CN101177529A - Silicone rubber composition and little-odour silicone rubber sponge using the same - Google Patents
Silicone rubber composition and little-odour silicone rubber sponge using the same Download PDFInfo
- Publication number
- CN101177529A CN101177529A CNA2007101657449A CN200710165744A CN101177529A CN 101177529 A CN101177529 A CN 101177529A CN A2007101657449 A CNA2007101657449 A CN A2007101657449A CN 200710165744 A CN200710165744 A CN 200710165744A CN 101177529 A CN101177529 A CN 101177529A
- Authority
- CN
- China
- Prior art keywords
- composition
- mass parts
- rubber composition
- silicon
- agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/22—After-treatment of expandable particles; Forming foamed products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
- C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a silastic composition which uses the traditional organic azo nitrogen foaming agent, needs no post solidification process and reduces the smells due to the use of the foaming agent, as well as a small-smell silastic sponge using the composition. The silastic composition comprises (A) an organic polysiloxane expressed in the following average component formula (I) and one molecule of which comprises at least two alkenyls; (B) an organic azo forming agent; (C) a composition consisting of water and silicon dioxide; and (D) a solidifying agent. In the R1ASiO(4-a)2 (I), the R1 refers to a same or different un-substituted or substituted one valence alkyl ; and a refers to a plus from 1.95 to 2.04.
Description
Technical field
The present invention relates to the little silicon rubber foam of stink, be particularly related to the little silicon rubber foam of the stink that is suitable in sponge roller, heat Insulation films etc. at office equipment such as building sealing-ring, various sponge sheet, industrial roller, duplicating machine and be used to prepare the rubber composition of this silicon rubber foam.
Background technology
Silicon rubber foam has the distinctive physical property of silicon rubber, has excellent character at aspects such as thermotolerance, winter hardiness, electrical insulating property, flame retardant resistance and compression sets.These silicon rubber foams are that the solidification compound that heat-curable silicone rubber compositions and solidifying agent and blowing agent combination are formed is heated basically, make it to foam, be solidified to form.At this moment, importantly can obtain following silicon rubber foam: the foaminess excellence of above-mentioned solidification compound, have even and fine foam structure, do not have binding property simultaneously, and do not damage the distinctive physical property of silicon rubber.
As the processing molding method of silicon rubber foam, be to make it in can carrying out continuously shaped normal pressure hot gas, to solidify, foam mostly.In order to obtain silicon rubber foam, use Diisopropyl azodicarboxylate (AIBN), 1 usually, organic azos such as 1 '-azo two (1-hexahydrobenzoic acid) dimethyl ester are whipping agent.But, because Diisopropyl azodicarboxylate (AIBN) generates organic cyanogen compound when it decomposes, so in the complete vulcanizing plant of treatment facility, the shortcoming that must carry out after fixing is fully arranged; 1,1 '-azo two (1-hexahydrobenzoic acid) dimethyl ester etc. are because generate the stink composition by decomposition, so the shortcoming of band stink in the silicon rubber foam that obtains is arranged.
Above-mentioned shortcoming is used as whipping agent by the organic azo-compound with safe noncyanide type and is solved (patent documentation 1), but because above-mentioned whipping agent be special compound but the high price, even to use the organic azo that used be whipping agent so seek to develop always in the past, also can overcome the method for above-mentioned shortcoming.
[patent documentation 1] TOHKEMY 2002-146078 communique
Summary of the invention
Therefore, the 1st purpose of the present invention be to provide used the organic azo that in the past always used be whipping agent not only do not need to carry out after fixing, and can reduce the use of following whipping agent and the rubber composition that produces stink.
The 2nd purpose of the present invention is to provide makes the silicon rubber foam that adaptability excellence and stink are lowered.
The inventor etc. have carried out deep investigation repeatedly in order to reach above-mentioned each purpose, found that, by containing water in the feedstock composition before the silicon rubber foam foaming, the stink that can produce when making the said composition foamable reduces, thereby has finished the present invention.
Therefore, the present invention relates to contain the rubber combination of following (A)～(D) composition, and the little silicon rubber foam of stink, it is characterized in that, make the said composition foamable and form.
(A) 100 mass parts are by a following average group accepted way of doing sth (I) expression and have the organopolysiloxane of at least 2 alkenyls in a part,
R
1 aSiO
(4-a)/2 (I)
(in the formula, R
1Be that the identical or different 1 valency alkyl, a that do not replace or replace is 1.95～2.04 positive number.)；
(B) the organic azoic foaming agent of 0.5～50 mass parts;
(C) composition formed by following component of 0.1～50 mass parts:
(C-1) 100 mass parts water,
(C-2) 1～1000 mass parts silicon-dioxide; With
(D) be used to make the solidifying agent of A composition solidified significant quantity.
Rubber composition of the present invention was because can use in the past the organic azo that uses was whipping agent always, thus be cheap, and when the preparation silicon rubber foam because do not need to carry out after fixing, so aspect the productivity of silicon rubber foam excellence.In addition, in the silicon rubber foam that obtains, be that whipping agent decomposes and the stink of generation because be difficult to adhere to, so can improve the value of silicon rubber foam goods by employed organic azo.
Embodiment
(A) composition of conduct the 1st constituent in rubber composition of the present invention is the organopolysiloxane of being represented and being had at least 2 alkenyls by a following average group accepted way of doing sth (I) in a part.
R
1 aSiO
(4-a)/2 (I)
R in the following formula
1Be that the identical or different 1 valency alkyl, a that do not replace or replace is 1.95～2.04 positive number.
R in the above-mentioned average group accepted way of doing sth (I)
1From alkyl such as methyl, ethyl, propyl group, butyl, hexyl, dodecyls, cycloalkyl such as cyclohexyl, alkenyls such as vinyl, allyl group, butenyl, hexenyl, aryl such as phenyl, tolyl, aralkyl such as β-hydrocinnamyl have perhaps replaced in the chloromethyl, trifluoro propyl, cyanoethyl etc. of part or all hydrogen atom on the carbon atom that is combined in these groups with halogen atom, cyano group etc. and have selected.A plurality of R
1Both can be identical, also can be different, but preferred carbonatoms is 1～12, preferred especially carbonatoms is 1～8 the 1 valency alkyl that does not replace or replace.Specifically, preferable methyl, vinyl, phenyl, trifluoro propyl are as above-mentioned R
1Particularly, preferable methyl be 80 moles of % of whole organic radicals above, further preferably 95 moles more than the %.In addition, a is 1.95～2.04 positive number.
Organopolysiloxane with an above-mentioned average group accepted way of doing sth (I) expression comes down to straight catenate, but also side chain can be arranged in the not impaired scope of the caoutchouc elasticity of the silicon rubber foam after curing.The molecule chain end of this organopolysiloxane can be with sealings such as trimethyl silyl, dimethyl vinyl silyl, dimethyl hydroxyl silyl, trivinyl silyls, but must have at least 2 alkenyls in molecule.In the present invention, preferred R
1In 0.001～5 mole of % be that alkenyl, preferred especially 0.01～0.5 mole of % are alkenyls, vinyl especially preferably.
Above-mentioned organopolysiloxane usually can be with selecteed organo-halogen-silane hydrolytic condensation more than a kind or 2 kinds, perhaps by using alkalescence or an acidic catalyst, cyclic polysiloxanes (3 polymers of siloxanes or 4 polymers etc.) is carried out ring-opening polymerization and obtains.This organopolysiloxane is straight catenate diorganopolysiloxanecompositions basically, but also can some side chain.In addition, also can be the different mixture more than 2 kinds or 2 kinds of molecular structure.
The mean polymerisation degree of above-mentioned organopolysiloxane in the present invention preferably 200～20000, be more preferably 2000～10000, further preferably 3000～8000.Mean polymerisation degree was less than 200 o'clock, and the viscosity of the rubber composition after this organopolysiloxane cooperates is low excessively, can not obtain the rubber sense sometimes.In addition, if greater than 20000, then produce problems such as cooperating difficulty sometimes.
From the viewpoint of the silicon rubber that obtains the physical strength excellence, rubber composition of the present invention preferably contains the reinforcement SiO 2 powder.From the viewpoint of physical strength, the specific surface area of above-mentioned reinforcement silicon-dioxide (BET) is 50m preferably
2/ g is above, 100～400m especially preferably
2/ g.If specific surface area is less than 50m
2/ g, then the physical strength of cured article becomes not enough sometimes.
Organic azoic foaming agent of (B) composition that uses in rubber composition of the present invention for example, can list N, N '-dimethyl-N, N '-dinitrosoterephthalamine, N, N '-nitroso compounds such as dinitroso pentamethylene tetramine; 1,1 '-azo two (1-hexahydrobenzoic acid) dimethyl ester, Cellmic C 121, Diisopropyl azodicarboxylate, azo cyclohexanenitrile, azo diaminobenzene, 2,2 '-azo, two-2-methylbutyronitrile, 2,2 '-azo two-2,4-methyl pentane nitrile, 1,1 '-azo two (1-acetoxyl group-1-diphenylphosphino ethane), azodicarbonamide, barium azodicarboxylate, 1,1 '-azo two (hexanaphthene-1-methyl carboxylic acids ester), 1,1 '-azo two (hexanaphthene-1-nitrile), 2,2 '-azo two organic azo-compounds such as [N-(2-propenyl)-2-methyl propanamide]; Benzenesulfonyl hydrazides, tosyl group hydrazides, p, p '-oxygen two (benzenesulfonyl hydrazides), sulfobenzides-3,3 '-disulfonyl base hydrazides, 4, alkylsulfonyl hydrazide compounds such as 4 '-oxygen two (benzenesulfonyl hydrazides), p-toluenesulfonyl hydrazides; Azide calcium, 4, triazo-compounds such as 4-phenylbenzene disulfonyl base trinitride, p-toluenesulfonyl trinitride etc.
In the present invention, preferred especially the use at intramolecularly do not have the silicon rubber of obstruction solidified sulphur compound among these, phosphoric acid salt, organic azo-compound of strong amine etc., for example, can preferably use 1,1 '-azo two (1-hexahydrobenzoic acid) dimethyl ester, Diisopropyl azodicarboxylate, 2,2 '-azo, two-2-methylbutyronitrile, 2,2 '-azo two-2, the 4-methyl pentane nitrile, 1,1 '-azo two (1-acetoxyl group-1-diphenylphosphino ethane), 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 organic azoic foaming agents both can use separately, also can make up more than 2 kinds and use.
With respect to 100 mass parts above-mentioned (A) composition, organic azoic foaming agent of above-mentioned (B) composition uses 0.5～50 mass parts, but preferably uses 1～20 mass parts.If this usage quantity is less than 0.5 mass parts, then to become for making the silicon rubber foaming easily be inadequate to the gas volume of Chan Shenging, so resulting cured article is difficult to become the sponge state.In addition, if this usage quantity greater than 50 mass parts, then is blended in the difficulty that physically becomes with (B) composition and other composition sometimes, and produces following situation: the gas that produces when the sponge moulding becomes many, it is inhomogeneous that thereby abscess becomes, and resulting sponge is isolated internally.
With respect to 100 mass parts (A) composition, " silicon-dioxide water " composition of (C) composition that uses in rubber composition of the present invention uses 0.1～50 mass parts.If consumption is less than 0.1 mass parts, then follow the decomposition of above-mentioned whipping agent and the stink that produces to reduce effect just little, even and add 50 mass parts more than, can not produce its above stink reduction effect.Here, the effect that is suppressed at the stink that produces when whipping agent decomposes is arranged, be used to make the water-dispersion of (C-1) composition as the silicon-dioxide of (C-2) composition as the glassware for drinking water of (C-1) composition.This is because of adding normally difficulty of water in hydrophobic silicon rubber, disperse jointly with silicon-dioxide by making it, and the dispersion of water in silicon rubber just becomes good.
The specific surface area of the silicon-dioxide that uses as (C-2) composition is 50m preferably
2/ g is above, be more preferably 100～400m
2/ g.As such silicon-dioxide, for example can list fumed silica (dry type silicon-dioxide) and precipitated silica (wet silicon dioxide), but especially preferably use fumed silica (dry type silicon-dioxide) in the present invention.In addition, also can use with organopolysiloxane, organic poly-silazane, chlorosilane, organoalkoxysilane etc. the surface of these silicon-dioxide is carried out that hydrophobization is handled and the material that obtains, but from the viewpoint of the water-dispersion that makes (C-1) composition, preferred to use the surface be hydrophilic surperficial untreated silica.
In the present invention, both can use separately above-mentioned silicon-dioxide, also two or more kinds may be used.In addition, must be more than 1 mass parts with respect to the addition of 100 mass parts water, silicon-dioxide, when 1 mass parts is following, make water-dispersion insufficient, so (C-1) water sepn of composition, rubber composition becomes uneven composition.In addition, even add the above silicon-dioxide of 200 mass parts, additive effect can not further improve, so be uneconomic.
Above-mentioned (C-1), (C-2) composition can be by using Banbury mixer, De ユ-ミ キ サ one compounding rubber machine uniform mixing such as (kneading machines), but especially by using three roller mixing rolls etc. can improve dispersiveness.
Solidifying agent as (D) composition in the rubber composition of the present invention, for example can list benzoyl peroxide, peroxidation 2,4-dichloro-benzoyl, peroxidation are to toluyl, peroxidation o-methyl-benzene formyl, peroxidation 2,4-dicumyl, 2,5-dimethyl-two (2, the 5-t-butylperoxy) hexane, di-t-butyl peroxide, t-butylperoxyl benzoate, 1,6-hexylene glycol-organic peroxide sulfuration agent such as di-t-butyl peroxy carbonates.(D) addition of the solidifying agent of composition is so long as to making (A) composition solidified significant quantity just passable, but is 0.1～15 mass parts, 0.2～10 mass parts especially preferably with respect to 100 mass parts (A) composition preferably.Even too much, curing speed can not further improve, just to spend unnecessary time for removing unreacted reactant and residue decomposition.
In addition, the present invention also can make the electroconductibility sponge by adding conductive material.
About conductive material, its kind, use level without limits, can use conductive carbon black, electroconductibility oxidized metal is particle, for example can use electroconductive zinc oxide, electroconductibility titanium dioxide etc.In addition, electro-conductive material both can use separately, also two or more kinds may be used.At this moment,, carbon hinders the crosslinked material of organo-peroxide, so preferably reduce the amount of carbon addition or increase organo-peroxide because becoming.
As above-mentioned carbon black, can use carbon black commonly used in common conductive rubber composition.For example, can list Shawinigan black, conduction furnace treated black (CF), extra conductive furuace carbon black (SCF), especially conduct electricity furnace treated black (XCF), conduction thermally oxidized black (CC), with the furnace treated black of 1500～3000 ℃ of left and right sides high-temperature heat treatment and thermally oxidized black etc.
About concrete commercially available product, Shawinigan black can list Denka Black (production of electrochemical company), シ ヤ ウ ニ ガ Application acetylene black (production of シ ヤ ウ ニ ガ Application chemical company) etc.; The conduction furnace treated black can list コ Application チ ネ Star Network ス CF (production of コ Application チ ネ Application Le カ one ボ Application company), Vulcan C (production of Cabot company) etc.; Extra conductive furuace carbon black can list コ Application チ ネ Star Network ス SCF (production of コ Application チ ネ Application Le カ one ボ Application company), Vulcan SC (production of Cabot company) etc.; Special conduction furnace treated black can list rising sun HS-500 (production of rising sun Carbon company), Vulcan XC-72 (production of Cabot company) etc.; The conduction thermally oxidized black can list コ ウ ラ Star Network ス L (production of Degussa company) etc.
In addition, also can use as furnace treated black a kind of Ketjen black EC and Ketjenblack EC-600JD (production of Ketjen black international company).Furnace treated black preferred impurity, particularly sulphur and sulphur compound amount are below the 6000ppm, are more preferably below the 3000ppm with the element sulphur densitometer.
In addition, among these, remarkable and big specific surface area from it is even also can preferably use low loading level also to demonstrate the Ketjen black EC300JD of superior electrical conductivity and Ketjen black EC-600JD etc.
With respect to the rubber constituent of 100 mass parts above-mentioned (A) composition, the addition of above-mentioned conductive carbon black is 1～30 mass parts preferably, especially preferably 5～20 mass parts.Addition can not get desirable electroconductibility during less than 1 mass parts sometimes, and during greater than 20 mass parts, and the possibility that then has the rubber solidified nature to descend and so on can not get the caoutchouc elasticity as target.
In addition, as the conductive metal oxide particulate, can list electroconductive zinc oxide, titanium dioxide, tin antimony is particulate etc.Object lesson as electroconductive zinc oxide, for example can list the zinc oxide 23-K (trade(brand)name) of HAKUSUI TECH Corporation production and the electroconductive zinc oxide FX (trade(brand)name) that this village chemical Co., Ltd. produces, as white conductive titanium dioxide, for example can list ET-500W (trade(brand)name, Ishihara Sangyo Kaisha, Ltd. produce).By these particulates are used separately or and carbon together and usefulness, add 1～300 mass parts altogether, thereby can obtain purpose resistance.
In rubber composition of the present invention, can also add crushed quartz, zinc oxide, alumina, aluminum oxide as required as giving thermally conductive materials, perhaps also add diatomite as beyond the non-reinforcement silicon-dioxide, also can add weighting agent, tinting material, thermotolerance rising agent, flame retardant resistance rising agent such as lime carbonate, be subjected to additive such as sour agent, thermal conductivity rising agent and releasing agent, organoalkoxysilane, diphenyl silanodiol, carbon functional group's silane, two ends is with the dispersion agents such as low molecular weight polyorganosiloxane of silanol sealing etc.
The manufacture method of rubber composition of the present invention is not specially limited, can be mixing and obtain with two roller mills, kneading machine, Banbury mixer etc.Specifically, can list (A) composition and other additive are carried out mixing, thermal treatment, after cooling, add (B), (C) and method (D) etc.
By carrying out foamable curing, can easily obtain silicon rubber foam through operating the rubber composition that is made into like this.This curing foaming method is so long as that the sulfuration of the decomposition of whipping agent and silicon rubber is applied the method for sufficient heat is just passable.In addition,, be not limited to the endless vulcanization of being undertaken by extrusion moulding especially, the moulding of being undertaken by compacting, injection such as molded about its forming method yet.In the present invention, be particularly suitable for adopting the sulfuration of normal pressure hot gas.Preferably 100～500 ℃, especially preferably 150～400 ℃ of the Heating temperatures of this moment, the time is several seconds～1 hour preferably, especially preferably 10 seconds～30 minutes.In addition, as required, also can carry out 2 sulfurations with about 180～250 ℃, 1～10 hour.
Below, specifically describe the present invention by embodiment and comparative example, but the present invention is not limited by these.In addition, remove the occasion of indicating especially, " part " in following is meant that " mass parts ", " % " are meant " quality % ".
[embodiment 1]
＜basic rubber size A 〉
Cooperate 100 parts to be made up of 99.825 moles of % dimethyl siloxane units, 0.15 mole of % methyl vinyl siloxane unit, 0.025 mole of % dimethyl vinylsiloxane unit and mean polymerisation degree is about 8000 organopolysiloxane with kneading machine, 40 parts of BET specific surface areas are 200m
2The dry type silicon-dioxide Aerosil200 of/g (Japanese Aerosil Co., Ltd. produce) and 5 parts have silanol group and viscosity during at 25 ℃ is the dimethyl polysiloxane of 29mPas at two ends, with 180 ℃ of thermal treatments 2 hours, make basic rubber size A.
＜compositions of additives A 〉
Mix 100 parts of water and 20 parts of dry type silicon-dioxide Aerosil200 (trade(brand)name, Japanese Aerosil Co., Ltd. produce) with planetary stirring machine, make compositions of additives A.
The making of＜rubber size sheet 〉
Add with two roller mills and to mix 100 parts of above-mentioned basic rubber size A, 1.5 parts as 1 of organic blowing agent, 1 '-azo two (1-hexahydrobenzoic acid) dimethyl ester (produce with the pure medicine of light Co., Ltd., trade(brand)name: VE-073), 2 parts of above-mentioned compositions of additives A and 1 part of dicumyl peroxide, make the thick rubber size sheet of 9mm.
The making of＜silicon rubber foam 〉
With 230 ℃ hot-air driers the thick rubber size sheet normal pressure hot gas of 9mm that obtains was vulcanized 30 minutes, obtain silicon rubber foam.
The evaluation of＜silicon rubber foam 〉
Take out silicon rubber foam from moisture eliminator, after 30 minutes, determine stink, estimate foul smell with the distance of 10cm.In addition, metewand is: with no foul smell is 0; To odorous, estimate with 5 grades of 1 (foul smell is little)～5 (foul smell is strong).
In addition, remove cortex from the silicon rubber foam that obtains after, use the state of observation by light microscope sponge abscess, estimate based on following metewand.In addition, about the sponge density of silicon rubber foam, measure according to JIS K6249.Evaluation result is shown in table 1～2.
[metewand]
Well: mean cell diameter is 100～400 μ m, evenly.
Slightly: mean cell diameter is 400～1000 μ m, and is roughly even.
Huge: mean cell diameter is more than the 1000 μ m, and deviation is arranged.
[embodiment 2]
Except using following compositions of additives B to replace the compositions of additives A and embodiment 1 similarly operate and comes the moulding sponge, the mensuration rerum natura.
＜compositions of additives B 〉
Mix 100 parts of water and 29 parts of dry type silicon-dioxide Aerosil200 (trade(brand)name, Japanese Aerosil Co., Ltd. produce) with planetary stirring machine, make compositions of additives B.
[embodiment 3]
Except using following compositions of additives C to replace replacing the compositions of additives A and embodiment 1 similarly operate and comes the moulding sponge, the mensuration rerum natura.
＜compositions of additives C 〉
Mix 100 parts of water and 34 parts of dry type silicon-dioxide Aerosil200 (trade(brand)name, Japanese Aerosil Co., Ltd. produce) with planetary stirring machine, make compositions of additives C.
[comparative example 1]
Except not adding compositions of additives A (water and dry type silicon-dioxide) and embodiment 1 similarly operate and come the moulding sponge, measure rerum natura.
[comparative example 2]
Except not adding 1, beyond 1 '-azo two (1-hexahydrobenzoic acid) dimethyl ester and embodiment 1 similarly operate and come the moulding sponge, measure rerum natura.
[comparative example 3]
Except not adding compositions of additives A (water and silicon-dioxide), and add 4.0 parts of sodium bicarbonates as beyond the whipping agent and embodiment 1 similarly operate and come the moulding sponge, measure rerum natura.
The characteristic of the sponge that in embodiment 1～3 and comparative example 1～3, obtains and the results are shown in table 1 and the table 2.As from shown in the result of table 1 and table 2, confirmed that the stink level of silicon rubber foam of the present invention after sponge moulding neutralization is taken out sponge from drying machine is low, obtained abscess silicon rubber foam in good condition.
[table 1]
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Sizing material A | 100 | 100 | 100 |
| Foaming agent composotion A | 1.5 | 1.5 | 1.5 |
| Foaming agent composotion B | |||
| Compositions of additives A | 2 | ||
| Compositions of additives B | 2 | ||
| Compositions of additives C | 2 | ||
| Vulcanizing agent A | 1 | 1 | 1 |
| Density | 0.60 | 0.55 | 0.48 |
| Foul smell | 1 | 2 | 3 |
| The state of sponge abscess | Well | Well | Well |
Foul smell 0: do not have foul smell
1 (foul smell is little) ← → (foul smell is strong) 5
[table 2]
| Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Sizing material A | 100 | 100 | 100 |
| Foaming agent composotion A | 1.5 | 1.5 | |
| Foaming agent composotion B | 4 | ||
| Compositions of additives A | 2 | ||
| Compositions of additives B | |||
| Compositions of additives C | |||
| Vulcanizing agent A | 1 | 1 | 1 |
| Density | 0.45 | 0.78 | 0.38 |
| Foul smell | 5 | 0 | 4 |
| The state of sponge abscess | Well | Huge | Slightly |
Foul smell 0: do not have foul smell
1 (foul smell is little) ← → (foul smell is strong) 5
Solidifying agent in the＜table, the explanation of whipping agent 〉
Foaming agent composotion A 1,1 '-azo two (1-hexahydrobenzoic acid) dimethyl ester (produce with the pure medicine of light Co., Ltd., trade(brand)name: VE-073)
Foaming agent composotion B NaHCO
3
Compositions of additives A water: Aerosil200 (trade(brand)name, Japanese Aerosil Co., Ltd. produce)=100: 20 (mass parts)
Compositions of additives B water: Aerosil200 (trade(brand)name, Japanese Aerosil Co., Ltd. produce)=100: 29 (mass parts)
Compositions of additives C water: Aerosil200 (trade(brand)name, Japanese Aerosil Co., Ltd. produce)=100: 34 (mass parts)
The vulcanizing agent A dicumyl peroxide
As mentioned above, because the stink level of silicon rubber foam of the present invention after sponge moulding neutralization is taken out sponge from drying machine is low, be cell density and abscess silicon rubber foam in good condition, so useful in sponge roller, heat Insulation films etc. at office equipment such as building sealing-ring, various sponge sheet, industrial roller, duplicating machine.
Claims (7)
1. a rubber composition is characterized in that, contains following (A)～(D) composition:
(A) 100 mass parts are by a following average group accepted way of doing sth (I) expression and have the organopolysiloxane of at least 2 alkenyls in a part,
R
1 aSiO
(4-a)/2 (I)
Wherein, the R in the following formula
1Be that the identical or different 1 valency alkyl, a that do not replace or replace is 1.95～2.04 positive number;
(B) the organic azoic foaming agent of 0.5～50 mass parts;
(C) composition formed by following component of 0.1～50 mass parts:
(C-1) 100 mass parts water,
(C-2) 1～1000 mass parts silicon-dioxide; With
(D) be used to make the solidifying agent of A composition solidified significant quantity.
2. rubber composition as claimed in claim 1, wherein said organic azoic foaming agent is 1,1 '-azo two (1-hexahydrobenzoic acid) dimethyl ester.
3. rubber composition as claimed in claim 1, the mean polymerisation degree of wherein said organopolysiloxane is 200～20000.
4. rubber composition as claimed in claim 1, the specific surface area of wherein said silicon-dioxide is 50m
2More than/the g.
5. as each described rubber composition of claim 1～4, wherein with respect to 100 mass parts (A) composition, the consumption of described solidifying agent is 0.1～15 mass parts.
6. rubber composition as claimed in claim 5, it also contains conductive material.
7. the silicon rubber foam that stink is little is characterized in that, makes each described rubber composition foamed solidification of claim 1～6 and forms.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006300122A JP2008115284A (en) | 2006-11-06 | 2006-11-06 | Silicone rubber composition and less smelling silicone rubber sponge using it |
| JP300122/2006 | 2006-11-06 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101177529A true CN101177529A (en) | 2008-05-14 |
Family
ID=39403964
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007101657449A Pending CN101177529A (en) | 2006-11-06 | 2007-11-06 | Silicone rubber composition and little-odour silicone rubber sponge using the same |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2008115284A (en) |
| KR (1) | KR20080041115A (en) |
| CN (1) | CN101177529A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI613257B (en) * | 2013-03-06 | 2018-02-01 | 信越化學工業股份有限公司 | Foaming polyoxymethylene rubber composition and polyoxyethylene rubber sponge |
| CN110157194A (en) * | 2019-04-25 | 2019-08-23 | 江门市蓬江区荷塘伟润橡胶有限公司 | A kind of dish-washing machine silicone sponge glue sizing sealing ring formula and preparation method thereof |
| CN115417790A (en) * | 2022-10-09 | 2022-12-02 | 山东大学 | Novel azo foaming agent and synthesis method thereof |
-
2006
- 2006-11-06 JP JP2006300122A patent/JP2008115284A/en not_active Withdrawn
-
2007
- 2007-11-05 KR KR1020070111872A patent/KR20080041115A/en not_active Application Discontinuation
- 2007-11-06 CN CNA2007101657449A patent/CN101177529A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI613257B (en) * | 2013-03-06 | 2018-02-01 | 信越化學工業股份有限公司 | Foaming polyoxymethylene rubber composition and polyoxyethylene rubber sponge |
| CN110157194A (en) * | 2019-04-25 | 2019-08-23 | 江门市蓬江区荷塘伟润橡胶有限公司 | A kind of dish-washing machine silicone sponge glue sizing sealing ring formula and preparation method thereof |
| CN115417790A (en) * | 2022-10-09 | 2022-12-02 | 山东大学 | Novel azo foaming agent and synthesis method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2008115284A (en) | 2008-05-22 |
| KR20080041115A (en) | 2008-05-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101880462B (en) | Silicon rubber sponge, its manufacture and image forming roller thereof | |
| TWI414549B (en) | High foam ratio of silicone rubber sponge | |
| US20080214688A1 (en) | Silicone rubber sponge composition | |
| CN102174260B (en) | Silicone rubber sponge composition and silicone rubber sponge | |
| JP4762781B2 (en) | Conductive silicone rubber composition and conductive silicone rubber sponge | |
| CN104031391A (en) | Foam silicone rubber composite and silicone rubber sponge | |
| JPH0563496B2 (en) | ||
| CN1775864B (en) | Silicon rubber composition for sponge | |
| CN101177529A (en) | Silicone rubber composition and little-odour silicone rubber sponge using the same | |
| JP4920399B2 (en) | Silicone rubber foam composition having open cells and silicone rubber foam | |
| JP4704954B2 (en) | Conductive silicone rubber composition and conductive silicone rubber sponge | |
| US6387971B1 (en) | Silicone rubber sponge composition and silicone rubber sponge obtained therefrom | |
| US6359026B1 (en) | Method for producing silicone foams | |
| JP3121773B2 (en) | Silicone rubber composition for sponge | |
| JP2001240712A (en) | Rubber composition | |
| JP3419279B2 (en) | Silicone rubber sponge composition | |
| JP4168219B2 (en) | Rubber composition for rubber roll and rubber roll | |
| JP3198847B2 (en) | Manufacturing method of semiconductive roll | |
| JP3611025B2 (en) | Silicone rubber composition | |
| JP3528595B2 (en) | Silicone rubber sponge composition | |
| JP3487200B2 (en) | Silicone rubber sponge composition | |
| JP4766244B2 (en) | Conductive silicone rubber composition and conductive silicone rubber sponge | |
| JP3644486B2 (en) | Silicone rubber sponge composition | |
| JPH0563497B2 (en) | ||
| JPH08217978A (en) | Production of nonfoamed silicone rubber molding |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20080514 |