing method that is divided into granulated glass sphere that soaks that makes.
(C) use level of composition can be a significant quantity, and particularly, the organopolysiloxane of per 100 mass parts (A) composition is generally 0.01～50 mass parts, preferred 0.5～10 mass parts.Even too much can significantly not improve curing speed yet, and the removing to become and need long time of unreacted reactant or residue decomposition.
In addition, as solidifying agent, preferred addition reaction-type solidifying agent, promptly, use the crosslinking reaction that causes simultaneously owing to use the addition reaction of solidifying agent (below, be called " crosslinking agent ") of the combination of the organic hydride polysiloxane that contains hydrosilylation reaction catalyst (addition reaction catalyst) and work as linking agent.At this moment, as mentioned above, after organo-peroxide solidified, if addition-crosslinkedly do not begin, owing to become the form of the passage that stops up foamed gas, so use simultaneously when addition-crosslinked, hope was the auxiliary addition-crosslinked system for crosslinked fully (A) composition.Particularly, as crosslinking agent, use crosslinked beginning temperature to be set at more than 160 ℃ or 160 ℃ preferred 170～190 ℃ crosslinking agent simultaneously.Crosslinked beginning temperature more than 160 ℃ or 160 ℃ is mixed (A) composition and crosslinking agent and after measuring with the torquemeter that is set at 160 ℃, can be confirmed not detect tackify.
Use as the organopolysiloxane that uses in (A) composition, can be used among the organic group that is combined in 1 molecule on the Siliciumatom during by the crosslinking reaction of addition reaction, and at least 1 is the organopolysiloxane of vinyl.As addition reaction catalyst, can make known material arbitrarily originally, particularly, can use the metal simple-substance and the compound thereof of platinum family.Can enumerate, for example, be adsorbed on the alcoholic solution, palladium catalyst, rhodium catalyst etc. of coordination compound, the Platinic chloride 6 water salt of microgranular platinum, platinum chloride, Platinic chloride, Platinic chloride 6 water salt and alkene or divinyl dimethyl polysiloxane on the such carrier of silicon-dioxide, aluminum oxide or silica gel.The addition of these catalyzer is a catalytic amount, usually, is scaled the platinum metals amount, can use the scope of 1～1000ppm, the scope of preferred 10～100ppm.If lack than 1ppm, then can not fully promote crosslinking reaction, solidify insufficiently, more than 1000ppm on the other hand, even increase reactive influence also fewly, and be uneconomic.As the addition reaction linking agent, can use the organic hydride polysiloxane of the SiH group that has in a part more than 2 or 2, this organic hydride polysiloxane, can be dendritic any one of straight chain shape, ring-type, branch, solidifying agent as addition reaction curing silica-gel composition, known organic hydride polysiloxane can be used, following general formula (II) can be used usually:
R
2 xH
ySiO
(4-x-y)/2????????????????????(II)
(in the formula, R
2Be 1 valency alkyl of non-replacement or replacement, x and y are respectively 1≤x≤2.2,0.002≤y≤1, and satisfy the positive number of 1.002≤x+y≤3) material of expression.Non-replacement of representing as the R2 in the formula (II) or 1 valency alkyl of replacement are with above-mentioned R
1Identical, preferred carbonatoms 1～12, particularly 1～8 alkyl are for R
1, can enumerate illustrative material.In a part, have more than 2 or 2, preferred above-mentioned SiH group more than 3 or 3, but it both can be at the end of molecular chain, and also can be at non-end.In addition, this organic hydride polysiloxane is 300mm 25 ℃ viscosity preferably
2/ s or 300mm
2Below/the s.
As such organic hydride polysiloxane, particularly, compound that can the illustration following structural formula.
The use level of organic hydride polysiloxane, organic hydride polysiloxane 100 mass parts with respect to (A) composition can cooperate 0.01～10 mass parts.With respect to 1 alkenyl in (A) composition, the ratio of the hydrogen atom of preferred combination on Siliciumatom is 0.5～10 scope, is more preferably 1～4 such scope.If very few, can not obtain fully to improve crosslinked effect, and also not improve physical strength., if too much, the physical property after the curing reduces, and particularly thermotolerance and permanent compression set significantly worsen sometimes.In addition, in this silica-gel composition, preferred add known platinum catalyst inhibitor such as poly-ethylene methacrylic radical siloxane ring compound, the alcohol that contains ethynyl, superoxide and adjust crosslinked beginning temperature.
-(D) composition-
In the present invention, preferably in composition of the present invention, add organic blowing agent, described organic blowing agent is with respect to basic rubber stock 100 mass parts, the mixture that optionally adds (D) composition of 0.7～10.0 mass parts and prepare is under 150 ℃, demonstrate than above-mentioned basic rubber stock separately more than the mooney viscosity of measuring under the identical temperature high 5% or 5% while making it the mooney viscosity ML (1+4) that thermolysis measures, the organic blowing agent of particularly high 10～300% value, wherein, described basic rubber stock be with 100 mass parts by 99.825 moles of % of dimethyl siloxane units, 0.15 mole of % of methyl vinyl siloxane unit, the 0.025 mole of % in dimethyl vinylsiloxane unit constitutes, the organopolysiloxane of polymerization degree average out to 8000 (below, be called the standard organopolysiloxane), the BET specific surface area 195m of 40 mass parts
2The wet silicon dioxide of/g, 4 parts have silanol group and viscosity is 29mm at two ends
2The dimethyl polysiloxane of/s (23 ℃) forms 180 ℃ of following thermal treatments 2 hours after cooperating with kneading machine.By containing the organic blowing agent of this (D) composition, composition of the present invention adds sulphur by HAV, and the average sponge aperture that can make foaming is 2mm or below the 2mm.
In the middle of above-mentioned, the standard organopolysiloxane, those skilled in the art can be by corresponding to the hydrolytic condensation of its molecular raw silicon hydride compounds mixture or by easily making corresponding to the equilibration reaction of molecular raw material polysiloxane oligomers mixture.
(D) organic blowing agent of composition has by thermolysis and can make composition tackify of the present invention or solidified characteristic, by and with such organic blowing agent, sponge hole become densification and homogeneous more more.Organic blowing agent with such feature, particularly, not only the decomposition by whipping agent produces gas, and can make methyl, alkenyl generation crosslinking reaction in the organopolysiloxane molecule that is present in (A) composition by free radical reaction, and polymer viscosity is risen.Therefore, because and the organic blowing agent of using the such viscosity of demonstration to rise, before the whipping agent of sodium bicarbonate class decomposes, because when the sponge moulding, take place simultaneously almost in rubber that decomposition by organic blowing agent causes " (A) tackify of composition; and curing according to circumstances " and " the generation gas that causes by the decomposition of organic blowing agent ", by the nuclear effect of making of performance sponge, the sponge hole homogeneous and fine that becomes steeps in the company of making.
; usually; though the frequent radical polymerization mixture as vinyl compound such as a kind of azo-compound as organic blowing agent use; but with respect to the alkenyl in the organopolysiloxane molecule; can not bring into play the effect of such polymerizing agent, the addition that uses in the common whipping agent also almost of no use can produce strong free radical to increase viscosity or cause the whipping agent of the rising of viscosity in the decomposition of whipping agent.Even the present Diisopropyl azodicarboxylate or 2 that in the silicon rubber of being everlasting, uses as the radical polymerization mixture, 2 '-azo two (2-methylbutyronitrile), 2,2 '-azo two (2, the 4-methyl pentane nitrile), 1,1 '-azo two (1-acetoxyl group-1-diphenylphosphino ethane) etc., owing to decompose, the viscosity that can not observe at short notice rises.As (D) of the present invention composition, these are unavailable.
(D) organic blowing agent of composition, because more preferably the sodium bicarbonate whipping agent of (B) composition produces carbon dioxide 150 ℃ of left and right sides thermal endothermic decomposition, therefore, preferably at the material that decomposes below 150 ℃ or 150 ℃.
Particularly, (D) organic blowing agent of composition, preferably to demonstrate the mooney viscosity of measuring under identical temperature separately than above-mentioned basic rubber stock high by 10～300% for the mooney viscosity ML (1+4) that the mixture that has added this above-mentioned whipping agent is measured on one side 150 ℃ of thermolysiss on one side, is more preferably the azo class organic blowing agent of the value of high 20～200% scope.In addition, this organic blowing agent preferably has the azo class organic blowing agent of the decomposition point below 150 ℃ or 150 ℃.By using such organic blowing agent, when the composition normal pressure hot gas that the present invention is used adds sulphur and makes it to foam, can so that to the average sponge aperture of sponge become 2mm or below the 2mm.As azo class organic blowing agent with such characteristic, can enumerate, for example, 1,1 '-azo two (hexanaphthene-1-methyl carboxylic acids ester), 1,1 '-azo two (hexanaphthene-1-nitrile), 2,2 '-azo two [N-(2-propenyl)-2-methyl propanamide] etc., these both can a kind of independent use, also can two or more be used in combination.
(D) addition of the organic blowing agent of composition with respect to organopolysiloxane 100 mass parts of (A) composition, is 0.1～20 mass parts, preferred 0.5～10 mass parts.(A) organopolysiloxane of composition is wished for finding tackified phenomenon but solidified addition by halves.(D) if the addition of composition less than 0.1 mass parts, viscosity rises few, and the miniaturization or the homogenization in sponge hole do not had effect, if more than 20 mass parts, tackify is excessive, blow(ing) pressure is suppressed, and is difficult to the company of obtaining and steeps sponge.In addition, (D) residue decomposition after the decomposition of composition is also residual more, carry out high temperature, for a long time thermal treatment,, then can take place to produce exudate or separate out problem such as crystallization to the sponge surface if residue decomposition further is not decomposed into low-molecular-weight hydrocarbon polymer etc. or makes it volatilization.Because above-mentioned reason, (B) scope that is more preferably of the addition of composition is 0.2～10.0 mass parts, preferred especially 0.2～5.0 mass parts.
-other compositions-
In the polysiloxane sponge composite that the present invention uses, wish to add enhancing property silicon-dioxide fines.Enhancing property silicon-dioxide fines is that for this purpose, its specific surface area is 50m for the material of necessity of the silicon rubber foam that obtains the physical strength excellence
2/ g or 50m
2More than/the g, preferred 100～400m
2/ g.As this silicon-dioxide fines, can illustration smog matter silicon-dioxide (dry type silicon-dioxide), precipitated silica (wet silicon dioxide), preferred smog matter silicon-dioxide (dry type silicon-dioxide).In addition, also hydrophobization can be carried out with organopolysiloxane, organic polysilazane, chlorosilane, organoalkoxysilane etc. in these surface handles.These silicon-dioxide both can a kind of independent use, also can be used in combination more than 2 kinds or 2 kinds.In addition, the addition of this silicon-dioxide fines is equivalent to organopolysiloxane 100 mass parts of (A) composition, and hope is 5～100 mass parts, preferred 10～90 mass parts, preferred especially 30～80 mass parts.During less than 5 mass parts, very few with respect to 100 mass parts, can not obtain sufficient reinforced effects, if more than 100 mass parts, the processibility variation, in addition, the physical property of the silicon rubber that obtains sometimes reduces.
In addition, the present invention can obtain conductive sponge by adding conductive material.As conductive material, its kind, use level can be used conductive carbon black, electroconductibility oxidized metal class particle without limits, for example, electroconductive zinc oxide, electroconductibility titanium oxide etc., in addition, electro-conductive material both can a kind uses separately, also can more than 2 kinds or 2 kinds and use.At this moment, because carbon becomes the crosslinked obstruction material of organo-peroxide, wish to increase the amount of organo-peroxide, or use above-mentioned high temperature modification crosslinking agent simultaneously.
As above-mentioned carbon black, can use material commonly used in common conductive rubber composition, can enumerate, for example, Shawinigan black, conductive furnace black (CF), super conductive furnace black (SCF), extra conductive furnace black(ECF) (XCF), conductive channel black (CC), heat treated furnace black or channel black etc. under the high temperature about 1500～3000 ℃.As concrete commercially available trade(brand)name, as Shawinigan black, can illustration electrification carbon black (electrochemical society system), Shawnigan Acetylene Black (シ ヤ ウ ニ ガ Application ア セ チ レ Application Block ラ Star Network) (Shawnigan Chemical company (シ ヤ ウ ニ ガ Application ケ ミ カ Le society) system) etc., as conductive furnace black, can illustration Continex (コ Application チ ネ Star Network ス) (Continental Carbon company (コ Application チ ネ Application タ Le カ one ボ Application society) system), Vulcan C (バ Le カ Application C) (Cabot company (キ ヤ ボ Star ト society) system) etc., as super conductive furnace black, can illustration Continex SCF (コ Application チ ネ Star Network ス SCF) (Continental Carbon corporate system), Vulcan SC (バ Le カ Application SC) (Cabot corporate system) etc., as extra conductive furnace black(ECF), can illustration rising sun HS-500 (XuCarbonShe system), VulcanXC-72 (Cabot corporate system) etc., as conductive channel black, can illustration Colax L (コ ウ ラ Star Network ス L) (Degussa company (デ グ Star サ society) system) etc., in addition, also can use a kind of Ketjen black EC (ケ Star チ エ Application Block ラ Star Network EC) and Ketjen black EC-600JD (ketjen Black International company (ケ Star チ エ Application Block ラ Star Network イ Application タ one Na シ ヨ Na Le society) system) as furnace black.Furnace black, its impurity be the amount of sulphur or sulphur compound particularly, with the concentration of element sulphur, wishes for 6000ppm or below the 6000ppm, is more preferably 3000ppm or below the 3000ppm.In addition, in the middle of these, not only the impurity containing ratio is few owing to Shawinigan black, and has flourishing 2 aggregated(particle) structures structure, so excellent electric conductivity is particularly suitable for using in the present invention.In addition, also preferably use the electroconductibility brilliance and have big specific surface area, even at Ketjen blackEC that hangs down the electroconductibility that also shows excellence under the loading level or Ketjen black EC-600JD etc.
The addition of above-mentioned conductive carbon black is with respect to rubber constituent 100 mass parts of above-mentioned (A) composition, preferred 1～100 mass parts, preferred especially 5～50 mass parts.Addition is during less than 1 mass parts, and if surpass 100 mass parts, there is the physical mixed difficulty that becomes in the electroconductibility that can not obtain to expect sometimes, or the possibility that descends of physical strength, can not obtain the caoutchouc elasticity as purpose sometimes.
In addition, as the conductive metal oxide particulate, can enumerate electroconductive zinc oxide, titanium oxide, tin antimony based fine particles etc., particularly, as electroconductive zinc oxide, can enumerate the zinc oxide 23-K (trade(brand)name) of Ha Network ス イ テ Star Network (strain) manufacturing or the electroconductive zinc oxide FX (trade(brand)name) that this village ケ ミ カ Le Co., Ltd. makes, as the white conductive titanium oxide, can enumerate, for example ET-500W (trade(brand)name, the former industry of stone (strain) system).Can add these particulates of 1～300 mass parts simultaneously by these particulates of independent interpolation 1～300 mass parts or with carbon, obtain the resistance of purpose.
In polysiloxane sponge composite of the present invention, also can optionally further add as heat conductivity and give the crushed quartz, zinc oxide, alundum, aluminum oxide of material or as the diatomite of non-enhancing silicon-dioxide, in addition, can also add dispersion agents such as additives such as weighting agent, tinting material, heat resistant accelerator, fire-retardant promotor, souring agent, thermal conduction promotor such as lime carbonate or releasing agent, organoalkoxysilane, diphenyl silanodiol, carbon functional silane, two terminal silanol stopped low molecular weight polyorganosiloxanes etc.
The manufacture method of rubber combination of the present invention, there is no particular limitation, can be with the mentioned component of specified amount by mixing obtaining such as 2 rollers, kneading machine, Banbury mixing tanks.In addition, optionally can also heat-treat (heating under mixing).Particularly, can enumerate, then after cooling, add the method for (B), (C), (D) etc. after (A) composition and enhancing property silicon-dioxide, other the mixing thermal treatment of additive.
Above-mentioned thermal treatment temp, time, there is no particular limitation.Can carry out thermal treatment in 30 minutes～5 hours at 100～250 ℃.
The curing foaming method of rubber combination of the present invention, owing to must improve company's bubble rate in sponge hole by carbon dioxide, so wish to adopt normal pressure hot gas to add sulphur, be fit to use process furnace by having used extrusion molding add sulphur continuously, crosslinked etc. by the hot gas of periodic dryer.But,, can guarantee not necessarily that also inside has sufficient space even metal die is crosslinked.Usually, can by 80～400 ℃, particularly in the normal pressure hot gas heating of carrying out under 100～300 ℃ about 5 seconds～1 hour, make it foamed solidification, obtain the high continued dunking rate sponge.In addition, also can be at the regelate that carries out under 100～230 ℃ about 10 minutes～10 hours.
To add the sulphur foaming by normal pressure hot gas and solidify company's bubble rate 15% or the 15% above high continued dunking rate silica-gel sponge that obtains relevant for above-mentioned sponge composite of the present invention, the layer that contains this sponge that manufacturing is had at least 1 layer be useful for the fixing roller of feature.As such fixing roller, can enumerate, have two layers or more the layer that contains the fixing roller that connects the individual layer steep sponge, will contain this sponge bonding PFA packing element etc. the top layer release materials the multilayer fixing roller, had solid rubber compound and the fixing roller of the toning agent fusion photographic fixing purposes of the multilayered structure fixing roller structure of gelatin sponge and toning agent release layer.
[embodiment]
Below, embodiment and comparative example are shown, specifically describe the present invention, but the present invention not only is defined in following embodiment.In addition, part expression mass parts in the following example.In addition, (D) the mooney viscosity characteristic of composition is concluded and is shown in table 5.
[embodiment 1]
100 parts contain 99.825 moles of % of dimethyl siloxane units, 0.15 mole of % of methyl vinyl siloxane unit, the 0.025 mole of % in dimethyl vinylsiloxane unit, mean polymerisation degree is 8000 organopolysiloxane, 40 parts of BET surface-area 200m
2The dry type silicon-dioxide Arosil200 of/g (Japanese エ ア ロ ジ Le (strain) system), 5 parts have silanol group and viscosity is 29mm at two ends
2The dimethyl polysiloxane of/s (23 ℃) 180 ℃ of following thermal treatments 2 hours, makes basic rubber stock after cooperating with kneading machine.
With respect to 100 parts of the basic rubber stocks that obtains, as whipping agent, with 4.0 parts of sodium bicarbonates (more than the purity 99% or 99% of reagent grade, particle diameter 40 μ m) and 0.6 part 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane adds mixing by 2 roller milling machines, makes the thick rubber stock sheet of 9mm.Then, the sheet that this 9mm is thick adds sulphur with the normal pressure hot gas that 230 ℃ hot-air drier carried out 30 minutes, obtains the polysiloxane sponge.Afterwards, carry out 200 ℃/4 hours 2 times and add sulphur.After removing the top layer from the sponge that obtains, by the mean pore size of the state in following method investigation sponge hardness, expansion ratio, sponge hole, sponge, connect the bubble rate.Evaluation result is shown in table 1～4.
Sponge hardness: the A Si card C hardness of JIS S 6050 regulations
The state in hole: use visual observation
Mean pore size: mean value in the aperture of sponge cut surface
The measuring method that connects the bubble rate
1) proportion and the weight of mensuration sponge sample.2) sponge is submerged in the water in the container of in vacuum vessel, placing, under this state with the vacuum vessel decompression for 10mmHg or below the 10mmHg.3) placed 5 minutes turning back in the vacuum vessel behind the normal pressure, make that sponge sucks in water.4) weight of metering sponge under the state of suction.Then, obtain even bubble rate according to following calculating.
[proportion (1.00) of (decompression is the weight of sponge test portion of the weight of the sponge test portion after the suction-originally down)/water]/[(1-(sponge proportion/not the elastomeric material proportion of foaming)) * (sponge test portion weight/sponge proportion)] * 100 (%)
[embodiment 2]
Except appending 1.0 parts organic blowing agent 1, as beyond hole miniaturization and the nucleator, 1 '-azo two (hexanaphthene-1-methyl carboxylic acids ester) is shaped sponge similarly to Example 1.
[embodiment 3]
Except with 1 of organic blowing agent, 1 '-azo two (cyclohexyl-1-methyl carboxylic acids ester) changes to beyond 2.0 parts, and sponge similarly to Example 2 is shaped.
[embodiment 4]
Except the sodium bicarbonate that replaces whipping agent used 4.0 parts of Diisopropyl azodicarboxylates, sponge similarly to Example 2 was shaped.
[embodiment 5]
Except the sodium bicarbonate that replaces whipping agent uses 4.0 parts of Diisopropyl azodicarboxylates, in addition, with the organo-peroxide solidifying agent by 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane changes to beyond the dicumyl peroxide, sponge similarly to Example 2 is shaped.
[embodiment 6]
Except the sodium bicarbonate decrement with whipping agent was 2.0 parts, sponge similarly to Example 2 was shaped.
[embodiment 7]
Except the sodium bicarbonate increment with whipping agent was 8.0 parts, sponge similarly to Example 2 was shaped.
[embodiment 8]
Except replace 0.6 part as 2 of the organo-peroxide of solidifying agent, 5-dimethyl-2,5-two (t-butyl peroxy) hexane uses beyond 0.6 part of dicumyl peroxide, sponge similarly to Example 2 is shaped.
[embodiment 9]
Except replace 0.6 part as 2 of the organo-peroxide of solidifying agent, 5-dimethyl-2,5-two (t-butyl peroxy) hexane uses beyond 0.6 part of uncle's hexyl peroxy isopropyl base monocarbonate, sponge similarly to Example 2 is shaped.
[embodiment 10]
Except the organic blowing agent 1 that will add as hole miniaturization and nucleator, 1 '-azo two (hexanaphthene-1-methyl carboxylic acids ester) changes to other organic blowing agent 2, in addition, 2 '-azo two [N-(2-propenyl)-2-methyl propanamide] is shaped sponge similarly to Example 2.
[embodiment 11]
Except with organic blowing agent by embodiment 2 use 1,1 '-azo two (cyclohexyl-1-methyl carboxylic acids ester) changes to beyond the organic blowing agent Diisopropyl azodicarboxylate, sponge similarly to Example 2 is shaped.
[embodiment 12]
Except with organic blowing agent by embodiment 2 use 1,1 '-azo two (cyclohexyl-1-methyl carboxylic acids ester) changes to other organic blowing agent 1,1 '-azo two (1-acetoxyl group-1-diphenylphosphino ethane) in addition, sponge similarly to Example 2 is shaped.
[embodiment 13]
As solidifying agent, for and with addition-crosslinked, append C-25A (platinum catalyst)/C-25B (Organhydridosiloxaneresins class linking agent) of adding crosslinked beginning temperature and being controlled to be about 170 ℃ addition-crosslinked system/contain acetylene group alcohol (respectively being 0.3 part/2.0 parts/0.7 part) (and, C-25A/C-25B is SHIN-ETSU HANTOTAI's chemical industry system), become and used addition-crosslinked cross-linking system, in addition, the sponge that is shaped similarly to Example 2.
[embodiment 14]
Similarly to Example 2, make the thick rubber stock sheet of 9mm after, with this sheet under 230 ℃/30 minutes, offer PCM (powder curing method), obtain silicon rubber foam.
[comparative example 1]
Except with respect to 100 parts of basic rubber stocks; as whipping agent; the sodium bicarbonate that adds 4.0 parts is (more than the purity 99% or 99% of reagent grade; particle diameter 40 μ m) and as the solidifying agent of organo-peroxide; the peroxidation of adding 0.6 part of diacyl class organo-peroxide is to beyond the toluyl, and sponge similarly to Example 1 is shaped.
[comparative example 2]
Add 1.0 part 1 except appending, 1 '-azo two (cyclohexyl-1-methyl carboxylic acids ester) is as beyond the organic blowing agent, with comparative example 1 sponge that similarly is shaped.
[comparative example 3]
Except adding 0.6 part 2; 5-dimethyl-2; outside 5-two (t-butyl peroxy) hexane; also add 0.2 part of peroxidation as diacyl class organo-peroxide to the solidifying agent of toluyl as organo-peroxide; become dioxane base class/diacyl class and with beyond the cross-linking system, sponge similarly to Example 2 is shaped.
[comparative example 4]
Except solidifying agent is changed to contain to toluyl by 0.6 part of peroxidation crosslinked beginning temperature is controlled to be the material of alcohol (each 0.5 part/2.0 parts/0.1 part) of C-25A (the platinum catalyst)/C-25B (Organhydridosiloxaneresins class linking agent) of about 120 ℃ addition-crosslinked system/contain acetylene group, with comparative example 1 sponge that similarly is shaped.
[comparative example 5]
Add 1.0 part 1 except appending, 1 '-azo two (cyclohexyl-1-methyl carboxylic acids ester) is as beyond the organic blowing agent, with comparative example 4 sponge that similarly is shaped.
[comparative example 6]
Except appending 0.6 part as 2 of organo-peroxide, 5-dimethyl-2,5-two (t-butyl peroxy) hexane becomes beyond the about 120 ℃ addition-crosslinked paralled system of the crosslinked and crosslinked beginning temperature of organo-peroxide, with comparative example 5 sponge that similarly is shaped.
[comparative example 7]
Except replacing 2 of 0.6 part of organo-peroxide, 5-dimethyl-2,5-two (t-butyl peroxy) hexane, solidifying agent changed to crosslinked beginning temperature is controlled to be C-25A (the platinum catalyst)/C-25B (Organhydridosiloxaneresins class linking agent) of about 160 ℃ addition-crosslinked system/the contain alcohol (each 0.5 part/2.0 parts/0.7 part) of acetylene group, become beyond the addition-crosslinked independent system, sponge similarly to Example 2 is shaped.
[comparative example 8]
Except with respect to 100 parts of basic rubber stocks, add 1.0 parts of organic blowing agent Diisopropyl azodicarboxylates as whipping agent and 0.6 part of organo-peroxide peroxidation to toluyl as beyond the solidifying agent, sponge similarly to Example 1 is shaped.
[comparative example 9]
Except appending 4.0 parts of sodium bicarbonates as whipping agent, and with the organic blowing agent Diisopropyl azodicarboxylate and with beyond, with comparative example 7 sponge that similarly is shaped.
[comparative example 10]
With respect to 100 parts of basic rubber stocks, as whipping agent, use 2.0 parts of sodium bicarbonates and 1.0 parts of organic blowing agents 1,1 '-azo two (1-acetoxyl group-1-diphenylphosphino ethane), as solidifying agent, only use C-25A (platinum catalyst)/C-25B (Organhydridosiloxaneresins class linking agent) of containing crosslinked beginning temperature and being controlled to be about 120 ℃ addition-crosslinked system/contain addition-crosslinked system of the alcohol (each 0.5 part/2.0 parts/0.1 part) of acetylene group, the forming method shaping sponge same with comparative example 1.
[comparative example 11]
Except with respect to 100 parts of basic rubber stocks, add 1.0 parts of organic blowing agent Diisopropyl azodicarboxylates as whipping agent, add 0.6 part organo-peroxide 1, as beyond the solidifying agent, two (t-butyl peroxy carboxyl) hexanes of 6-(peroxy esters class, 163 ℃) are shaped sponge similarly to Example 1.
With the sponge that embodiment 2～comparative example 11 obtains, estimate similarly to Example 1.The results are shown in table 1～4.
[table 1]
| ? | Composition | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 |
| Basic rubber stock NaHCO 3Whipping agent organic blowing agent A organic blowing agent B organic blowing agent C organic blowing agent D PO solidifying agent A PO solidifying agent B PO solidifying agent C PO solidifying agent D crosslinking agent A crosslinking agent B | (B) (D) (D) (B) (B) (C) (C) (C) relatively (E) (E) | ??100??4.0??????0.6 | ??100??4.0??1.0?????0.6 | ??100??4.0??2.0?????0.6 | ??100???1.0???4.0???0.6????? | ??100???1.0???4.0????0.6???? | ??100??2.0??1.0?????0.6 | ??100??8.0??1.0?????0.6 |
| ?? The sponge stateHardness (A Si card C) the poroid attitude of expansion ratio % aperture (μ m) | ? | 60 150 slightly heterogeneity 1000＜ | 21 300 homogeneous 400 | 24 280 homogeneous 280 | 22 300 homogeneous 600 *2 | 21 310 homogeneous 170 *2 | 30 210 homogeneous 330 | 18 350 homogeneous 600 |
| Connect bubble rate % | ? | ??78 | ??95 | ??82 | ??49 | ??32 | ??63 | ??97 |
| Other | ? | ? | ? | ? | Part is damaged | Part is damaged | ? | ? |
[0133][table 2]
| ? | Composition | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 | Embodiment 14 |
| Basic rubber stock NaHCO 3Whipping agent organic blowing agent A organic blowing agent B organic blowing agent C organic blowing agent D PO solidifying agent A PO solidifying agent B PO solidifying agent C PO solidifying agent D crosslinking agent A crosslinking agent B | (B) (D) (D) (B) (B) (C) (C) (C) relatively (E) (E) | ??100??4.0??1.0??????0.6 | ??100??4.0??1.0???????0.6 | ??100??4.0???1.0????0.6????? | ??100??4.0????1.0???0.6????? | ??100??4.0?????1.0??0.6????? | ??100??4.0??1.0?????0.6??????0.3/2.0 | ??100??4.0??1.0?????0.6????? |
| ?? The sponge stateHardness (A Si card C) the poroid attitude of expansion ratio % aperture (μ m) | ? | 19 320 homogeneous 350 | 45 240 slightly heterogeneity 500＜ | 19 240 homogeneous 350 | 62 140 slightly heterogeneity 1000＜ | 61 150 slightly heterogeneity 1000＜ | 23 280 homogeneous 350 | 22 290 homogeneous 380 |
| Connect bubble rate % | ? | ??62 | ??36 | ??90 | ??74 | ??76 | ??80 | ??97 |
| Other | ? | ? | ? | ? | ? | ? | Surface-crosslinked property is good | ? |
[0135][table 3]
| ? | Composition | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 |
| Basic rubber stock NaHCO 3Whipping agent organic blowing agent A organic blowing agent B organic blowing agent C organic blowing agent D PO solidifying agent A PO solidifying agent B PO solidifying agent C PO solidifying agent D PO solidifying agent E crosslinking agent A crosslinking agent B | (B) (D) (D) (B) (B) (C) (C) (C) compare (E) (E) | ??100??4.0?????????0.6 | ??100??4.0??1.0????????0.6 | ??100??4.0??1.0?????0.6????0.2??? | ??100??4.0????????????0.5/2.0 | ??100??4.0??1.0???????????0.5/2.0 | ??100??4.0??1.0?????0.6???????0.5/2.0 | ??100??4.0??1.0??????????0.3/2.0 |
| ?? The sponge stateHardness (A Si card C) the poroid attitude of expansion ratio % aperture (μ m) | ? | Firm breakage *1 | Firm breakage *1 | 20 300 heterogeneities 800 *2 | Firm breakage *1 | Firm breakage *1 | Firm breakage *1 | 25 280 heterogeneities *3 |
| Connect bubble rate % | ? | ??- | ??- | ??12 | ??- | ??- | ??- | ??8 |
| Other | ? | Solid-state breakage | Solid-state breakage | The independent bubbles part is damaged | Solid-state breakage | Solid-state breakage | Solid-state breakage | Independent bubbles has collapse |
[0137][table 4]
| ? | Composition | Comparative example 8 | Comparative example 9 | Comparative example 10 | Comparative example 11 |
| Basic rubber stock NaHCO 3Whipping agent organic blowing agent A organic blowing agent B organic blowing agent C organic blowing agent D PO solidifying agent A PO solidifying agent B PO solidifying agent C PO solidifying agent D PO solidifying agent E crosslinking agent A crosslinking agent B | (B) (D) (D) (B) (B) (C) (C) (C) compare (E) (E) | ??100??0????1.0????0.6???0.6 | ??100??4.0????1.0????0.6???0.6??? | ??100??2.0?????1.0????????0.5/2.0 | ??100??0????1.0???????0.6?? |
| ?? The sponge stateHardness (A Si card C) the poroid attitude of expansion ratio % aperture (μ m) | ? | 35 220 homogeneous 200 | 28 320 heterogeneities 280 *2 | 18 280 homogeneous 700 | 20 300 homogeneous 400 |
| Connect bubble rate % | ? | ??4 | ??8 | ??4 | ??12 |
| Other | ? | Common independent bubbles sponge | Common independent bubbles part is damaged | Common independent bubbles sponge | Common independent bubbles sponge |
[notes 1 of his-and-hers watches 1～4]
*1: solid state does not almost have the state (part has several millimeters bubble) that foams
*2: produce gas in inside and become piece (huge cavity) or breakage.The inhomogenous state of sponge outward appearance
*3: the foamed gas in the sponge outside is escaped sponge hole heterogeneity.The sponge middle body is an independent bubbles
[notes 2 of his-and-hers watches 1～4]
NaHCO
3Whipping agent: sodium bicarbonate (median size 20 μ m) (gas produces temperature: about 150 ℃)
Organic blowing agent A): 1,1 '-azo two (cyclohexyl-1-methyl carboxylic acids ester) (with reference to table 5)
Organic blowing agent B): 2,2 '-azo two [N-(2-propenyl)-2-methyl propanamide] (with reference to table 5)
Organic blowing agent C): Diisopropyl azodicarboxylate (gas produces temperature: about 106 ℃)
Organic blowing agent D): 1,1 '-azo two (1-acetoxyl group-1-diphenylphosphino ethane) (gas produces temperature: about 107 ℃)
PO solidifying agent A:2,5-dimethyl-2,5-di-t-butyl hexane peroxide (dioxane base class, 1 minute half life temperature: 180 ℃)
PO solidifying agent B: dicumyl peroxide (dioxane base class, 1 minute half life temperature: 175 ℃)
PO solidifying agent C: uncle's hexyl peroxy isopropyl base monocarbonate (peroxyesters, 1 minute half life temperature: 155 ℃)
PO solidifying agent D: peroxidation is to toluyl (diacyl class, 1 minute half life temperature: 128 ℃)
PO solidifying agent E:1, two (t-butyl peroxy carboxyl) hexanes (peroxy esters class, 1 minute half life temperature: 163 ℃) of 6-
Crosslinking agent A: crosslinked beginning temperature is set at about 170 ℃ crosslinking agent
(in the title complex of C-25A/C-25B=0.3 part/2.0 part, having appended 0.7 part of material that contains the alcohol of acetylene group)
Crosslinking agent B: crosslinked beginning temperature is set at about 120 ℃ crosslinking agent (C-25A/C-25B=0.5/2.0)
(in the title complex of C-25A/C-25B=0.5 part/2.0 part, having appended 0.1 part of material that contains the alcohol of acetylene group)
C-25A: platinum catalyst
C-25B: Organhydridosiloxaneresins class linking agent
-(D) the tackify test of composition-
Measured the rising characteristic of mooney viscosity (ML1+4) of the organic blowing agent of (D) composition of in embodiment, comparative example, putting down in writing in accordance with the following methods.
With 100 parts of BET specific surface area 195m by 99.825 moles of % of dimethyl siloxane units, 0.15 mole of % of methyl vinyl siloxane unit, the 0.025 mole of % in dimethyl vinylsiloxane unit organopolysiloxane that constitute, polymerization degree average out to 8000 (below, be called the standard organopolysiloxane), 40 mass parts
2Nipsil LP (Japanese silicon-dioxide (strain) system)), 4 parts to have silanol group and viscosity at two ends be after the dimethyl polysiloxane of 29cs (23 ℃) cooperates with kneading machine the wet silicon dioxide of/g (trade(brand)name:, 180 ℃ of following thermal treatments 2 hours, make basic rubber stock.
In this basic rubber stock, the various organic blowing agents shown in the table 5 of umber (with respect to 100 parts of above-mentioned organopolysiloxane) are made each mixture shown in the interpolation table 5.
Each mixture and basic rubber stock to such manufacturing are determined at the not viscosity of foamed state under 40 ℃.In addition, with the mooney viscosity ML (1+4) of 150 ℃ basic rubber stocks as 100, the relative value of the mooney viscosity ML (1+4) that obtains at each mixture of uniform temp.
These the results are shown in table 5.In addition, in this table, BC is meant the meaning of basic rubber stock.
[table 5]
[remarks]
Condition) use machine to be TOYOSEIKI RLM-1
Whipping agent A) 1,1 '-azo two (cyclohexyl-1-methyl carboxylic acids ester)
Whipping agent B) 2,2 '-azo two [N-(2-propenyl)-2-methyl propanamide]
Whipping agent C) Diisopropyl azodicarboxylate
Whipping agent D) 1,1 '-azo two (1-acetoxyl group-1-diphenylphosphino ethane)
Industrial applicibility
It is master's office machine sponge roller, particularly toner melting fixing roller, feed roll, toner transport roller and cleaning roller etc. with image processing systems such as sponge, heat shield, industrial roller, duplicator, facsimile machine, printers that high continued dunking rate silicon rubber cellular rubber composition of the present invention can be used in building packing ring, various sponge sheet, suction.
Claims (19)
1. high continued dunking rate silicon rubber foam, wherein, described high continued dunking rate silicon rubber foam be by the sponge composite foaming, to solidify the company's bubble rate that obtains be silicon rubber foam more than 15%, described sponge composite contains:
(A) a following average group accepted way of doing sth (I)
R
1aSiO
4-a/2????????????????????(I)
At least the organopolysiloxane that contains 2 alkenyls in a part of expression: 100 mass parts,
R
1Be the group of identical or different kind, this group is that the carbonatoms that is selected from alkyl, cycloalkyl, alkenyl, aryl, aralkyl is the monovalence alkyl that 1～12 non-replacement or halogen replace, and a is 1.95～2.04 positive number,
(B) produce the whipping agent of gas in the temperature province more than 90 ℃: 0.5～50 mass parts,
This whipping agent is selected from organic blowing agent or inorganic foaming agent, described organic blowing agent is selected from: N, N '-dimethyl-N, in N '-dinitroso pentamethylene tetramine, organic azo-compound, sulfonyl hydrazide compound, the triazo-compound one or more, described organic azo-compound is selected from Diisopropyl azodicarboxylate, azo cyclohexanenitrile, azo diaminobenzene, 2,2 '-azo is two-2-methylbutyronitrile, 2,2 '-azo two-2,4-methyl pentane nitrile, 1,1 '-azo two (1-acetoxyl-1-diphenylphosphino ethane), azoformic acid chromium; Described mineral compound be selected from yellow soda ash, bicarbonate of ammonia, volatile salt, the ammonium nitrite more than a kind or 2 kinds, and
(C) 1 minute half life temperature is the non-acyl group class organo-peroxide more than 150 ℃: the significant quantity that can solidify (A) composition.
2. according to the high continued dunking rate silicon rubber foam of claim 1 record, wherein, (B) composition is organic azoic foaming agent, and (C) 1 minute half life temperature of the non-acyl group class organo-peroxide of composition is more than 170 ℃.
3. according to the high continued dunking rate polysiloxane sponge of claim 1 record, wherein, (C) the non-acyl group class organo-peroxide of composition is that 1 minute half life temperature is the dialkyl peroxide class organo-peroxide more than 170 ℃.
4. according to the high continued dunking rate polysiloxane sponge of claim 2 record, wherein, (C) the non-acyl group class organo-peroxide of composition is that 1 minute half life temperature is the dialkyl peroxide class organo-peroxide more than 170 ℃.
5. according to the high continued dunking rate polysiloxane sponge of each record in the claim 1～4, it also contains crosslinked beginning temperature and is set at the crosslinking agent of the temperature more than 160 ℃ as (E) composition.
6. according to the high continued dunking rate polysiloxane sponge of claim 1 record, wherein, the R of a described average group accepted way of doing sth (I)
1Be selected from methyl, vinyl, phenyl, trifluoro propyl.
7. high continued dunking rate silicon rubber foam, wherein, described high continued dunking rate silicon rubber foam be by the sponge composite foaming, to solidify the company's bubble rate that obtains be silicon rubber foam more than 15%, described sponge composite contains:
(A) a following average group accepted way of doing sth (I)
R
1aSiO
4-a/2???????????????(I)
At least the organopolysiloxane that contains 2 alkenyls in a part of expression: 100 mass parts,
R
1Be the group of identical or different kind, this group is that the carbonatoms that is selected from alkyl, cycloalkyl, alkenyl, aryl, aralkyl is the monovalence alkyl that 1～12 non-replacement or halogen replace, and a is 1.95～2.04 positive number,
(B) produce the whipping agent of gas in the temperature province more than 90 ℃: 0.5～50 mass parts, and
(C) 1 minute half life temperature is the non-acyl group class organo-peroxide more than 150 ℃: can solidify the significant quantity of (A) composition,
This non-acyl group class organo-peroxide is selected from uncle's hexyl peroxy isopropyl base monocarbonate, 2,5-dimethyl-2, and 5-di-tert-butyl peroxide hexin, ditertiary butyl peroxide, cumenyl tert-butyl peroxide, hydrogen peroxide are right
In the alkane one or more.
8. according to the high continued dunking rate silicon rubber foam of claim 7 record, wherein, (B) composition is a sodium bicarbonate.
9. according to the high continued dunking rate silicon rubber foam of claim 7 record, wherein, (B) composition is organic azoic foaming agent, and (C) 1 minute half life temperature of the non-acyl group class organo-peroxide of composition is more than 170 ℃.
10. according to the high continued dunking rate silicon rubber foam of claim 8 record, wherein, (B) composition is organic azoic foaming agent, and (C) 1 minute half life temperature of the non-acyl group class organo-peroxide of composition is more than 170 ℃.
11. according to the high continued dunking rate polysiloxane sponge of each record in the claim 7～10, wherein, (C) the non-acyl group class organo-peroxide of composition is that 1 minute half life temperature is the dialkyl peroxide class organo-peroxide more than 170 ℃.
12. according to the high continued dunking rate polysiloxane sponge of each record in the claim 7～10, it also contains crosslinked beginning temperature and is set at the crosslinking agent of the temperature more than 160 ℃ as (E) composition.
13. according to the high continued dunking rate polysiloxane sponge of claim 11 record, it also contains crosslinked beginning temperature and is set at the crosslinking agent of the temperature more than 160 ℃ as (E) composition.
14. according to the high continued dunking rate polysiloxane sponge of claim 7 record, wherein, the R of a described average group accepted way of doing sth (I)
1Be selected from methyl, vinyl, phenyl, trifluoro propyl.
15. company's bubble rate is the manufacture method of the high continued dunking rate silicon rubber foam more than 15%, wherein, contains by crosslinked sponge composite foaming, the solidified process that makes each record in the claim 1～14 of normal pressure hot gas.
16. a fixing roller, it has 1 layer of layer that contains following high continued dunking rate silicon rubber foam at least,
Described high continued dunking rate silicon rubber foam be by sponge composite foaming, to solidify the company's bubble rate that obtains be silicon rubber foam more than 15%, described sponge composite contains:
(A) a following average group accepted way of doing sth (I)
R
1aSiO
4-a/2??????????????(I)
At least the organopolysiloxane that contains 2 alkenyls in a part of expression: 100 mass parts,
R
1Be the group of identical or different kind, this group is that the carbonatoms that is selected from alkyl, cycloalkyl, alkenyl, aryl, aralkyl is the monovalence alkyl that 1～12 non-replacement or halogen replace, and a is 1.95～2.04 positive number,
(B) produce the whipping agent of gas in the temperature province more than 90 ℃: 0.5～50 mass parts, and
(C) 1 minute half life temperature is the non-acyl group class organo-peroxide more than 150 ℃: the significant quantity that can solidify (A) composition.
17. according to the fixing roller of claim 16 record, wherein, the R of a described average group accepted way of doing sth (I)
1Be selected from methyl, vinyl, phenyl, trifluoro propyl.
18. an electro photography image processing system, wherein, described image processing system possesses following fixing roller, and this fixing roller has 1 layer of layer that contains following high continued dunking rate silicon rubber foam at least,
Described high continued dunking rate silicon rubber foam be by sponge composite foaming, to solidify the company's bubble rate that obtains be silicon rubber foam more than 15%, described sponge composite contains: (A) following average group accepted way of doing sth (I)
R
1aSiO
4-a/2????????????????(I)
At least the organopolysiloxane that contains 2 alkenyls in a part of expression: 100 mass parts,
R
1Be the group of identical or different kind, this group is that the carbonatoms that is selected from alkyl, cycloalkyl, alkenyl, aryl, aralkyl is the monovalence alkyl that 1～12 non-replacement or halogen replace, and a is 1.95～2.04 positive number,
(B) produce the whipping agent of gas in the temperature province more than 90 ℃: 0.5～50 mass parts, and
(C) 1 minute half life temperature is the non-acyl group class organo-peroxide more than 150 ℃: the significant quantity that can solidify (A) composition.
19. according to the electro photography image processing system of claim 18 record, wherein, the R of a described average group accepted way of doing sth (I)
1Be selected from methyl, vinyl, phenyl, trifluoro propyl.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004261677A JP4767516B2 (en) | 2004-09-08 | 2004-09-08 | High foaming rate silicone rubber sponge, method for producing the same, and fixing roll using the silicone rubber sponge |
| JP261677/04 | 2004-09-08 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200510098145 Division CN1746225B (en) | 2004-09-08 | 2005-09-08 | Silicon rubber sponge, its manufacture and image forming roller thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101880462A true CN101880462A (en) | 2010-11-10 |
| CN101880462B CN101880462B (en) | 2012-07-04 |
Family
ID=36156822
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200510098145 Expired - Fee Related CN1746225B (en) | 2004-09-08 | 2005-09-08 | Silicon rubber sponge, its manufacture and image forming roller thereof |
| CN2010101355296A Active CN101880462B (en) | 2004-09-08 | 2005-09-08 | Silicon rubber sponge, its manufacture and image forming roller thereof |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200510098145 Expired - Fee Related CN1746225B (en) | 2004-09-08 | 2005-09-08 | Silicon rubber sponge, its manufacture and image forming roller thereof |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4767516B2 (en) |
| CN (2) | CN1746225B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516770A (en) * | 2011-12-13 | 2012-06-27 | 西北橡胶塑料研究设计院 | Environmentally-friendly flame-retardant silicone rubber sponge and preparation method thereof |
| CN104822746A (en) * | 2013-01-04 | 2015-08-05 | 马里瑟尔公司 | Process for production of rigid foamed objects made of polymer materials |
Families Citing this family (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006193609A (en) * | 2005-01-13 | 2006-07-27 | Shin Etsu Chem Co Ltd | Silicone rubber sponge composition |
| JP4787068B2 (en) * | 2006-05-12 | 2011-10-05 | 信越化学工業株式会社 | High ream rate silicone rubber sponge |
| JP4762781B2 (en) * | 2006-05-12 | 2011-08-31 | 信越化学工業株式会社 | Conductive silicone rubber composition and conductive silicone rubber sponge |
| JP4704954B2 (en) * | 2006-05-12 | 2011-06-22 | 信越化学工業株式会社 | Conductive silicone rubber composition and conductive silicone rubber sponge |
| CN101100551B (en) * | 2006-07-07 | 2010-12-01 | 厚生股份有限公司 | Foaming silicon rubber composition for continuous wide breadth separated foam and processing method thereof |
| JP4854480B2 (en) * | 2006-11-17 | 2012-01-18 | 信越化学工業株式会社 | Silicone rubber sponge, method for producing the same, fixing roll using the same, and electrophotographic image forming apparatus using the fixing roll |
| US20110021649A1 (en) * | 2007-02-07 | 2011-01-27 | Atsushi Sakuma | Sponge-Forming Liquid Silicone-Rubber Composition and Silicone Rubber Sponge Made Therefrom |
| JP5057036B2 (en) * | 2007-03-01 | 2012-10-24 | 信越化学工業株式会社 | Conductive silicone rubber sponge composition and method for producing conductive silicone rubber sponge |
| JP2008214440A (en) * | 2007-03-01 | 2008-09-18 | Shin Etsu Chem Co Ltd | Silicone rubber sponge composition |
| JP6626082B2 (en) | 2014-03-21 | 2019-12-25 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンＨｅｎｋｅｌ ＡＧ ＆ Ｃｏ． ＫＧａＡ | Heat-expandable preparation |
| JP5849128B2 (en) * | 2014-06-20 | 2016-01-27 | 昭和電線デバイステクノロジー株式会社 | Manufacturing method of rubber roller for heat fixing |
| JP6312544B2 (en) * | 2014-07-16 | 2018-04-18 | キヤノン株式会社 | NIP FORMING MEMBER, IMAGE HEATING DEVICE, AND METHOD FOR PRODUCING NIP FORMING MEMBER |
| JP2016031516A (en) * | 2014-07-30 | 2016-03-07 | キヤノン株式会社 | Fixation device |
| JP6439917B2 (en) * | 2014-10-09 | 2018-12-19 | シンジーテック株式会社 | Manufacturing method of fixing / pressure roll |
| DE102014221060A1 (en) | 2014-10-16 | 2016-04-21 | Henkel Ag & Co. Kgaa | Thermally expandable composition |
| CN108292113B (en) * | 2015-11-30 | 2020-09-25 | 住友理工株式会社 | Elastic roller for electrophotographic apparatus and method for manufacturing the same |
| JP6565850B2 (en) * | 2016-09-27 | 2019-08-28 | 信越化学工業株式会社 | Method for producing high-ream silicone rubber sponge, liquid silicone rubber composition for high-ream silicone rubber sponge, and silicone rubber sponge |
| CN106543737A (en) * | 2016-12-06 | 2017-03-29 | 上海新益电力线路器材有限公司 | Cable high-low temperature resistant sheath material, restrictive coating and preparation method thereof |
| JP6976657B2 (en) * | 2017-11-30 | 2021-12-08 | 旭化成ワッカーシリコーン株式会社 | Manufacturing method of silicone rubber sponge |
| US20190219953A1 (en) * | 2018-01-12 | 2019-07-18 | Sumitomo Rubber Industries, Ltd. | Rubber composition, rubber roller, and image forming device |
| US11123903B2 (en) * | 2018-10-25 | 2021-09-21 | Biosense Webster (Israel) Ltd. | Controlling bubble formation in silicone foam filler of breast implants |
| CN113661216B (en) * | 2019-04-10 | 2023-09-19 | 汉高股份有限及两合公司 | Thermally conductive silicone potting composition |
| CN113956667B (en) * | 2021-10-22 | 2023-04-07 | 东莞市曦晨启明新材料科技有限公司 | Foaming silicone rubber and preparation method and application thereof |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5341710B2 (en) * | 1973-09-04 | 1978-11-06 | ||
| FR2474517A1 (en) * | 1979-12-20 | 1981-07-31 | Rhone Poulenc Ind | ORGANOSILIC COMPOSITIONS CONTAINING NEW PRECIPITATION SILICA WITH IMPROVED REINFORCING PROPERTIES |
| JPH01247433A (en) * | 1988-03-29 | 1989-10-03 | Shin Etsu Chem Co Ltd | Expandable organosiloxane composition |
| JPH039932A (en) * | 1989-06-07 | 1991-01-17 | Shin Etsu Chem Co Ltd | Foamable silicone rubber composition and foam thereof |
| JP2001131415A (en) * | 1999-07-19 | 2001-05-15 | Dow Corning Toray Silicone Co Ltd | Silicone rubber sponge-forming composition, silicone rubber sponge and preparation process of silicone rubber sponge |
| JP2001261962A (en) * | 2000-03-22 | 2001-09-26 | Shin Etsu Chem Co Ltd | Electrically conductive expandable silicone rubber composition |
| JP3990094B2 (en) * | 2000-04-25 | 2007-10-10 | 東レ・ダウコーニング株式会社 | Silicone rubber sponge-forming composition, silicone rubber sponge and method for producing them |
| JP3628935B2 (en) * | 2000-04-28 | 2005-03-16 | 東レ・ダウコーニング・シリコーン株式会社 | Silicone rubber sponge-forming composition, silicone rubber sponge and method for producing them |
| JP3647389B2 (en) * | 2000-08-01 | 2005-05-11 | ジーイー東芝シリコーン株式会社 | Polyorganosiloxane foam, foam and method for producing the same |
| JP3705349B2 (en) * | 2000-11-15 | 2005-10-12 | 信越化学工業株式会社 | Silicone rubber sponge composition and silicone rubber sponge using the same |
| JP4061455B2 (en) * | 2001-08-17 | 2008-03-19 | 信越化学工業株式会社 | Olefin sponge composition |
| JP2003096223A (en) * | 2001-09-21 | 2003-04-03 | Dow Corning Toray Silicone Co Ltd | Silicone rubber sponge-forming composition, silicone rubber sponge and process for producing same |
| CN100344701C (en) * | 2004-03-22 | 2007-10-24 | 徐英强 | Making process silicone rubber sponge backing board |
-
2004
- 2004-09-08 JP JP2004261677A patent/JP4767516B2/en not_active Expired - Fee Related
-
2005
- 2005-09-08 CN CN 200510098145 patent/CN1746225B/en not_active Expired - Fee Related
- 2005-09-08 CN CN2010101355296A patent/CN101880462B/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102516770A (en) * | 2011-12-13 | 2012-06-27 | 西北橡胶塑料研究设计院 | Environmentally-friendly flame-retardant silicone rubber sponge and preparation method thereof |
| CN104822746A (en) * | 2013-01-04 | 2015-08-05 | 马里瑟尔公司 | Process for production of rigid foamed objects made of polymer materials |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1746225A (en) | 2006-03-15 |
| JP4767516B2 (en) | 2011-09-07 |
| JP2006077099A (en) | 2006-03-23 |
| CN1746225B (en) | 2010-05-26 |
| CN101880462B (en) | 2012-07-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1746225B (en) | Silicon rubber sponge, its manufacture and image forming roller thereof | |
| TWI414549B (en) | High foam ratio of silicone rubber sponge | |
| US6552096B2 (en) | Hollow filler-containing silicone rubber and method of production | |
| JP4854480B2 (en) | Silicone rubber sponge, method for producing the same, fixing roll using the same, and electrophotographic image forming apparatus using the fixing roll | |
| US20080214688A1 (en) | Silicone rubber sponge composition | |
| WO2000055251A1 (en) | Crosslinkable rubber composition and use thereof | |
| JP2008150447A (en) | Foamable organopolysiloxane composition and silicone rubber sponge | |
| CN102174260B (en) | Silicone rubber sponge composition and silicone rubber sponge | |
| JP2007302829A (en) | Electrically conductive silicone rubber composition and electrically conductive silicone rubber sponge | |
| EP0497565B1 (en) | Foamable silicone rubber composition and silicone rubber sponge | |
| EP0278854B1 (en) | A curable and foamable organopolysiloxane composition | |
| JP2014051560A (en) | Ethylene-propylene-diene rubber foam, production method thereof and sealing material | |
| EP1149859B1 (en) | Silicone rubber sponge composition | |
| CN1775864B (en) | Silicon rubber composition for sponge | |
| US6967221B2 (en) | Hollow filler-containing silicone rubber and method of production | |
| JP4704954B2 (en) | Conductive silicone rubber composition and conductive silicone rubber sponge | |
| JP2018009089A (en) | Silicone rubber sponge | |
| JP5057036B2 (en) | Conductive silicone rubber sponge composition and method for producing conductive silicone rubber sponge | |
| JP2001240712A (en) | Rubber composition | |
| CN101177529A (en) | Silicone rubber composition and little-odour silicone rubber sponge using the same | |
| JP3277748B2 (en) | Foamable silicone rubber composition | |
| JPH10182972A (en) | Silicone rubber sponge composition | |
| JP2007154112A (en) | Electroconductive silicone rubber composition and electroconductive silicone rubber sponge |
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 |