CN1651517A - Room temp solidified organic polysiloxane composition - Google Patents
Room temp solidified organic polysiloxane composition Download PDFInfo
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- CN1651517A CN1651517A CNA2005100079620A CN200510007962A CN1651517A CN 1651517 A CN1651517 A CN 1651517A CN A2005100079620 A CNA2005100079620 A CN A2005100079620A CN 200510007962 A CN200510007962 A CN 200510007962A CN 1651517 A CN1651517 A CN 1651517A
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
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- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
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- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
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- 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
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Abstract
The invention relates to an organic polysiloxane composition cured at room temperature, which comprises (A) organic polysiloxane in the formula (1) and/or (2), (B) colloidal calcium carbonate, (C) heavy calcium carbonate, (D) alkoxy silane compound, the partial hydrolysate or the mixture, (E) organic oxygen-based titanium in the formula (4) and (F) silane coupling agent. The organic polysiloxane composition cured at room temperature of the organic polysiloxane composition has the advantages of good storage stability and resin adhesiveness, less stink (especially odor of silane) and no discomfort during use. (R is Me or Et; R <1> is an one-valence alkyl; X is an integer of 10 or larger than 10; Y is an alkylidene, N is 0 or 1, R <2> is a branched chain in the formula (3)), (R <3> is a tert-alkyl, R <4> is a radical without tertiary carbon, a is an integer from 0 to 2.).
Description
Technical field
The present invention relates to normal temperature cured organic polysiloxane composition, especially relate to storage stability, resin adhesiveness is good and the obvious few normal temperature cured organic polysiloxane composition of foul smell (especially silane foul smell).
Background technology
In the past, as everyone knows kind type is arranged by contact the normal temperature cured organic polysiloxane composition that at room temperature is cured with airborne moisture.So but wherein emit alcohol be cured type organopolysiloxane composition because not corroding metal mainly the sealing of electric/electronic device etc. with, adhesion with, coating with in use.As the typical example of this pure type, can enumerate special public clear 39-27643 communique (patent documentation 1), this communique discloses the composition of being made up of hydroxy-end capped organopolysiloxane and organoalkoxysilane and organic titanic compound.In addition, the spy opens clear 55-43119 communique (patent documentation 2) and discloses the composition that alkoxysilyl end-sealed type organopolysiloxane and organoalkoxysilane and titan-alkoxide are formed.Recently, special fair 7-39547 communique (patent documentation 3) discloses the good composition of storage stability under the relevant sealed state, and the spy opens the disclosing of composition that the adhesion good endurance is arranged in the flat 11-338090 communique (patent documentation 4) in addition.
[patent documentation 1] special public clear 39-27643 communique
[patent documentation 2] spy opens clear 55-43119 communique
[patent documentation 3] special fair 7-39547 communique
[patent documentation 4] spy opens flat 11-338090 communique
Summary of the invention
[problem that invention will solve]
Yet, special public clear 39-27643 communique (patent documentation 1), spy open clear 55-43119 communique (patent documentation 2) and have problems aspect storage stability, Te Kaiping 7-39547 communique (patent documentation 3), spy open flat 11-338090 communique (patent documentation 4) and have problems aspect resin adhesiveness, confirm to have the unhappy stink of silane foul smell when using lower boiling organoalkoxysilane.
The present invention seeks to eliminate aforesaid shortcoming, provide storage stability, resin adhesiveness good, and foul smell (especially silane is smelly) is few, do not have the normal temperature cured organic polysiloxane composition of discomfort in the use.
[solving the method that problem is used]
The result that present inventors study with great concentration in order to achieve the above object, by using the organopolysiloxane of following general formula (1) and/or (2) expression, use the calcene on fatty acid treatment surface, use the water-ground limestone of paraffin series treatment agent treat surface, on average have in 1 molecule more than 2 or 2 and the water-disintegrable base of Siliciumatom bonded, and the boiling point under the normal pressure is alkoxysilane compound containing trialkylsilyl group in molecular structure and/or its partial hydrolystate more than 150 ℃ or 150 ℃, intramolecularly has organic oxygen base titanium of 2 tertiary carbon atoms and the organic oxygen base of hydrogen atom bonded at least, has reached this purpose.
Therefore, the object of the invention provides following (A)～(F) for must composition, storage stability, resin adhesiveness be good, and the obvious few normal temperature cured organic polysiloxane composition of foul smell (especially silane is smelly):
(A) organopolysiloxane 100 mass parts of the organopolysiloxane of following general formula (1) expression and/or following general formula (2) expression
[changing 1]
(in the formula, R is methyl or ethyl, R
1Be C
1～10Replacement or the monovalence alkyl of non-replacement, X is the integer more than 10 or 10.Y is C
1～5Alkylidene group, N is 0 or 1 integer independently)
[changing 2]
(in the formula, R, R
1, X, Y, N as mentioned above.And R
2It is the side chain that contains the water-disintegrable base shown in the following general formula (3).)
[changing 3]
(in the formula, R, R
1, Y, N as mentioned above.)
(B) calcene 50～150 mass parts on use fatty acid treatment surface
(C) water-ground limestone 10～50 mass parts of use paraffin series treatment agent treat surface
(D) on average have in 1 molecule more than 2 or 2 and the water-disintegrable base of Siliciumatom bonded, and the boiling point under the normal pressure is the alkoxysilane compound containing trialkylsilyl group in molecular structure more than 150 ℃ or 150 ℃, its partial hydrolystate or these mixture 0.1～20 mass parts
(E) organic oxygen base titanium 1～15 mass parts of following general formula (4) expression
[changing 4]
(R
4O)
aTi(OR
3)
4-a?????????????????(4)
(in the formula, R
3Be with Sauerstoffatom bonded carbon atom be the C of tertiary carbon
4～10The tertiary hydrocarbon base, R
4Be C
1～10Replacement or the monovalence alkyl of non-replacement, but do not have tertiary carbon atom.A is 0～2 integer.)
(F) silane coupling agent 0～10 mass parts
The effect of invention
Can provide storage stability, resin adhesiveness good according to the present invention, and foul smell (especially silane is smelly) is few, does not have the normal temperature cured organic polysiloxane composition of discomfort in the use.
The preferred plan that carries out an invention
(A) composition that uses among the present invention is the composition that becomes the base polymer of this composition, in order to obtain storage stability, must be the organopolysiloxane of following general formula (1) expression and/or the organopolysiloxane of following general formula (2) expression:
[changing 5]
In the formula, R is methyl or ethyl, R
1Be C
1～10Replacement or the monovalence alkyl of non-replacement, X is the integer more than 10 or 10.Y is C
1～5Alkylidene group, N is 0 or 1 integer independently.)
[changing 6]
(in the formula, R, R
1, X, Y, N as mentioned above.In addition, R
2Be contain below shown in the following general formula of usefulness (3) shown in the side chain of water-disintegrable base.)
[changing 7]
(in the formula, R, R
1, Y, N as mentioned above.)
As the desired viscosity of (A) composition, under 25 ℃ condition, be 100～1,000,000mPas.This viscosity might can not be given excellent physicals, especially flexibility and high elongation to the elastomerics after solidifying during less than 100mPas, and greater than 1,000, during 000mmPas.The viscosity increased of composition, extrudability might the reduction significantly during construction.Therefore, be more preferably 5,000～100,000mPas.And this viscosity is to use the value of rotary viscosity design determining.
In above-mentioned general formula (1), (2), R is methyl or ethyl, preferable methyl.R
1Be C
1～10, preferred C
1～6Replacement or the univalent alkyl of non-replacement, for example, can enumerate the base that the cycloalkyl such as alkyl, cyclohexyl of methyl, ethyl, propyl group etc. and these basic hydrogen bonds are partly replaced by halogen atom etc., for example 3,3,3-trifluoro propyl etc., preferable methyl, ethyl, propyl group, phenyl, 3,3,3-trifluoro propyl, most preferable.A plurality of R in above-mentioned general formula (1), (2)
1Can be identical base, also can be different types of base.
In addition, Y is C
1～5Alkylidene group, can enumerate methylene radical, ethylidene, propylidene, butylidene etc. as alkylidene group, preferred ethylidene.
Also knowing Y is the polymkeric substance of Sauerstoffatom, but keeping quality is insufficient when Y is Sauerstoffatom among the present invention.
Use fatty acid treatment the calcene on the present invention (B) composition surface of using, use the water-ground limestone on (C) composition surface that the paraffin series treatment agent handled, be to give this composition storage stability, the necessary composition that resin adhesiveness and appropriate rubber rerum natura are used is also given in good operation simultaneously.
Here, as the reason of also using (B), (C) composition, be because be difficult to obtain for being referred to as awkward bonding resin clung body (PPS during only with (B) composition, acrylic resin etc.) good tackiness, (C) composition by adding requirement is good to the tackiness of these difficult adhering resin adherends, can obtain the cause of appropriate operation, and the obvious variation of resin adhesiveness not only when only using (C) composition, and the drippage of composition, the operation variation.
(B) fatty acid treatment must be used in the surface of composition, and the calcene that uses other treatment agents (resinous acid etc.) to handle, or the surface the composition of the calcene of not handling is all inferior to the tackiness of difficult adhering resin and operation etc.In addition, (C) composition must use the paraffin series treat surface, the water-ground limestone that uses other treatment agents (lipid acid, resinous acid etc.) to handle, or the surface the composition of the water-ground limestone of not handling all inferior to the tackiness and the operation of difficult adhering resin.
This occasion, as the calcene of (B) composition, the median size that the assay method of use electron microscope records is 0.01～0.1 μ m preferably, most preferably is 0.03～0.06 μ m.In addition, the air penetrant method specific surface area of calcene preferably is equal to or greater than 3m
2/ g most preferably is 4～7m
2/ g.As the lipid acid of handling this calcene, can enumerate C
10～20, C most preferably
12-18Lipid acid, also can be mixed fatty acid.Lipid acid can be that saturated fatty acid also can be a unsaturated fatty acids, but preferred saturated fatty acid.Can enumerate oleic acid, palmitinic acid, stearic acid etc. particularly, can use these more than a kind or 2 kinds or 2 kinds.Its treatment capacity most preferably is 2.0～4.0 quality % with respect to preferred 0.5～5 quality % of lime carbonate.
On the other hand, as the water-ground limestone of (C) composition, the median size that the assay method of employing electron microscope records is 0.5～3.0 μ m, most preferably be 0.7～2.5 μ m, and the air penetrant method specific surface area of water-ground limestone is 0.5～2.5m
2/ g most preferably is 0.8～2.0m
2/ g.As the paraffin series treatment agent of handling water-ground limestone, so long as a straight chain shape or a chain paraffin then do not have particular restriction, preferred C
20～30Paraffin, preferably use these more than a kind or 2 kinds or 2 kinds.This treatment capacity is 0.1～5 quality % with respect to lime carbonate, most preferably is 1.0～2.5 quality %.
Moreover the surface treatment of above-mentioned lime carbonate can adopt known method to carry out.
(B), (C) composition can use pretreated lime carbonate, can also when making this composition, handle.In order to improve the storage stability of this composition significantly, importantly do not make surface treatment agent in fact, by product during processing and catalyzer etc. remain in this composition.Therefore the pretreated lime carbonate of preferred use.
(B) addition of composition is 50～150 mass parts with respect to (A) composition 100 mass parts usually, preferably 70～120 mass parts.Resin adhesiveness viscosity inferior and composition rises when too many, mix and extrudability poor during construction, and the rubber poor properties after solidifying very little the time.
(C) addition of composition is 10～50 mass parts with respect to (A) composition 100 mass parts usually, preferably 15～35 mass parts.Resin adhesiveness and rubber rerum natura reduce when too many, mix and extrudability poor during construction, and the tackiness to difficult adhering resin clung body reduce very little the time.
(D) composition among the present invention, be on average to have more than 2 or 2 in 1 molecule, preferably have more than 3 or 3 and the water-disintegrable base of Siliciumatom bonded (alkoxyl group), and the boiling point under the normal pressure is alkoxysilane compound containing trialkylsilyl group in molecular structure and/or its partial hydrolystate more than 150 ℃ or 150 ℃.Beyond the water-disintegrable base with remaining base of Siliciumatom bonded so long as C
1～10The monovalence alkyl then do not have particular restriction, the aryl etc. of the alkenyl, phenyl etc. of the alkyl, vinyl etc. of methyl, ethyl, propyl group etc. can illustratively be arranged particularly, then be to have boiling point person more than 150 ℃ or 150 ℃ under the normal pressure as the condition that satisfies.Methyltrimethoxy silane (b.p.102 ℃), Union carbide A-162 (b.p.143 ℃), the boiling point of vinyltrimethoxy silane (b.p.123 ℃) and so on is less than 150 ℃ residual sometimes intensive foul smell.
As the concrete example of (D) composition, can enumerate 4 functional alkoxysilanes classes such as tetraethoxysilane, methyl Cellosolve ortho-silicate, ethyl triethoxysilane (b.p.160 ℃), vinyl three ethoxy silane (b.p.158 ℃), normal-butyl Trimethoxy silane (b.p.164.8 ℃), propyl trimethoxy silicane, phenyltrimethoxysila,e (b.p.130 ℃/45mmHg), 3 functional alkoxysilanes classes such as butyl trimethoxy silane and partial hydrolysis condenses thereof etc.If even above-mentioned boiling point less than 150 ℃ silane but the dipolymer or the trimer of hydrolytic condensation then also can use.These can use separately, also can mix use more than 2 kinds or 2 kinds.In addition, in order to give low modulus, also can additionally add 2 functional alkoxysilanes classes of dimethoxydiphenylsilane etc. to the rubber elastomer after solidifying.
(D) use level of composition, can be with respect to (A) composition 100 mass parts in the scope of 0.1～20 mass parts, preferably use in the scope of 1～10 mass parts, can not obtain crosslinked fully during less than 0.1 mass parts, rare to composition with desired caoutchouc elasticity, and the cured article mechanicalness that obtains when surpassing 20 mass parts reduces, and the foul smell of composition worsens.
(E) composition that uses among the present invention is to solidify the catalyzer that this composition is used, and is to have 2 organic oxygen base titaniums with Sauerstoffatom bonded tertiary carbon atom shown in the following general formula (4) at least:
[changing 8]
(R
4O)
aTi(OR
3)
4-a??????????????????(4)
(in the formula, R
3Be with Sauerstoffatom bonded carbon atom be the C of tertiary carbon
4～10Tertiary hydrocarbon base, R
4Be C
1～10Replacement or the monovalence alkyl of non-replacement, but do not have tertiary carbon atom.A is 0～2 integer).R
4As C
1～10The monovalence alkyl, be the monovalence alkyl that does not have the tertiary carbon alkyl, the alkyl of straight chain shape or 1 side chain is most preferably arranged, can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl etc., preferred C
1～4Alkyl.R
3Be C
4～10The tertiary carbon alkyl, the preferred tertiary butyl.As the concrete example of above-mentioned organic oxygen base titanium, can enumerate four tert.-butoxy titaniums, isopropoxy-three tert.-butoxy titanium, butoxy-three tert.-butoxy titanium, diisopropoxy-three tert.-butoxy titanium etc.
(E) addition of composition is scopes of 1～15 mass parts with respect to (A) composition 100 mass parts, preferably the scope of 3～10 mass parts.Addition can not obtain good storage stability after a little while, and this composition makes the time lengthening of cured article.Otherwise surface cure is too fast when too many, or the deep solidified nature is poor, and storage stability is poor.
(F) silane coupling agent of composition is to have in the normal temperature cured organic polysiloxane composition of the present invention as giving the composition of the effect of tackiness composition.Can suitably use known compound as silane coupling agent; can enumerate (methyl) acryl silane coupling agent; epoxy silane coupling agent; amino silicane coupling agent; mercaptosilane coupling agents etc.; can enumerate γ-methacryloxypropyl trimethoxy silane particularly; β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane; γ-glycidoxypropyltrime,hoxysilane; γ-glycidoxy Union carbide A-162; N-β-(amino-ethyl) gamma-amino propyl trimethoxy silicane; γ-An Jibingjisanyiyangjiguiwan; γ-Qiu Jibingjisanjiayangjiguiwan etc.
The use level of this silane coupling agent, per 100 mass parts (A) composition uses 0～10 mass parts, preferably uses 0.1～5 mass parts.Utilize weighting agent and clung body not to use silane coupling agent to carry out also can not using silane coupling agent when bonding, if the occasion of use is unfavorable on price when surpassing 10 mass parts.
In addition, in the normal temperature cured organic polysiloxane composition of the present invention, cooperate (G) non-reacted silicone oil, preferably cooperate the two terminal end capped polydimethylsiloxanes of trimethyl silyl that use.By cooperating this composition to improve operation, broken end property etc. can also be regulated the rubber rerum natura after the curing simultaneously.
This viscosity (25 ℃) is preferred 5～50, and 000mPas most preferably is 50～5,000mPas, and use level is 0～100 mass parts with respect to (A) composition 100 mass parts, most preferably is 5～80 mass parts.
Normal temperature cured organic polysiloxane composition of the present invention, except aforesaid (A)～(F) composition, in order to improve the flow characteristics before solidifying, give necessary mechanical property to the rubber-like elastic body after solidifying, can also add little powdered inorganic filler as required.As inorganic filler, can enumerate quartz micropowder end, smog matter silicon-dioxide, settleability silicon-dioxide, smog matter titanium dioxide, diatomite, aluminium hydroxide, finely particulate aluminium sesquioxide, magnesium oxide, zinc oxide, zinc carbonate and these are carried out surface-treated weighting agent etc. with silicane, silazane class, low polymerization degree type siloxane, organic compound etc.
In addition, normal temperature cured organic polysiloxane composition of the present invention can also add organic solvent, mould inhibitor, fire retardant, heat-resistant agent, softening agent, thixotropy imparting agent, adhesion promoters, curing catalyst, pigment etc.
Normal temperature cured organic polysiloxane composition of the present invention by (A)～(F) composition and as required various additives, mixes under the state of moisture-barrier and makes.The composition that makes directly is kept in the encloses container, is solidified into rubber-like elastic body by being exposed under the airborne moisture during use.Can be used as so-called single package-type normal temperature cured organic polysiloxane composition uses.
Normal temperature cured organic polysiloxane composition of the present invention is applicable to packaged material, the tackiness agent or damp proof with the coating agent of coating agent, fibre product, glasswork, metal products, plastics etc. or the purposes of tackiness agent as sealing material for building, electric and electronic device.
This occasion, normal temperature cured organic polysiloxane composition of the present invention, can be used for effectively and difficult tackiness resin, for example acrylic resin, polycarbonate resin, polybutylene terephthalate (PBT) resin, polystyrene, ABS resin, polyvinyl chloride (PVC) RESINS etc. is bonding.
[embodiment]
Below enumerate synthesis example, and embodiment and comparative example, specifically describe the present invention, but the present invention is not limited by following embodiment.Moreover " part " expression mass parts, viscosity are the measured values of the assay method of the rotational viscosimeter under expression is used 25 ℃ in the following example.
[synthesis example 1]
In the there-necked flask of 2 liters of the internal volumes that has thermometer, stirrer, water cooler, adding viscosity is 30, the α of 000mPas, ω-dimethyl vinyl-dimethyl polysiloxane 2,500g and toluene 400g, Trimethoxy silane 11.9g and as 50% Platinic chloride toluene solution 1.0g of catalyzer, mixed at room temperature is 9 hours under nitrogen gas stream.Then 10mmHg decompression under be heated to 100 ℃, the distillation remove thinner toluene and remaining Trimethoxy silane, obtain viscosity 40,000mPas, the colourless transparent liquid 2 of nonvolatile component 99.9%, 350g.In tackify immediately not after 100: 1 ratios (mass ratio) metatitanic acid orthocarbonate and the resulting liquid mixing, 1 day after fixing.Can confirm thus that on the vinyl of polymer ends addition has methyltrimethoxy silane.This polymkeric substance as polymer A.
[synthesis example 2]
In the there-necked flask of 2 liters of the internal volumes that has thermometer, stirrer, water cooler, add viscosity 30, the α that 2 vinyl are arranged on the side chain of 000mPas, ω-dimethyl vinyl-dimethyl based polysiloxane 2,500g and toluene 400g, Trimethoxy silane 15g and as 50% Platinic chloride toluene solution 1.0g of catalyzer, at N
2Mixed at room temperature is 9 hours under the air-flow.Be heated to 100 ℃ then under the decompression of 10mmHg, the toluene and the remaining Trimethoxy silane of dilution are removed in distillation, obtain viscosity 52,000mPas, the colourless transparent liquid 2 of nonvolatile component 99.9%, 250g.Behind the tetrabutyl titanate and resulting liquid mixing in 100: 1 ratios (mass ratio).Tackify immediately not, 1 day after fixing.Can confirm thus on the vinyl contained in polymkeric substance that addition has methyltrimethoxy silane.This polymkeric substance as polymer B.
[embodiment 1]
45 parts of 100 parts of end capped polydimethylsiloxanes of two terminal methyl group with viscosity 100mPa.S of polymer A, carry out surface-treated calcene (カ one レ ッ Network ス 300 with lipid acid, ball tail calcium corporate system) 90 part, water-ground limestone (MC コ one ト P-10 with the paraffin surface processing, ball tail calcium corporate system) 30 parts are mixed equably, then, under moisture-barrier, and to wherein mix phenyltrimethoxysila,e (b.p.130 ℃/45mmHg) 9 parts of 9 parts and four-tert.-butoxy titaniums prepare composition until being mixed into even shape.
[embodiment 2]
45 parts of the two terminal methyl group end-blocking polydimethylsiloxanes of 100 parts of polymer B and viscosity 100mPas, with lipid acid surface-treated calcene (カ one レ ッ Network ス 300, ball tail calcium corporate system) 90 part, water-ground limestone (MC コ one ト P-10 with the paraffin surface processing, ball tail calcium corporate system) 30 parts are mixed equably, prepare composition to wherein mixing 9 parts of 9 parts of phenyltrimethoxysila,e and four-tert.-butoxy titaniums until becoming even shape then under moisture-barrier.
[embodiment 3]
45 parts of the two terminal methyl group end-blocking polydimethylsiloxanes of 100 parts of polymer A and viscosity 100mPas, with lipid acid surface-treated calcene (カ one レ ッ Network ス 300, ball tail calcium corporate system) 90 part, water-ground limestone (MC コ one ト P-10 with the paraffin surface processing, ball tail calcium corporate system) 30 parts are mixed equably, prepare composition to wherein mixing 9 parts of 9 parts of phenyltrimethoxysila,e and isopropoxy three tert.-butoxy titaniums until becoming even shape then under moisture-barrier.
[embodiment 4]
45 parts of 100 parts of end capped polydimethylsiloxanes of two terminal methyl group with viscosity 100mPas of polymer A, with lipid acid surface-treated calcene (カ one レ ッ Network ス 300, ball tail calcium corporate system) 90 part, water-ground limestone (MC コ one ト P-10 with the paraffin surface processing, ball tail calcium corporate system) 30 parts are mixed equably, prepare composition to wherein mixing 9 parts of 9 parts of phenyltrimethoxysila,e and diisopropoxy two tert.-butoxy titaniums until becoming even shape then under moisture-barrier.
[comparative example 1]
Among the embodiment 1, substitute with the lipid acid surface-treated calcene except using with the acid-treated calcene of resin (MT-100. ball tail calcium corporate system), other adopt method similarly to Example 1 to prepare composition.
[comparative example 2]
Among the embodiment 1, except using with beyond the alternative water-ground limestone with the paraffin surface processing of the water-ground limestone (ス ノ ラ ィ ト, ball tail calcium corporate system) of fatty acid treatment, other adopt method similarly to Example 1 to prepare composition.
[comparative example 3]
Among the embodiment 1, substitute the phenyltrimethoxysila,e except using methyltrimethoxy silane (b.p.102 ℃), other adopt method similarly to Example 1 to prepare composition.
[comparative example 4]
Among the embodiment 1, except using the alternative four tert.-butoxy titaniums of tetraisopropoxy titanium, other adopt method similarly to Example 1 to prepare composition.
These embodiment, the composition of comparative example carry out moulding and make the thick sheet of 2mm, at 23 ± 2 ℃, solidify after 7 days under the ambiance of 50 ± 5%RH, measure its rubber rerum natura (hardness, elongation, tensile strength) according to JIS K6249.At this moment, confirm whether to smell the foul smell of composition and whether feel offending atmosphere.Side by side the composition that makes is coated on the thick resin clung body of 25 * 100 * 2mm in addition, at room temperature place become rubber elastomer after, the tackiness of the cured article Visual Confirmation clung body that obtains by stretching.Here the resin clung body is selected for use than the rigid polyvinyl chloride resin, polystyrene, polycarbonate, the propylene ester resin that are easier to as structure material.Storage stability test adopts the mode of wound packages uncured composition to heat in 70 ℃ drying machine, then at 23 ± 2 ℃, solidifies 7 days under the ambiance of 50 ± 5%RH, similarly carries out rubber rerum natura and adhesive mensuration with the composition at initial stage.The table 1 that the results are shown in of embodiment 1～4, the table 2 that the results are shown in of embodiment 1 and comparative example.
Table 1
| Umber | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Polymkeric substance | 100 | ????A | ????B | ????A | ????A |
| Thinner | 45 | Two terminal methyl group end-blocking polydimethylsiloxanes | Two terminal methyl group end-blocking polydimethylsiloxanes | Two terminal methyl group end-blocking polydimethylsiloxanes | Two terminal methyl group end-blocking polydimethylsiloxanes |
| Calcene (treatment agent) | 90 | (lipid acid) | (lipid acid) | (lipid acid) | (lipid acid) |
| Water-ground limestone (treatment agent) | 30 | (paraffin) | (paraffin) | (paraffin) | (paraffin) |
| Linking agent | 9 | Phenyltrimethoxysila,e | Phenyltrimethoxysila,e | Phenyltrimethoxysila,e | Phenyltrimethoxysila,e |
| Catalyzer | 9 | Four tert.-butoxy titaniums | Four tert.-butoxy titaniums | Isopropoxy three tert.-butoxy titaniums | Diisopropoxy two tert.-butoxy titaniums |
| Initial stage rerum natura (unit) | |||||
| The not sticking time | Minute | ????3 | ????2 | ????3 | ????3 |
| Hardness | Duro. A | ????33 | ????36 | ????34 | ????33 |
| Elongation at break | ％ | ????500 | ????400 | ????520 | ????500 |
| Tensile strength | MPa | ????1.60 | ????1.80 | ????1.55 | ????1.70 |
| Resin adhesiveness * | |||||
| Hard vinyl chloride resin | ????○ | ????○ | ????○ | ????○ | |
| Polystyrene | ????○ | ????○ | ????○ | ????○ | |
| Polycarbonate | ????○ | ????○ | ????○ | ????○ | |
| Acrylic resin | ????○ | ????○ | ????○ | ????○ | |
| Foul smell *2 | ????○ | ????○ | ????○ | ????○ | |
| Preserve back rerum natura (unit) | |||||
| The not sticking time | Minute | ????4 | ????2 | ????4 | ????4 |
| Hardness | Duro. A | ????30 | ????35 | ????32 | ????30 |
| Elongation at break | ％ | ????590 | ????420 | ????600 | ????620 |
| Tensile strength | MPa | ????1.55 | ????1.60 | ????1.62 | ????1.52 |
* 1 resin adhesiveness; Zero: good.△: part is peeled off.*: can not
* 2 foul smell; Zero: good.*: unhappiness
Table 2
| Umber | Embodiment 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Polymkeric substance | ??100 | ????A | ????A | ????A | ????A | ????A |
| Thinner | ??45 | Two terminal methyl group end-blocking polydimethylsiloxanes | Two terminal methyl group end-blocking polydimethylsiloxanes | Two terminal methyl group end-blocking polydimethylsiloxanes | Two terminal methyl group end-blocking polydimethylsiloxanes | Two terminal methyl group end-blocking polydimethylsiloxanes |
| Calcene (treatment agent) | ??90 | (lipid acid) | (resinous acid) | (lipid acid) | (lipid acid) | (lipid acid) |
| Water-ground limestone (treatment agent) | ??30 | (paraffin) | (paraffin) | (lipid acid) | (paraffin) | (paraffin) |
| Linking agent | ??8 | Phenyltrimethoxysila,e | Phenyltrimethoxysila,e | Phenyltrimethoxysila,e | Methyltrimethoxy silane | Phenyltrimethoxysila,e |
| Catalyzer | ??4 | Four tert.-butoxy titaniums | Four tert.-butoxy titaniums | Four tert.-butoxy titaniums | Four tert.-butoxy titaniums | Tetraisopropoxy titanium |
| Initial stage rerum natura (unit) | ||||||
| The not sticking time | Minute | ????3 | ????4 | ????3 | ????6 | ????8 |
| Hardness | ??Duro. ??A | ????33 | ????36 | ????36 | ????38 | ????30 |
| Elongation at break | ??％ | ????500 | ????520 | ????600 | ????520 | ????720 |
| Tensile strength | ??MPa | ????1.60 | ????1.65 | ????1.50 | ????1.60 | ????1.60 |
| Resin adhesiveness *1 | ||||||
| Hard vinyl chloride resin | ????○ | ????○ | ????○ | ????○ | ????△ | |
| Polystyrene | ????○ | ????× | ????× | ????○ | ????○ | |
| Polycarbonate | ????○ | ????○ | ????○ | ????○ | ????△ | |
| Acrylic resin | ????○ | ????× | ????× | ????○ | ????○ | |
| Foul smell *2 | ????○ | ????○ | ????○ | ????× | ????× | |
| Initial stage rerum natura (unit) | ||||||
| The not sticking time | Minute | ????4 | ????8 | ????5 | ????10 | Uncured |
| Hardness | ??Duro. ??A | ????30 | ????26 | ????30 | ????30 | Uncured |
| Elongation at break | ??％ | ????590 | ????720 | ????620 | ????550 | Uncured |
| Tensile strength | ??MPa | ????1.55 | ????1.40 | ????1.60 | ????1.70 | Uncured |
* 1 resin adhesiveness; Zero: good.△: part is peeled off.*: can not
* 2 foul smell; Zero: good.*: unhappiness
Claims (3)
1. normal temperature cured organic polysiloxane composition is characterized in that, with following (A)～(F) as must composition:
(A) organopolysiloxane of following general formula (1) expression and/or following general formula (2) expression is organic poly-
Siloxanes 100 mass parts
[changing 1]
(in the formula, R is methyl or ethyl, R
1Be C
1～10Replacement or the monovalence alkyl of non-replacement, X is the integer more than 10 or 10, Y is C
1～5Alkylidene group, N is 0 or 1 integer independently)
[changing 2]
(in the formula, R, R
1, X, Y, N as mentioned above, and R
2Be the side chain that contains the water-disintegrable base shown in the following general formula (3))
[changing 3]
(in the formula, R, R
1, Y, N as mentioned above),
(B) surface calcene 50～150 mass parts of fatty acid treatment,
(C) surface water-ground limestone 10～50 mass parts that the paraffin series treatment agent is handled,
(D) on average have in 1 molecule more than 2 or 2 and the water-disintegrable base of Siliciumatom bonded, and the boiling point under the normal pressure be more than 150 ℃ or 150 ℃ alkoxysilane compound containing trialkylsilyl group in molecular structure, its partial hydrolystate or
These mixture 0.1～20 mass parts,
(E) organic oxygen base titanium 1～15 mass parts of following general formula (4) expression
[changing 4]
(R
4O)
aTi(OR
3)
4-a??????????????????(4)
(in the formula, R
3Be with Sauerstoffatom bonded carbon atom be the C of tertiary carbon
4～10The tertiary hydrocarbon base, R
4Be C
1～10Replacement or the monovalence alkyl of non-replacement, but do not have tertiary carbon atom, a is 0～2 integer),
(F) silane coupling agent 0～10 mass parts.
2. the described normal temperature cured organic polysiloxane composition of claim 1 is characterized in that, (B) the air penetrant method specific surface area of calcene is 3m
2/ g or 3m
2More than/the g, (C) the air penetrant method specific surface area of water-ground limestone is 0.5～2.5m
2/ g.
3. claim 1 or 2 described normal temperature cured organic polysiloxane compositions is characterized in that, also contain (G) non-reactive silicone oil.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP028990/04 | 2004-02-05 | ||
| JP028990/2004 | 2004-02-05 | ||
| JP2004028990A JP4438937B2 (en) | 2004-02-05 | 2004-02-05 | Room temperature curable organopolysiloxane composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1651517A true CN1651517A (en) | 2005-08-10 |
| CN100368478C CN100368478C (en) | 2008-02-13 |
Family
ID=34879175
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100079620A Expired - Fee Related CN100368478C (en) | 2004-02-05 | 2005-02-04 | Room temp solidified organic polysiloxane composition |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4438937B2 (en) |
| KR (1) | KR101127301B1 (en) |
| CN (1) | CN100368478C (en) |
| TW (1) | TW200535193A (en) |
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| CN101143964B (en) * | 2006-06-05 | 2011-09-07 | 信越化学工业株式会社 | Room temperature-curable organopolysiloxane composition |
| CN101275016B (en) * | 2006-12-11 | 2011-11-30 | 信越化学工业株式会社 | Room temperature curable organopolysiloxane compositions |
| CN101233172B (en) * | 2005-08-25 | 2012-05-23 | 瓦克化学有限公司 | Organopolysiloxanes and method for the production thereof |
| CN101139464B (en) * | 2006-06-05 | 2012-05-30 | 信越化学工业株式会社 | Room temperature-curable organopolysiloxane composition |
| CN109705397A (en) * | 2014-04-25 | 2019-05-03 | 信越化学工业株式会社 | The novel silicon compound and preparation method thereof containing bis- (alkoxysilyl-Asia ethylene) bases |
| CN110982482A (en) * | 2019-12-25 | 2020-04-10 | 广西华纳新材料科技有限公司 | Low-modulus high-elongation silicone sealant with good adhesion and preparation method thereof |
| CN112714784A (en) * | 2018-10-23 | 2021-04-27 | 信越化学工业株式会社 | Heat-conductive silicone composition and cured product thereof |
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| JP4530136B2 (en) * | 2004-04-06 | 2010-08-25 | 信越化学工業株式会社 | Room temperature curable organopolysiloxane composition and method for producing the same |
| JP4466846B2 (en) * | 2004-09-24 | 2010-05-26 | 信越化学工業株式会社 | Room temperature curable organopolysiloxane composition |
| JP5019036B2 (en) * | 2006-04-03 | 2012-09-05 | 信越化学工業株式会社 | Silicone rubber adhesive |
| JP5266788B2 (en) * | 2008-02-25 | 2013-08-21 | 株式会社スリーボンド | Oil surface adhesive room temperature curable organopolysiloxane composition and cured product thereof |
| KR101864504B1 (en) * | 2016-11-11 | 2018-06-29 | 주식회사 케이씨씨 | Organosiloxane compositions |
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| JPH0778158B2 (en) * | 1986-11-04 | 1995-08-23 | 旭有機材工業株式会社 | Powdered phenolic resin composition for binder |
| JP2784045B2 (en) * | 1989-06-15 | 1998-08-06 | 東芝シリコーン株式会社 | Room temperature curable silicone rubber composition |
| JP3176213B2 (en) * | 1994-03-08 | 2001-06-11 | 丸尾カルシウム株式会社 | Modified silicone resin composition having improved storage stability and sealant comprising the same |
| JP3685031B2 (en) * | 1998-04-10 | 2005-08-17 | 丸尾カルシウム株式会社 | Surface treated calcium carbonate filler for synthetic resin, method for producing the same, and resin composition comprising the filler |
| JP4494543B2 (en) * | 1998-11-20 | 2010-06-30 | 東レ・ダウコーニング株式会社 | Room temperature curable silicone rubber composition |
| JP3871824B2 (en) * | 1999-02-03 | 2007-01-24 | キャボットスーパーメタル株式会社 | Tantalum powder for high capacity capacitors |
| JP2001072890A (en) * | 1999-09-06 | 2001-03-21 | Maruo Calcium Co Ltd | Surface-treated calcium carbonate, resin composition for porous film, and production of porous film |
| DE19957336A1 (en) * | 1999-11-29 | 2001-07-12 | Wacker Chemie Gmbh | Crosslinkable organopolysiloxane compositions |
| JP5101762B2 (en) * | 1999-11-29 | 2012-12-19 | 東レ・ダウコーニング株式会社 | Room temperature curable silicone rubber composition |
| JP2002069300A (en) * | 2000-08-31 | 2002-03-08 | Dow Corning Toray Silicone Co Ltd | Vibration-insulating silicon compound |
| JP2003034760A (en) * | 2001-05-18 | 2003-02-07 | Maruo Calcium Co Ltd | Surface-treated calcium carbonate heavy and method for producing the same, and resin composition containing surface-treated calcium carbonate heavy |
| JP2003026954A (en) * | 2001-07-23 | 2003-01-29 | Maruo Calcium Co Ltd | Surface-treated calcium carbonate and sealing composition comprising the same |
| JP3957486B2 (en) * | 2001-10-12 | 2007-08-15 | コニシ株式会社 | Polysulfide curable composition |
| JP2004292724A (en) * | 2003-03-28 | 2004-10-21 | Shin Etsu Chem Co Ltd | Room temperature curable organopolysiloxane composition |
| JP4912754B2 (en) * | 2006-06-05 | 2012-04-11 | 信越化学工業株式会社 | Room temperature curable organopolysiloxane composition |
-
2004
- 2004-02-05 JP JP2004028990A patent/JP4438937B2/en not_active Expired - Fee Related
-
2005
- 2005-02-04 TW TW094103705A patent/TW200535193A/en not_active IP Right Cessation
- 2005-02-04 CN CNB2005100079620A patent/CN100368478C/en not_active Expired - Fee Related
- 2005-02-04 KR KR1020050010327A patent/KR101127301B1/en active IP Right Grant
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| CN112714784B (en) * | 2018-10-23 | 2022-12-27 | 信越化学工业株式会社 | Heat-conductive silicone composition and cured product thereof |
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Also Published As
| Publication number | Publication date |
|---|---|
| KR101127301B1 (en) | 2012-03-30 |
| JP4438937B2 (en) | 2010-03-24 |
| CN100368478C (en) | 2008-02-13 |
| TW200535193A (en) | 2005-11-01 |
| TWI367919B (en) | 2012-07-11 |
| JP2005220215A (en) | 2005-08-18 |
| KR20060041688A (en) | 2006-05-12 |
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