CN1803924A - Silicon rubber sponge composite - Google Patents
Silicon rubber sponge composite Download PDFInfo
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- CN1803924A CN1803924A CN 200610005721 CN200610005721A CN1803924A CN 1803924 A CN1803924 A CN 1803924A CN 200610005721 CN200610005721 CN 200610005721 CN 200610005721 A CN200610005721 A CN 200610005721A CN 1803924 A CN1803924 A CN 1803924A
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Abstract
The invention provides a silicone rubber sponge composition reduced in the toxicity of decomposed products in its expansion, high in expansibility even with no consideration of the crosslinking rate control of the composition and the delicate balance between a foaming agent and an organic peroxide, and giving a silicone rubber sponge having uniform and fine cellular structure and smooth skin layer, especially a silicone rubber sponge of low hardness and high expansion ratio. The silicone rubber sponge composition comprises (A) 100 pts.mass of an organopolysiloxane of the average compositional formula(1):R<SB>a</SB>SiO<SB>4-a/2</SB>(Rs are the same as or different from each other and each a nonsubstituted or substituted monovalent hydrocarbon group; and (a) is a positive number of 1.95-2.04), (B) 0.1-20 pts.mass of an organic foaming agent capable of thickening or curing the component(A) by thermal decomposition, (C) 0.5-20 pts.mass of sodium bicarbonate and (D) such an amount of a curing agent as to enable the component(A) to be cured.
Description
Technical field
The present invention relates to a kind of silicon rubber sponge composite, particularly relate to the silicon rubber sponge composite of giving the soft silicon rubber foam.
Background technology
Silicon rubber foam is built packing ring, various sponge sheet, industrial roller, office machine roller, heat shield etc. owing to its good thermotolerance, winter hardiness, electrical insulating property, flame retardant resistance, compression set characteristic etc. and be widely used in.
Silicon rubber foam generally is behind mixed foaming agent and the solidifying agent, to make it foamed solidification by heating and form sponge in the heat-curing type silastic mixture.At this moment, foaminess is good, have homogeneous and fine pore structure, top layer level and smooth and do not have binding property, what do not damage the distinctive characteristic of silicon rubber is important condition, but the balance of expansion rate and curing speed is very delicate, when this balance is poor slightly, can not get the sponge of above-mentioned characteristic, composition and forming method are had various restrictions.
For example, as the processing molding method of silicon rubber foam, be to carry out mostly making it to solidify in the normal pressure hot gas of continuous molding, foaming.Obtain 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, for before whipping agent decomposes, make the silicon rubber sponge composite compacting live blow(ing) pressure, tackify, solidified necessity are arranged.Therefore, when the sponge moulding, generally wish: 1) make (A) composition tackify or curing (not exclusively) with solidifying agent as reaction sequence; 2) decompose generation gas by whipping agent; 3) make (A) composition completely solidified.
Therefore, addition-crosslinked type is by adjusting catalytic amount or using the reaction control agent to react control and carry out; And the organo-peroxide cross-linking type to be the decomposition temperature of decomposition temperature and whipping agent by selecting organo-peroxide identical or the decomposition temperature that is lower than whipping agent is carried out.
Yet the control of the initial cure of such rubber is difficulty very, as adopts addition-crosslinkedly, has the problem that often changes according to the amount of control agent or activity of such catalysts degree; As adopt organo-peroxide crosslinked, and then exist when the whipping agent of selecting decomposition temperature and use about equally or during the organo-peroxide below it, must be chosen to be at the problem of the interior similar linking agent of decomposition behavior of whole temperature ranges of sponge mold temperature.
As the whipping agent that silicon rubber foam is used, AIBN (Diisopropyl azodicarboxylate) the most representative (special public clear 44-461 number, patent documentation 1), this is owing to the sponge characteristic good that obtains, but because resolvent toxicity height must carry out the secondary treatment of sponge.
In addition, the spy opens flat 8-134350 number (patent documentation 2) and has proposed 1, and 1 '-azo two (1-acetoxyl group-1-diphenylphosphino ethane) is used as whipping agent, but exists its resolvent that the problem of the offending stink of intensive is arranged.Te Kaiping 8-259816 number (patent documentation 3) proposed the organic azo-compound beyond the AIBN is used as whipping agent, though reduced the toxicity of resolvent, sponge characteristic, particularly soft sponge characteristic can not be fully satisfied.
In addition, the spy opens flat 5-156061 number (patent documentation 4) and has proposed to use inorganic salts such as sodium bicarbonate as safe whipping agent, but has the problem of sponge hole homogeneity and compactness equal difference.In addition, the spy opens 2002-146078 number (patent documentation 5) and has proposed to use the organic azo-compound of nonnitriles of having considered security as whipping agent, but in the soft sponge, the homogeneity in hole, compactness can not be fully satisfied.
[patent documentation 1] special public clear 44-461 communique
[patent documentation 2] spy opens flat 8-134350 communique
[patent documentation 3] spy opens flat 8-259816 communique
[patent documentation 4] spy opens flat 5-156061 communique
[patent documentation 5] spy opens the 2002-146078 communique
Summary of the invention
[problem that invention will solve]
The present invention In view of the foregoing, even resolvent toxicity reduced the control of the rate of crosslinking of not considering silicon rubber sponge composite or the trickle balance of whipping agent and organo-peroxide when a kind of the foaming was provided, foaminess is also excellent, have homogeneous and the fine level and smooth silicon rubber foam in pore structure, top layer, and the silicon rubber sponge composite as the silicon rubber foam of soft high foamability particularly can be provided.
What present inventors concentrated one's attention on to study in order to achieve the above object found that, used simultaneously and can make (A) composition tackify or solidified organic blowing agent and sodium bicarbonate silicon rubber sponge composite by thermolysis as whipping agent, the toxicity of resolvent reduces during foaming, even do not consider the control of rate of crosslinking of silicon rubber sponge composite or the trickle balance of whipping agent and organo-peroxide, it is good also to obtain foaminess, have homogeneous and fine pore structure, the silicon rubber foam that the top layer is level and smooth, particularly obtain silicon rubber foam as the soft high foamability, based on above discovery, finished the present invention.
Therefore, the invention provides a kind of silicon rubber sponge composite, it is characterized in that, contain:
(A) organopolysiloxane of following column average composition formula (1) expression:
R
aSiO
4-a/2 (1)
(R is the identical or different monovalence alkyl that does not replace or replace, and a is 1.95～2.04 positive number)
100 mass parts
(B) can make (A) composition tackify or solidified organic blowing agent by thermolysis
0.1～20 mass parts
(C) sodium bicarbonate 0.5～50 mass parts
(D) solidifying agent can make (A) composition solidified amount
[effect of invention]
According to the present invention, even resolvent toxicity reduced the control of the rate of crosslinking of not considering silicon rubber sponge composite or the trickle balance of whipping agent and organo-peroxide when a kind of the foaming was provided, also can obtain foaminess good, have homogeneous and the fine level and smooth silicon rubber foam in pore structure, top layer, particularly can access the silicon rubber sponge composite of the silicon rubber foam of giving the soft high foamability.
Embodiment
The present invention is described in more detail below.
(A) organopolysiloxane of composition is represented with a following average group accepted way of doing sth (1).
R
aSiO
(4-a)/2 (1)
(R represents the identical or different monovalence alkyl that does not replace or replace, and a is 1.95～2.04 positive number).
In an above-mentioned average group accepted way of doing sth (1), R represents the identical or different monovalence alkyl that does not replace or replace, and carbonatoms is 1～12 usually, and preferred especially carbonatoms is 1～8, particularly, can enumerate alkyl such as methyl, ethyl, propyl group, butyl, hexyl, octyl group; Cycloalkyl such as cyclopentyl, cyclohexyl; Alkenyls such as vinyl, allyl group, propenyl; The closed chain thiazolinyl; Aryl such as phenyl, tolyl; Aralkyl such as benzyl, 2-phenylethyl; The perhaps trifluoro propyl that replaced by halogen atom or cyano group of part or all of the hydrogen atom in these groups etc., preferable methyl, vinyl, phenyl, trifluoro propyl, special preferable methyl, vinyl.80 moles of % among the preferred R or 80 moles are more than the %, and particularly 90 moles of % or 90 moles of % are above is methyl.
Particularly, the main chain of preferred this organopolysiloxane comprises the material of dimethyl siloxane units, perhaps imported in this dimethyl polysiloxane main chain part have phenyl, vinyl, 3,3, diphenyl siloxane unit, methyl vinyl siloxane unit, the methyl-3 of 3-trifluoro propyl etc., 3, the material of 3-trifluoropropyl siloxane unit etc.
In addition, this organopolysiloxane when addition-crosslinked, must have 2 or 2 above alkenyls in 1 molecule, preferred vinyl, and preferred 0.01～10 mole of %, particularly 0.02～5 mole of % is an alkenyl.
When organic peroxide crosslinking, according to the organo-peroxide kind, alkenyl also may not be essential, but preferred 0.01～10 mole of %, particularly 0.02～5 mole of % is an alkenyl.
In addition, this alkenyl both can be bonded on the molecule chain end Siliciumatom, also can be bonded on the Siliciumatom of side chain, also can be bonded on both, but preferably be bonded at least on the molecule chain end Siliciumatom.Particularly, end capped alkenyls such as preferred molecule chain end dimethyl vinyl silanes base, methyl divinyl silylation, trivinyl silylation.
Have an amount of alkenyl, when particularly end had alkenyl, particularly curing characteristics was good, and resulting rubber property is also good.
A is 1.95～2.04 positive number, is the straight chain shape substantially, but in the scope of not damaging caoutchouc elasticity, also can be a chain.
The polymerization degree of this organopolysiloxane is more than 100 or 100, preferred 3,000～100,000, preferred especially 4,000～20,000.When the polymerization degree is lower than 100, can not obtain sufficient rubbery intensity.
In addition, this organopolysiloxane both can use a kind, also can use simultaneously the molecular structure or the polymerization degree different more than 2 kinds or 2 kinds.
Such organopolysiloxane can adopt known method, for example organo-halogen-silane more than a kind or 2 kinds or 2 kinds by (being total to) hydrolytic condensation, or cyclic polysiloxanes carried out ring-opening polymerization with alkalescence or an acidic catalyst and obtain.
(B) whipping agent of composition is to make (A) composition tackify or solidified organic blowing agent by thermolysis.This whipping agent be with the organopolysiloxane of (A) composition and (B) organic blowing agent of composition mix, heat and when making the organic blowing agent thermolysis, have the organopolysiloxane tackify that can make (A) composition or the organic blowing agent of solidified characteristic.At this moment curing is not completely solidified, is meant the state that can be cured.
This organic blowing agent not only produces substituting groups such as gas, and methyl that exists in the organopolysiloxane molecule with (A) composition or alkenyl because of whipping agent decomposes, and is undertaken crosslinked and can make the polymer viscosity rising by free radical reaction.
The organic blowing agent that has such characteristic by use, when the sponge moulding, because the generation gas that the base polymer tackify by the solidifying agent effect in the rubber, curing and the decomposition by whipping agent cause almost takes place simultaneously, therefore, can be adjusted at catalytic amount control reaction when addition-crosslinked, or freely select linking agent, be not subjected to the restriction ground of organic peroxide breakdown temperature to obtain hardness or the compression set characteristic that silicon rubber foam requires.In addition, can also be in the low temperature temperature range wide to pyritous at the mold temperature of sponge, moulding sponge stably, in forming method, not only can pass through normal pressure hot gas vulcanizing/forming sponge, even and pressure expansion or in cylindrical tube, foam, also moulding sponge stably.
(B) organic blowing agent of composition, as long as having above-mentioned characteristic gets final product and is not particularly limited, but (C) the composition sodium bicarbonate is 150 ℃ of left and right sides thermal endothermic decomposition, produce carbonic acid gas, therefore preferably at the organic blowing agent that decomposes below 150 ℃ or 150 ℃, particularly preferably in the azo class organic blowing agent that decomposes below 150 ℃ or 150 ℃.Particularly, organopolysiloxane 100 mass parts of (A) composition are mixed with organic blowing agent 0.2～5 mass parts of (B) composition, when 150 ℃ of thermolysiss, preferably the mooney viscosity ML (1+4) of the organopolysiloxane of (A) composition is more than 5% or 5%, particularly can make the organic blowing agent of viscosity rising 10～300%.
Particularly, can especially preferably use 1,1 '-azo two (hexanaphthene-1-methyl carboxylic acids ester), 1,1 '-azo two (hexanaphthene-1-methyl nitrile), 2,2 '-azo two [N-(2-propenyl)-2-methyl propanamide].
(B) use level of the organic blowing agent of composition is 0.1～20 mass parts with respect to organopolysiloxane 100 mass parts of (A) composition, preferred 0.2～10 mass parts, special preferred 0.2～5 mass parts.When being lower than 0.1 mass parts, (A) the organopolysiloxane viscosity of composition rises few, can not stay in the sponge by the gas that (C) composition takes place, generation gas releases, and does not form sponge, also is heterogeneity and coarse sponge even perhaps form sponge, when surpassing 20 mass parts, undue tackify suppresses blow(ing) pressure, can not obtain the sponge (soft sponge) of high foamability.
(C) sodium bicarbonate of composition plays the effect of foaming simultaneously with (B) organic blowing agent of composition.Sodium bicarbonate is different with inorganic foaming agents such as volatile salt or ammonium nitrite, triazo-compounds, can not produce strong acid or alkali, odorless owing to decomposing, and do not hinder the crosslinked or addition-crosslinked curing of organo-peroxide, for expansion ratio is risen, obtain the soft sponge, can add morely.In addition, nontoxic, security is also high.
Sodium bicarbonate also can be that sodium bicarbonate is carried out the processing of sponge nucleation or adds nucleator, a small amount of acid or micro-sodium bicarbonate that adds other inorganic foaming agents that adds as decomposition accelerating agent.
If the addition of sodium bicarbonate is many, expansion ratio uprises, and the also attenuation of sponge hole wall, therefore, can easily control sponge proportion, sponge hardness, expansion ratio with this addition.
This addition is 0.5～50 mass parts with respect to organopolysiloxane 100 mass parts of (A) composition, preferred 1～20 mass parts.When being lower than 0.5 mass parts, gas takes place insufficient, can not obtain the soft sponge, and when surpassing 50 mass parts, it is too much that gas takes place, and sponge is broken internally sometimes.
Solidifying agent as (C) composition, as long as can make rubber combination curing of the present invention get final product and not be particularly limited, as the silicon rubber solidifying agent, preferred known crosslinking reaction by organo-peroxide, by the crosslinking reaction of addition reaction, promptly preferably use organic hydride polysiloxane and hydrosilylation catalysts simultaneously.
As organo-peroxide, for example, can enumerate benzoyl peroxide, 2, the 4-dichlorobenzoperoxide, to methyl benzoyl peroxide, adjacent methyl benzoyl peroxide, 2,4-dicumyl peroxide, 2, two (2, the 5-t-butyl peroxy) hexanes of 5-dimethyl, ditertiary butyl peroxide, t-butylperoxyl benzoate, cumenyl tert-butyl peroxide, 1,6-hexylene glycol dual-tert-butyl peroxycarbonates etc.These can use more than a kind or 2 kinds or 2 kinds.Wherein, half life temperature was more than 160 ℃ or 160 ℃ in preferred 1 minute, particularly 160～200 ℃ organo-peroxide.The addition of organo-peroxide is 0.1～20 mass parts with respect to organopolysiloxane 100 mass parts of (A) composition, preferred especially 0.2～10 mass parts.
Being used for the hydrosilylation catalysts by the crosslinking reaction of addition reaction, is to the aliphatics unsaturated link(age) (alkenyl and dialkylene etc.) of (A) composition and the catalyzer of the addition reaction of the silicon atom bonding hydrogen atom (SiH yl) of organic hydride polysiloxane.
As hydrosilylation catalysts, can enumerate platinum metals class catalyzer, platinum metals class simple substance and compound thereof are arranged, in the middle of these, can use catalyzer known substances as original addition reaction curing rubber composition.For example, the alcoholic solution of the microgranular platinum of absorption, platinum chloride, Platinic chloride, Platinic chloride 6 water salt, palladium catalyst, rhodium catalyst etc. on carriers such as silicon-dioxide, aluminum oxide or silica gel, but preferred platinum or platinic compound.The addition of catalyzer, so long as can promote the catalytic amount of addition reaction to get final product, preferably being converted into the platinum amount is 1～1000ppm, preferred especially 10～500ppm scope.When addition is very few, can not fully promote addition reaction, insufficient when being solidified with, on the other hand, served as for a long time, even it is interpolation is more, also few, uneconomic often to reactive influence.
As the organic hydride polysiloxane, if contain 2 or 2 above SiH in 1 molecule, preferably contain the SiH group more than 3 or 3, then can be any for straight chain shape, ring-type, a catenate, linking agent as addition reaction curing rubber composition, known organic hydride polysiloxane can be used, for example, the organic hydride polysiloxane of following column average composition formula (2) expression can be used:
R
1 pH
qSiO
(4-P-q)/2 (2)
In an above-mentioned average group accepted way of doing sth (2), R
1The monovalence alkyl that expression does not replace or replaces both can be the same or different, preferably except the alkyl of aliphatics unsaturated link(age).Usually, carbonatoms is 1～12, preferred especially 1～8 alkyl, particularly, can enumerate alkyl such as methyl, ethyl, propyl group, cycloalkyl such as cyclohexyl, alkenyls such as vinyl, allyl group, butenyl, hexenyl, aryl such as phenyl, tolyl, aralkyl such as benzyl, 2-phenylethyl, 2-phenyl propyl, and part or all group that is replaced by halogen atom of the hydrogen atom of these groups, for example 3,3,3-trifluoro propyl etc.In addition, p, q are for satisfying the positive number of 0≤p＜3, preferred 1≤p≤2.2,0＜q≤3, preferred 0.002≤q≤1,0＜p+q≤3, preferred 1.002≤p+q≤3.
Organic hydride polysiloxane, SiH group have more than 2 or 2 in 1 molecule, preferably have more than 3 or 3, and this group both can also can also be in both at molecule chain end in the middle of molecular chain.In addition, as the organic hydride polysiloxane, be 0.5～10 25 ℃ viscosity, 000cSt, preferred especially 1～300cSt.
The use level of above-mentioned organic hydride polysiloxane is with respect to organopolysiloxane 100 weight parts of base polymer, preferred 0.1～40 weight part.In addition, with respect to the aliphatics unsaturated link(age) (alkenyl and dialkylene) of the organopolysiloxane of 1 base polymer, the ratio of bonded hydrogen atom on the Siliciumatom (≡ SiH group) is that 0.5～10 scope is suitable, is preferably 0.7～5 scope.When being lower than 0.5, crosslinked insufficient, can not obtain sufficient mechanical sometimes, and when greater than 10 the time, the physical property after the curing reduces, particularly thermotolerance and compression set characteristic variation sometimes.
In addition, be purpose to adjust curing speed, can also use addition-crosslinked control agent.Particularly, can enumerate alcohol or Fourth Ring methylvinyl-polysiloxane, the hydrogen peroxide etc. that ethynylcyclohexanol etc. contains ethynyl.
In addition, preferably in silicon rubber sponge composite of the present invention, cooperate enhancing property silicon-dioxide, as enhancing property silicon-dioxide, can enumerate fumed silica, precipitated silica, preferred fumed silica.The preferred 50m of specific surface area (BET method)
2/ g or 50m
2More than/the g, preferred especially 100～400m
2/ g.When specific surface area (BET method) was too small, giving of physical strength was insufficient sometimes.
Can carry out the hydrophobization surface treatment with known treatment agents such as organopolysiloxane, chlorosilane, hexamethyldisilazane, organoalkoxysilanes as required to these silicon-dioxide.
The addition of this silicon-dioxide is 10～100 mass parts with respect to (A) composition organopolysiloxane 100 mass parts, preferred 20～70 mass parts, preferred especially 30～60 mass parts.When being lower than 10 mass parts, addition is very few, the effect that can not be enhanced, and when surpassing 100 mass parts, the processibility variation, in addition, physical strength reduces sometimes.
When the organopolysiloxane of (A) composition mixes with the wet silicon dioxide of (B) composition, preferably cooperate the polymerization degree to be lower than two terminal (E) dispersion agents such as organoalkoxysilane such as silazane compound, dimethyldimethoxysil,ne or vinyltrimethoxy silane such as diorganopolysiloxanecompositions, hexamethyldisilazane such as end capped dimethyl polysiloxane of silanol or ethylene methacrylic radical siloxane of using of 100.
Its use level is 0.1～30 mass parts with respect to organopolysiloxane 100 mass parts of (A) composition, particularly 0.5～20 mass parts.When use level was very few, additive effect was little, had served as for a long time, sometimes the rubber rerum natura that obtains was had detrimentally affect.
Add the sulphur condition as normal pressure hot gas, add the sulphur temperature and be generally 100～600 ℃, preferred 200～500 ℃, preferred especially 250～400 ℃, add the sulphur time and be several seconds～20 minute, preferred about 10 seconds～10 minutes.In addition, can also be at the after fixing that carries out under 100～250 ℃ about 30 minutes～10 hours.
In addition, in the silicon rubber sponge composite that uses among the present invention, in the scope that does not hinder effect of the present invention, can also in silicon rubber sponge composite, cooperate known additive.Can enumerate, stearic acid for example, palmitinic acid, oleic acid, senior lipid acid such as lauric acid, Zinic stearas, nickel stearate, calcium stearate, Magnesium Stearate, zinc oleate, senior fatty acid metal salt such as calcium oleate, Stearic ethyl stearate, the stearic acid stearyl ester, ethyl oleate, butyl oleate, castor seeds oil senior lipid acid such as (ricinoleates of glycerol) and pure ester, stearylamide, oleylamide, the releasing agents such as amides of senior lipid acid such as palmitic amide, ferric oxide, halogenide, titanium oxide, flame retardant resistance rising agent and thermotolerance rising agents such as cerium oxide, UV light absorber, mould inhibitor, tinting material etc.
Embodiment
Embodiment and comparative example are shown below, specifically describe the present invention, but the present invention is not subjected to the restriction of the following example.Also has part expression mass fraction in the following example.
Embodiment 1
In 100 parts of the heat-curable silicone rubber compositions KE951U (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacturing) that contains the about 30 quality % of enhancing property silicon-dioxide, interpolation is as 1 of organic blowing agent, 0.5 part of 1 '-azo two (hexanaphthene-1-methyl carboxylic acids ester), 0.5 part of 4 parts, addition-crosslinked dose C-25A of sodium bicarbonate (median size 5～10 μ m) (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacturing), 2 parts of C-25B (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacturing), carry out mixingly with two rollers, make the thick sheet of 5mm.It is placed in 200 ℃ moisture eliminator made sponge in 10 minutes, carry out 4 hours after fixing in 200 ℃ then.The sponge that obtains is measured sponge state, sponge hardness (A Si card C hardness), expansion ratio.It the results are shown in table 1.
Embodiment 2
Except making 1, the amount of 1 '-azo two (hexanaphthene-1-methyl carboxylic acids ester) is beyond 2 parts, similarly to Example 1 operation.
Embodiment 3
Except making 1, the amount of 1 '-azo two (hexanaphthene-1-methyl carboxylic acids ester) is beyond 5 parts, similarly to Example 1 operation.
Embodiment 4
Except making 1, the amount of 1 '-azo two (hexanaphthene-1-methyl carboxylic acids ester) is beyond 10 parts, similarly to Example 1 operation.
Embodiment 5
Except with 1,1 '-azo two (hexanaphthene-1-methyl carboxylic acids ester), is operated beyond 1 '-azo two (hexanaphthene-1-nitrile) replaces similarly to Example 2 with 1.
Embodiment 6
Except with 1,1 '-azo two (hexanaphthene-1-methyl carboxylic acids ester), is operated beyond 2 '-azo two [N-(2-propenyl)-2-methyl propanamide] replaces similarly to Example 2 with 2.
Embodiment 7
Except making solidifying agent is as 2 of organo-peroxide, beyond the 5-dimethyl-2,0.5 part of 5-di-t-butyl hexane peroxide, and operation similarly to Example 2.
Embodiment 8
Except the amount of sodium bicarbonate is 2 parts, operation similarly to Example 2.
Embodiment 9
Except the amount of sodium bicarbonate is 10 parts, operation similarly to Example 2.
Embodiment 10
Except the amount of sodium bicarbonate is 20 parts, operation similarly to Example 2.
[table 1]
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | |
| The sponge state | ||||||||||
| Hardness (A Si card C) | 25 | 12 | 6 | 5 | 10 | 9 | 11 | 24 | 5 | 2 |
| Expansion ratio (%) | 300 | 500 | 510 | 520 | 460 | 550 | 220 | 510 | 670 | 900 |
| Poroid attitude | Fine | Fine | Fine | Fine | Fine | Fine | Carefully | Fine | Carefully | Thick slightly |
| Aperture (μ m) | 200 | 300 | 350 | 500 | 350 | 220 | 300 | 250 | 500 | 700 |
Comparative example 1
Except not adding 1,1 '-azo two (hexanaphthene-1-methyl carboxylic acids ester) is operated in addition similarly to Example 1.It the results are shown in table 2.
Comparative example 2
Except with 1, beyond 1 '-azo two (hexanaphthene-1-methyl carboxylic acids ester) replaces with Diisopropyl azodicarboxylate, operation similarly to Example 2.
Comparative example 3
Except with 1,1 '-azo two (hexanaphthene-1-methyl carboxylic acids ester) is with 2, and 2 '-azo is two-beyond the 2-methylbutyronitrile replaces, operates similarly to Example 2.
Comparative example 4
Except with 1,1 '-azo two (hexanaphthene-1-methyl carboxylic acids ester), is operated beyond 1 '-azo two (1-acetoxyl group-1-diphenylphosphino ethane) replaces similarly to Example 2 with 1.
Comparative example 5
Except not adding sodium bicarbonate, operation similarly to Example 2.
[table 2]
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| The sponge state | |||||
| Hardness (A Si card C) | 70 | 66 | Uncured | 71 | 35 |
| Expansion ratio (%) | 153 | * | * | 300 | |
| Poroid attitude | Slightly | Fine | |||
| Aperture (μ m) | More than 1000 or 1000 | 250 |
*: foamed gas releases, and can not be called sponge
Embodiment 11
In 100 parts of heat-curable silicone rubber compositions KE951U (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacturing), add 1,2 parts of 1 '-azos two (hexanaphthenes-1-methyl carboxylic acids ester), 4 parts of sodium bicarbonates, as 2 of organo-peroxide solidifying agent, 5-dimethyl-2,0.5 part of 5-di-t-butyl hexane peroxide, carry out mixingly with two rollers, make 2mm sheet mat.In the thick metal die of the 6mm that is heated to 170 ℃ in advance, the rubber of packing into makes mold volumes is reached 30% with it, at 170 ℃, and 30 minutes (pressure that puts on metal die is 3.5MPa) of foaming in metal die, then, 200 ℃ of after fixing 4 hours.The sponge that obtains is measured sponge state, sponge hardness (A Si card C hardness), expansion ratio.It the results are shown in table 3.
Embodiment 12
Except making 1, the amount of 1 '-azo two (hexanaphthene-1-methyl carboxylic acids ester) is beyond 5 parts, similarly to Example 11 operation.
Embodiment 13
Except the amount of sodium bicarbonate is 10 parts, operation similarly to Example 11.
Comparative example 6
Except not adding 1,1 '-azo two (hexanaphthene-1-methyl carboxylic acids ester) is operated in addition similarly to Example 11.
Comparative example 7
Except not adding sodium bicarbonate, operation similarly to Example 11.
Comparative example 8
Except not adding sodium bicarbonate, operation similarly to Example 12.
[table 3]
| Embodiment 11 | Embodiment 12 | Embodiment 13 | Comparative example 6 | Comparative example 7 | Comparative example 8 | |
| The sponge state | ||||||
| Hardness (A Si card C) | 15 | 13 | 6 | 60 | 40 | 50 |
| Expansion ratio (%) | 300 | 350 | 360 | 200 | 170 | 270 |
| Poroid attitude | Fine | Fine | Fine | Slightly | Fine | Fine |
| Aperture (μ m) | 100 | 50 | 50 | More than 1000 or 1000 ** | 50 ** | 50 ** |
*: in metal die, the insufficient expansion of sponge, the insufficient state of material
Claims (4)
1. a silicon rubber sponge composite is characterized in that, wherein contains:
(A) organopolysiloxane of a following average group accepted way of doing sth (1) expression:
R
aSiO
4-a/2 (1)
(R is the identical or different monovalence alkyl that does not replace or replace, and a is 1.95～2.04 positive number)
100 mass parts
(B) can make (A) composition tackify or solidified organic blowing agent by thermolysis
0.1～20 mass parts
(C) sodium bicarbonate 0.5～50 mass parts
(D) solidifying agent can make (A) composition solidified amount.
2. according to the silicon rubber sponge composite of claim 1 record, wherein, (B) organic blowing agent of composition is to be selected from 1,1 '-azo two (hexanaphthene-1-methyl carboxylic acids ester), 1,1 '-azo two (hexanaphthenes-1-nitrile), 2, at least a in 2 '-azo two [N-(2-propenyl)-2-methyl propanamide].
3. according to the silicon rubber sponge composite of claim 1 or 2 records, wherein, (D) solidifying agent of composition is the addition reaction solidifying agent.
4. according to the silicon rubber sponge composite of any one record in the claim 1～3, wherein, resulting sponge is that hardness (A Si card C) is the soft sponge below 30 or 30.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP006216/05 | 2005-01-13 | ||
| JP2005006216A JP2006193609A (en) | 2005-01-13 | 2005-01-13 | Silicone rubber sponge composition |
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| CN107531997A (en) * | 2015-03-31 | 2018-01-02 | 罗杰斯公司 | Two temperature curable organosilicon composition, manufacture method and product prepared therefrom |
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| JP5110962B2 (en) * | 2006-10-31 | 2012-12-26 | 関西ペイント株式会社 | Cationic electrodeposition coating composition and articles coated with the electrodeposition coating |
| 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 |
| JP5655106B2 (en) * | 2013-03-21 | 2015-01-14 | 住友ゴム工業株式会社 | Conductive rubber composition, transfer roller, and image forming apparatus |
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| 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 |
| JP4767516B2 (en) * | 2004-09-08 | 2011-09-07 | 信越化学工業株式会社 | High foaming rate silicone rubber sponge, method for producing the same, and fixing roll using the silicone rubber sponge |
| JP4777629B2 (en) * | 2004-09-14 | 2011-09-21 | 信越化学工業株式会社 | Silicone rubber sponge composition and silicone rubber sponge |
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| CN107531997A (en) * | 2015-03-31 | 2018-01-02 | 罗杰斯公司 | Two temperature curable organosilicon composition, manufacture method and product prepared therefrom |
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