CN103360768B - Double-liquid mixing type organopolysiloxane composition - Google Patents
Double-liquid mixing type organopolysiloxane composition Download PDFInfo
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Abstract
The invention provides a dealcoholized double-liquid mixing type organopolysiloxane composition having moderate usable time and excellent curing properties in deep portions after mixing. The double-liquid mixing type organopolysiloxane composition contains a first composition and a second composition and is solidified by mixing the first and the second compositions. The first composition is a composition that contains the following components: (A) organopolysiloxane, (B) a compound selected from a ketene silyl acetal type compound, a 2-methyl dialkoxy silyl propionate and a partial hydrolysate of the ketene silyl acetal type compound and the 2-methyl dialkoxy silyl propionate, (C) an organic compound and/or a silane compound having more than one nitrogen atom in a molecule, and (D) a silane compound having more than two alkoxies in a molecule and/or partial hydrolytic condensation compound thereof. The second composition is a composition that contains the following components: (E) organopolysiloxane, (F) an organic tin catalyst, and (G) an ester compound.
Description
Technical field
The present invention relates to after mixing have appropriateness up time, and the excellent dealcoholized type of deep curability biliquid
Mixed type organopolysiloxane composition.
Background technology
For the room temperature fast-curing organopolysiloxane composition of condensation cured type, so far, it is known that relative to
Based on polymer two terminal hydroxyl organopolysiloxanes crosslinking agent is reduced to the limit and make hydrolysis produce crosslinking speed
Spend the composition of the one-pack-type for improving and two terminal hydroxyl organopolysiloxanes of polymer and crosslinking agent are distinguished by based on
The composition of the dual liquid type mixed when packing, using.
The above-mentioned composition of one-pack-type is the fast curing rate from surface, because deep solidification needs certain hour, because
This difficulty deserves to be called rapidly-curable.Accordingly, it would be desirable in the case of rapidly-curable, the composition of dual liquid type is effective, but dual liquid type
Above-mentioned composition in, although it is more excellent for deep curability, but due to biliquid mixing ratio be not volume ratio 1：1,
Therefore process complicated, and have the shortcomings that to be difficult to be applied to automatic blender etc..Additionally, in order to fully be cured to deep,
Two terminal hydroxyl amounts of organopolysiloxane and the addition of crosslinking agent must closely be specified, or further added water as depth
Portion's curing agent.
On the other hand, in the organopolysiloxane composition of addition curable, the ratio of biliquid mixing is 1：1, workability
It is excellent, but generally solidification needs heating furnace.Additionally, making curing catalysts be poisoned in the presence of poisonous substance is added, therefore there is work
The shortcoming that industry environment is limited to.
Therefore, No. 3916403 publication of patent（Patent document 1）In, it is proposed that for the water-disintegrable first in strand two ends
The diorganopolysiloxanecompositions of silylation end-blocking contain has at least one carbonyl in 1 molecule（C=O bases）Organic compound and 1
There is at least one primary amino radical in molecule（NH2Base）Organic compound composition.It utilizes to be entered by carbonyl and primary amino radical
The water of capable ketimide reaction of formation by-product, improves deep curability, rapidly-curable, although deep curability, quick solid
The property changed is excellent, but when uncured in the case of heating, the dialkyl group ketoxime as condensation reaction product hastily gasifies,
Bubble is produced in solidfied material, sealing is greatly reduced, particularly there is problem in the oil sealing purposes of automobile.Asked as this
The countermeasure of topic, in No. 3970484 publication of patent（Patent document 2）In, it is proposed that by further limiting solidification in above-mentioned
Agent species, curing dose, so as to produce bubble in suppressing solidfied material.Above-mentioned 2 publications are all for the effective method of oxime type.
In recent years, as the rapid solidification techniques in dealcoholized type, it is proposed that JP 2006-131824 publications and JP
2011-37968 publications（Patent document 3,4）.In JP 2006-131824 publications, it is proposed that by with terminal silane
The polymer of alcohol radical and end have the composition that the condensation reaction of the polymer of alkoxyalkyl improves deep curability.But
It is, although workability is good, but due to until composition solidification is, it is necessary to about 1 day, therefore exists to be transferred to next operation
Need the rough sledding of time.Proposed in JP 2011-37968 publications by by 2- trialkoxysilyl propionic esters
It is mixed with the composition that there is silanol group or their partial hydrolystate is added in the composition that there's almost no silanol group
Close, so as to improve the composition of curability by leaps and bounds.Although said composition rapidly-curable is improved by leaps and bounds really, due to mixed
Solidification after conjunction is too fast, thus have that the bonding up time is short, paste base material after position can not the rough sledding such as micro-adjustment.Cause
This, it is desirable to there is usable time and the excellent composition of deep curability of appropriateness after mixing.
Prior art literature
Patent document
Patent document 1：No. 3916403 publication of patent
Patent document 2：No. 3970484 publication of patent
Patent document 3：JP 2006-131824 publications
Patent document 4：JP 2011-37968 publications
The content of the invention
The invention problem to be solved
The present invention in view of above-mentioned actual conditions and complete, its object is to provide have after mixing appropriateness it is usable when
Between and the excellent dealcoholized type of deep curability biliquid mixed type organopolysiloxane composition.
Means for solving the problems
The present inventor furthers investigate repeatedly to achieve these goals, as a result finds, by will be by following formulas（6）It is shown
Ester compounds, intramolecular have at least one nitrogen-atoms organic compound and/or silane compound mix, carry out ketimide
Reaction of formation.The usable time for carrying out speed appropriateness of the reaction is successfully found, thus, it is possible to suppress JP 2011-
Curing reaction drastically in No. 37968 publications, and water using by-product improves deep curability, completes the present invention.
R6COCH2COOR6（6）
（In formula, R6It is the alkyl of carbon number 1~5, R6Can be with mutually the same, or different group.）
Therefore, the present invention provides following shown biliquid mixed type organopolysiloxane compositions.
[1] biliquid mixed type organopolysiloxane composition, it is characterised in that comprising following the 1st shown compositions and
2nd composition, is solidified by the way that the 1st composition and the 2nd composition are mixed.
1st composition, is the composition containing following component：
（A）By following formulas（1）The mass parts of organopolysiloxane 50~190 of expression,
HO（SiR1 2O）nH （1）
（In formula, R1Represent the monovalent hydrocarbon of the non-substituted of carbon number 1~10 or substitution, R1Can also may be used with mutually the same
Being different groups.N is more than 10 integer.）
（B）From by following formulas（2）The ketenes silylacetal type compound of expression, by following formulas（3）Represent
The compound 0.1~20 of at least a kind selected in 2- methyl dioxanes epoxide silicyl propionic ester and their partial hydrolystate
Mass parts,
（R2O）2Si（R3）OC（OR3）CHCH3（2）
（R2O）2Si（CH3）CH（CH3）COOR3（3）
（In formula, R2Represent the alkyl of carbon number 1~4, R3Represent the alkane of the non-substituted of carbon number 1~12 or substitution
Base, R2、R3Can be with mutually the same, or different group.）
（C）Intramolecular has the organic compound and/or the mass parts of silane compound 0.01~20 of at least one nitrogen-atoms,
（D）There are more than 2 by following formulas in 1 molecule（4）The silane compound of the alkoxy of expression and/or its part
The mass parts of hydrolytic condensate 0.1~30,
R5 mSi（OR4）4-m（4）
（In formula, R4Represent the monovalent hydrocarbon of the non-substituted or alkoxy substitution of carbon number 1~4, R5Represent carbon number 1
~10 non-substituted or substitution monovalent hydrocarbon, m is 0,1 or 2.）
2nd composition, is the composition containing following component：
（E）By following formulas（5）The mass parts of organopolysiloxane 150~10 of expression,
HO（SiR1 2O）nH （5）
（In formula, R1, n it is same as described above.）
（F）The mass parts of organotin catalysts 0.01~10,
（G）Following formulas（6）The mass parts of ester compounds 0.1~10 of expression
R6COCH2COOR6（6）
（In formula, R6It is the alkyl of carbon number 1~5, R6Can be with mutually the same, or different group.）
Wherein,（A）、（E）Composition adds up to 200 mass parts, contains in the 1st composition（B）~（D）Composition and the 2nd
Contain in composition（F）、（G）The use level of composition represent respectively relative to（A）、（E）Total 200 mass parts of composition are matched somebody with somebody
Resultant.
[2] composition described in [1], wherein,（A）Composition is 80~120 mass parts,（E）Composition is 120~80 mass
Part, wherein,（A）Composition and（E）Composition adds up to 200 mass parts.
[3] composition described in [1] or [2], it is automobile component or electrical and electronic parts sealant.
The effect of invention
Biliquid mixed type organopolysiloxane composition of the invention, due to the usable time with appropriateness,
Therefore the bonding up time is long, and deep curability is good, and excellent rubber-like elastic body is obtained therefore, it is possible to the short time.
Composition of the invention can be suitable for various adhesives, sealant, especially for mobile applications and electric and electronic purposes
Deng sealant it is effective.
Specific embodiment
The present invention is illustrated in greater detail below.
Biliquid mixed type organopolysiloxane composition of the invention is by containing described later（A）~（D）1st combination of composition
Thing and containing described later（E）~（G）The 2nd composition composition of composition, and consolidated by the way that the 1st composition and the 2nd composition are mixed
Change.
In 1st composition（A）Composition is by following formulas（1）The organopolysiloxane of expression.
HO（SiR1 2O）nH （1）
Above-mentioned formula（1）In, R1Represent the monovalent hydrocarbon of carbon number 1~10 non-substituted or substitution, for example, for methyl,
The alkyl such as ethyl, propyl group, butyl, hexyl, octyl group；The cycloalkyl such as cyclohexyl；Vinyl, pi-allyl, acrylic, cyclobutenyl, oneself
The alkenyls such as alkenyl；The aryl such as phenyl, tolyl；The aralkyl such as benzyl, phenylethyl, or one of hydrogen atom of these groups
Point or all by substituted groups such as such as chlorine, fluorine, the halogen atoms of bromine, such as trifluoro propyl etc., preferably methyl, phenyl, especially
It is preferred that methyl.The R1Can be identical group, or different groups.
Additionally, formula（1）In n be more than 10 integer, preferably the viscosity at the 25 of the organopolysiloxane DEG C be 25~
500,000mPas scope, specifically for the scope of 500~100,000mPas.Further, in the present invention, viscosity is using rotation
Turn the value of viscosimeter measure.
In composition of the invention,（A）Composition and（E）Composition adds up to 200 mass parts, the 1st composition（A）Composition
It is 50~190 mass parts（（E）Composition is 150~10 mass parts）, preferably 70~150 mass parts（（E）Composition is 130~50
Mass parts）, more preferably 80~120 mass parts（（E）Composition is 120~80 mass parts）, particularly preferably 90~110 mass parts
（（E）Composition is 110~90 mass parts）.If（A）The amount of composition is less than 50 mass parts（（E）The amount of composition is more than 150 mass
Part）, or more than 190 mass parts（（E）Composition is less than 10 mass parts）, sometimes rapidly-curable become insufficient.
Next, as（B）Composition by following formulas（2）The ketenes silylacetal type compound of expression, by following
Formula（3）The 2- methyl dioxanes epoxide silicyl propionic ester of expression or their partial hydrolystate, are in the present compositions to use
In making（A）The neccessary composition of two end alkoxy groups of composition.
（R2O）2Si（R3）OC（OR3）CHCH3（2）
（R2O）2Si（CH3）CH（CH3）COOR3（3）
（In formula, R2Represent the alkyl of carbon number 1~4, R3Represent the alkane of the non-substituted of carbon number 1~12 or substitution
Base, R2、R3Can be with mutually the same, or different group.）
Above-mentioned formula（2）、（3）In, as R2Carbon number 1~4 alkyl, can be the alkane of straight-chain, branch-like
Base, can enumerate such as methyl, ethyl, propyl group, normal-butyl, isopropyl, the tert-butyl group, sec-butyl, isobutyl group.These groups can phase
Together, it is also possible to different.
Additionally, as R3Carbon number 1~12 alkyl, can be the alkyl of straight-chain, ring-type, branch-like, can arrange
The rings such as citing such as methyl, ethyl, propyl group, normal-butyl, hexyl, heptyl, octyl group, nonyl, the alkyl of decyl straight-chain, cyclohexyl
The alkyl of the branch-likes such as alkyl and the tert-butyl group, the 2- ethylhexyls of shape, the hydrogen atom of these groups part or all by chlorine,
The substituted groups such as the halogen substitution monovalent hydrocarbon such as chloromethyl, bromoethyl, trifluoro propyl of the substitution of the halogen atoms such as fluorine, bromine
Deng.These groups can be with identical, it is also possible to different.
In the present invention, R2It is preferred that methyl, ethyl, wherein more preferably methyl.Additionally, R3It is preferred that methyl, ethyl, normal-butyl, 2-
Ethylhexyl, wherein more preferably 2- ethylhexyls.（B）1 kind can be used alone or be two kinds or more and used by composition.
Wherein, by formula（2）The ketenes silylacetal type compound of expression and by formula（3）The 2- methyl dioxane oxygen of expression
There is the relation of isomers in base silicyl propionic ester, can be for example, by the hydrogenation of acrylate and methyl dioxane TMOS
Silanization reaction and obtained as mixture.It is further possible to using commercially available product, as commercially available product, OCMS-2 can be enumerated（SHIN-ETSU HANTOTAI
Chemical industry（Strain）System）Deng.
Above-mentioned ketenes silylacetal type compound, 2- methyl dioxanes epoxide silicyl propionic ester or their part
Hydrolysate, relative to（A）Composition and（E）Total 200 mass parts of composition, with 0.1~20 mass parts, preferably 1~15 mass parts
Scope use.If use level is very few, it is impossible to fully make（A）Two end alkoxy groups of composition, thus composition guarantor
Sustainability, deteriorated appearance, the viscosity of composition increase.Additionally, if use level is excessive, due to（B）Composition becomes superfluous, therefore solid
Change time delay, the result of the mechanical properties as the rubber for obtaining, and also become unfavorable on cost.
Next, as（C）The intramolecular of composition has the organic compound and/or silane compound of at least one nitrogen-atoms,
As for above-mentioned（A）Composition and（B）Composition is with the short time and expeditiously carries out terminal-modified catalyst, is necessary
Composition,（C）Composition with it is described later（G）Composition carries out ketimide reaction of formation, and its reactant also has catalyst action.
As（C）The organic compound with least one nitrogen-atoms, can preferably use amines in component molecules,
As concrete example, the primary amine class such as methylamine, ethamine, propylamine, butylamine, octylame, dimethylamine, diethylamine, di-n-propylamine, two fourths can be illustrated
The tertiary amines such as the secondary amine classes such as amine, dioctylamine, trimethylamine, triethylamine, tripropyl amine (TPA), tri-n-butylamine, trioctylamine.As（C）Component molecules
The interior silane compound with least one nitrogen-atoms, can illustrate 3- aminopropyls diethoxymethylsilane, 3- aminopropyls three
Ethoxysilane, 3- aminopropyldimethoxies methyl-monosilane, 3- TSL 8330s, the ethoxy of 3- amino methyls three
Base silane, 3- amino methyls trimethoxy silane, 3-（2- aminoethylaminopropyls）Dimethoxymethylsilane, 3-（2- ammonia
Base diethylaminobutyyl）Trimethoxy silane, 2- aminoethylaminomethyls dimethoxymethylsilane, 2- aminoethylaminos
MTMS, 1,1,3,3- tetramethyl -2- [3-（Trimethoxysilyl）Propyl group] the alkoxyl silicone alkanes such as guanidine.
Intramolecular has the organic compound or silane compound of at least one nitrogen-atoms, as long as the material of alkalescence is shown in atmosphere,
There is no particular restriction.Wherein, preferably APTES, 1,1,3,3- tetramethyl -2- [3-（Trimethoxy first
Silylation）Propyl group] guanidine, more preferably using 1,1,3,3- tetramethyl -2- [3-（Trimethoxysilyl）Propyl group] guanidine.（C）Into
Divide and be not limited to a kind, two or more can be used.
Above-mentioned intramolecular has the organic compound and/or silane compound of at least one nitrogen-atoms, relative to（A）Into
Point and（E）Total 200 mass parts of composition, are used with the scope of 0.01~20 mass parts, preferably 0.1~10 mass parts, if
Use level is very few, it is impossible to fully use（B）Composition will（A）Two end alkoxy groups of composition, if use level is excessive, smell,
Keeping quality deteriorates.
Next, as（D）With more than 2, preferably more than 3 by following formulas in 1 molecule of composition（4）Represent
The silane compound of alkoxy and/or its partial hydrolysis condensate are the compositions for giving the curability of this composition appropriateness.
R5 mSi（OR4）4-m（4）
（In formula, R4It is the monovalent hydrocarbon that the non-substituted or alkoxy of carbon number 1~4 replaces, R5It is carbon number 1~10
It is non-substituted or substitution monovalent hydrocarbon, m be 0,1 or 2.）
Above-mentioned formula（4）In, R4It is the monovalent hydrocarbon that the non-substituted or alkoxy of carbon number 1~4 replaces, as monovalent hydrocarbon
Base, can enumerate the alkyl of the carbon numbers such as methyl, ethyl, propyl group, butyl 1~4；As alkoxy-substituted alkyl, first can be enumerated
Epoxide methyl, ethoxyl methyl, propoxy methyl, butoxymethyl, amoxy methyl, methoxy ethyl, ethoxyethyl group, third
Epoxide ethyl, butoxyethyl group, methoxy-propyl, ethoxycarbonyl propyl, propoxypropyl, methoxybutyl, ethoxybutyl, first
Epoxide amyl group etc..In these, preferably methyl, ethyl.
R5Be the non-substituted of carbon number 1~10 or substitution monovalent hydrocarbon, be for example methyl, ethyl, propyl group, butyl,
The alkyl such as hexyl, octyl group；The cycloalkyl such as cyclohexyl；The alkenyls such as vinyl, pi-allyl, acrylic, cyclobutenyl, hexenyl；Phenyl,
The aryl such as tolyl；The aralkyl such as benzyl, phenylethyl, or these groups hydrogen atom part or all by as chlorine,
The substituted groups such as fluorine, the halogen atom of bromine, such as trifluoro propyl etc., preferably methyl, phenyl, particularly preferred methyl.The R5Can
Being identical group, or different groups.
As above-mentioned（D）The concrete example of composition, can illustrate tetramethoxy-silicane, silester, silicic acid propyl ester, methyl trimethoxy
TMOS, MTES, vinyltrimethoxy silane, VTES, phenyl trimethoxy
Silane, phenyl triethoxysilane, methyl three（Methoxy ethoxy）Silane, vinyl three（Methoxy ethoxy）Silane, two
Methyl dimethoxysilane, dimethyldiethoxysilane, dimethoxydiphenylsilane, vinyl methyl dimethoxysilane
Deng alkoxy silane, or part thereof hydrolytic condensate, during the partial hydrolysis condensate can be straight-chain, branch-like, ring-type
Arbitrary portion hydrolytic condensate.The partial hydrolysis condensate is typically the oligomer of the degree of polymerization 2~8 or so.（D）Composition is not limited
Due to a kind, two or more can be used.
There is the silane compound of above-mentioned alkoxy of more than 2 or part thereof hydrolytic condensate in 1 molecule, relative to
（A）Composition and（E）Total 200 mass parts of composition, are used, such as with the scope of 0.1~30 mass parts, preferably 1~15 mass parts
Fruit use level is very few, excessive rapid curing, and workability is deteriorated, if use level is excessive, the mechanical properties of the rubber for obtaining.
Secondly, in the 2nd composition（E）Composition is by following formulas（5）The organopolysiloxane of expression.
HO（SiR1 2O）nH （5）
（In formula, R1, n and above-mentioned formula（1）R1, n it is identical.）
Above-mentioned formula（5）In, R1Represent the monovalent hydrocarbon of carbon number 1~10 non-substituted or substitution, for example, for methyl,
The alkyl such as ethyl, propyl group, butyl, hexyl, octyl group；The cycloalkyl such as cyclohexyl；Vinyl, pi-allyl, acrylic, cyclobutenyl, oneself
The alkenyls such as alkenyl；The aryl such as phenyl, tolyl；The aralkyl such as benzyl, phenylethyl, or one of hydrogen atom of these groups
Point or all by substituted groups such as such as chlorine, fluorine, the halogen atoms of bromine, such as trifluoro propyl etc., preferably methyl, phenyl, especially
It is preferred that methyl.The R1Can be identical group, or different groups.
Additionally, formula（5）In n be more than 10 integer, preferably the viscosity at the 25 of the organopolysiloxane DEG C be 25~
500,000mPas scope, specifically for the scope of 500~100,000mPas.
（E）Composition can be with（A）Composition substitution base, in the degree of polymerization it is different, but preferably with（A）Composition is identical.
Additionally, for（E）The use level of composition, as described above.
（F）Composition organotin catalysts are the neccessary compositions for making this composition solidify well.
As（F）The concrete example of the organotin catalysts of composition, can enumerate dimethylformamide dimethyl epoxide tin, oxalic acid dibutyl
Tin, two sad dibutyl tins, dibutyl tin two（Malaysia acid benzyl ester）, dioctyl tin diacetate, two tertiary carboxylic acid dioctyl tins etc. have
Machine tin compound, using a kind in these, or two or more can be applied in combination.
（F）The use level of composition, relative to（A）Composition and（E）Total 200 mass parts of composition, preferably cooperation 0.01~
10 mass parts, particularly 0.05~1 mass parts.If less than 0.01 mass parts, surface cure is slack-off, if more than 10 mass
The amount of part, it is too fast except solidifying, become beyond manufacture difficulty, the elongation reduction of the composition for obtaining, the mechanical property of rubber
Deteriorate.
（G）Following formulas of composition（6）Shown ester compounds, be for by with it is above-mentioned（C）The intramolecular tool of composition
There are organic compound and/or the silane compound mixing of at least one nitrogen-atoms and cause ketimide reaction of formation, using anti-by this
The water of by-product is answered to give the neccessary composition of this composition rapidly-curable and deep curability.
R6COCH2COOR6（6）
（In formula, R6It is the alkyl of carbon number 1~5, R6Can be with mutually the same, or different group.）
Above-mentioned formula（6）In, R6It is the alkyl of carbon number 1~5, is such as methyl, ethyl, propyl group, butyl, amyl group etc.,
It is preferred that methyl, ethyl, butyl, particularly preferred methyl, ethyl.The R6Can be identical group, or different groups.
As above-mentioned（G）The concrete example of composition, can illustrate methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate,
The secondary butyl ester of isopropyl acetoacetate, butyl-acetoacetate, acetoacetate, tert-butyl acetoacetate, acetoacetate pentyl ester, acetyl second
Isoamyl valerate etc..Wherein, preferably ethyl acetoacetate, propyl acetoacetate, more preferably ethyl acetoacetate.（G）Composition is not
1 kind is defined in, two or more can be used.
（G）The use level of composition, relative to（A）Composition and（E）Total 200 mass parts of composition, preferably coordinate 0.1~10
Mass parts, particularly 0.5~4 mass parts.If less than 0.1 mass parts, the solidification of this composition is slack-off, rapidly-curable drop
It is low, if more than the amount of 10 mass parts, the excess stickiness reduction of the 2nd composition has a negative impact to cementability.
Biliquid mixed type organopolysiloxane composition of the invention, except above-mentioned（A）~（G）Beyond composition, enter one
Step as needed, in order to improve the flow behavior before solidification, assigns the necessary engineering properties of rubber elastomer after solidification, more excellent
Choosing at least a kind filler of addition.
As the concrete example of the filler of addition, can illustrate and be processed with organo-silicon compound such as silane, silazane, siloxanes
Or the silica such as untreated fumed silica, wet silica, carbon dust, talcum, bentonite, surface fat
Acid, resin acid etc. treatment or untreated calcium carbonate, zinc carbonate, magnesium carbonate, surface treatment, untreated calcium oxide, zinc oxide,
Magnesia, aluminum oxide, aluminium hydroxide etc., the surface treatment of preferred pair filler and the few filler of amount of moisture.
The addition of above-mentioned filler, relative to（A）Composition and（E）Total 200 mass parts of composition, preferably cooperation 2~
600 mass parts.Filler can be matched with the 1st composition and/or the 2nd composition.
Biliquid mixed type organopolysiloxane composition of the invention, it is above-mentioned by making（A）~（D）Composition is used as the 1st group
Compound, makes above-mentioned（E）~（G）Composition mixes various additives in the state of moisture is blocked as needed as the 2nd composition
And obtain.
1st composition can be by will be above-mentioned（A）~（D）Composition, as needed together with various additives, according to known
Method mixing and modulate；And the 2nd composition can be by will be above-mentioned（E）~（G）Composition, as needed with various additives
Together, mix according to known methods and modulate.
These compositions for obtaining, can as being preserved as former state in respective closed container respectively, mixing when using and
The so-called 2 package-type organopolysiloxane composition for being cured as rubber-like elastic body is used.
Biliquid mixed type organopolysiloxane composition of the invention, by with（A）、（E）Composition adds up to 200 mass parts
Mode mix, by what is contained in the 1st composition（C）Organic compound in component molecules with least one nitrogen-atoms and/or
Contain in silane compound and the 2nd composition（G）Composition ester compounds mix and cause ketimide reaction of formation, using by this
The water cure of by-product is reacted, is solidified using the presence of the moisture in air, while（A）Composition,（B）Composition and（D）Composition with
（E）Composition in atmosphere,（C）Reacted in the presence of composition, so that not only from surface cure, and also solidify from inside it,
Therefore rapidly-curable and deep curability are improved.Additionally, polymer based on by making（A）Composition and（E）Composition
Viscosity, addition change such that it is able to rapidly-curable is controlled, simultaneously because the solidfied material for obtaining has excellent mechanicalness
Matter, therefore, it is possible to provide the sealant of excellent property.
Composition of the invention is suitable for sealant, adhesive etc., for the spy such as mobile applications and electric and electronic purposes
It is ineffective.
Further, condition of cure of biliquid mixed type organopolysiloxane composition of the invention etc. is unrestricted, for public affairs
Can also solidify well under the conditions of the unaccommodated low temperature and low humidity degree of normal temperature cured organic polysiloxane composition known.
Embodiment
Embodiment described below and comparative example, specifically describe to the present invention, but the present invention does not receive following embodiments
Limitation.
[embodiment 1]
Viscosity at 25 DEG C is the matter of dimethyl silicone polymer 100 of the end capped silanol groups of 20,000mPas
The reactant of 2-EHA and dimethoxymethylsilane is added in amount part（Trade name：OCMS-2, SHIN-ETSU HANTOTAI's chemistry work
Industry（Strain）System）3 mass parts, 1,1,3,3- tetramethyl -2- [3-（Trimethoxysilyl）Propyl group] mass parts of guanidine 0.6, with mixed
Conjunction machine mixes, and after reaction, adds the partial hydrolysis condensate of MTMS（Trade name：KC-89E, SHIN-ETSU HANTOTAI's chemistry work
Industry（Strain）System）1 mass parts, the mass parts of vinyltrimethoxy silane 1, are thoroughly mixed under reduced pressure, have obtained the 1st composition.
Additionally, the viscosity at 25 DEG C is the dimethyl silicone polymer of the end capped silanol groups of 20,000mPas
The mass parts of ethyl acetoacetate 2, the mass parts of two tertiary carboxylic acid dioctyl tin 0.2 are added in 100 mass parts, is mixed with mixer, obtained
To the 2nd composition.
With volume ratio about 1：1 ratio mixes above-mentioned 1st composition and the 2nd composition, has obtained sample 1.
[embodiment 2]
Viscosity at 25 DEG C is the matter of dimethyl silicone polymer 100 of the end capped silanol groups of 20,000mPas
The reactant of 2-EHA and dimethoxymethylsilane is added in amount part（Trade name：OCMS-2, SHIN-ETSU HANTOTAI's chemistry work
Industry（Strain）System）3 mass parts, 1,1,3,3- tetramethyl -2- [3-（Trimethoxysilyl）Propyl group] mass parts of guanidine 0.6, with mixed
Conjunction machine mixes, and after reaction, adds the partial hydrolysis condensate of MTMS（Trade name：KC-89E, SHIN-ETSU HANTOTAI's chemistry work
Industry（Strain）System）1 mass parts, the mass parts of vinyltrimethoxy silane 1, the mass parts of APTES 5, are subtracting
Pressure is thoroughly mixed, and has obtained the 1st composition.
Additionally, the viscosity at 25 DEG C is the dimethyl silicone polymer of the end capped silanol groups of 20,000mPas
The mass parts of ethyl acetoacetate 1, the mass parts of two tertiary carboxylic acid dioctyl tin 0.2 are added in 100 mass parts, is mixed with mixer, obtained
To the 2nd composition.
With volume ratio about 1：1 ratio mixes above-mentioned 1st composition and the 2nd composition, has obtained sample 2.
[comparative example 1]
In embodiment 1, except not including 2-EHA and dimethoxymethylsilane in the 1st composition
Beyond reactant, modulate under identical condition, obtained sample 3.
[comparative example 2]
In embodiment 1, in addition to the ethyl acetoacetate in not including the 2nd composition, modulate under identical condition,
Sample 4 is obtained.
[comparative example 3]
In embodiment 1, except not including 1,1,3,3- tetramethyl -2- [3- in the 1st composition（Trimethyoxysilane
Base）Propyl group] beyond guanidine, modulate under identical condition, obtain sample 5.
[comparative example 4]
In embodiment 1, in addition to two tertiary carboxylic acid dioctyl tins in not including the 2nd composition, under identical condition
Modulation, has obtained sample 6.
[comparative example 5]
In embodiment 1, in addition to the ethyl acetoacetate in replacing the 2nd composition has used the mass parts of water 2, same
Modulated under conditions of sample, obtained sample 7.
[comparative example 6]
In embodiment 1, except replace the 2nd composition in ethyl acetoacetate and used the mass parts of acetylacetone,2,4-pentanedione 2 with
Outward, modulate under identical condition, obtained sample 8.
[comparative example 7]
In embodiment 1, in addition to the ethyl acetoacetate in replacing the 2nd composition has used the mass parts of acetone 2,
Modulated under conditions of same, obtained sample 9.
[comparative example 8]
In embodiment 1, in addition to the ethyl acetoacetate in replacing the 2nd composition has used the mass parts of ethanol 2,
Modulated under conditions of same, obtained sample 10.
Using the sample obtained in above-described embodiment and comparative example, various experiments are carried out using following shown methods.
Test method
The biliquid mixed type organopolysiloxane composition of above-described embodiment, comparative example, is for about 1 by with volume ratio：1 will
1st composition and the 2nd composition mix in being filled into sealing container, have obtained the sample of target.To adopt and mix with the aforedescribed process
The composition of conjunction（Each sample）Be cast to 2mm it is framed in, be aged 3 under 23 DEG C, 50%RH, obtained the thick sheet rubbers of 2mm
Material.Additionally, using time as the rubbery time as rubber after mixing, its assay method is by determining using above-mentioned side
The composition of method mixing time as rubber under the air-proof condition confirms.As the index for obtaining good workability, will
The rubbery time be more than 60 minutes as qualified, additionally, as the index of good curability, the rubbery time is less than
360 minutes used as qualified.According to method specified in JIS A5758, determine and do not glue the time（Drying time of finger-touching）, according to JIS
K6249, rubber physical property is determined by 2mm thick sheets.
Additionally, each 1st composition of the embodiment that will be obtained at normal temperatures, comparative example and the 2nd composition are preserved 6 months,
Various experiments have been carried out as described above.
The result of embodiment 1,2 and comparative example 1~8 is shown in table 1 below.
[table 1]
Claims (9)
1. 2- trialkoxysilyls propionic ester or the biliquid mixed type organopolysiloxane of their partial hydrolystate are free of
Composition, it is characterised in that comprising following shown the 1st compositions and the 2nd composition, combined by by the 1st composition and the 2nd
Thing mixes and solidifies,
1st composition, is the composition containing following component：
(A) mass parts of organopolysiloxane 50~190 represented by following formulas (1),
HO(SiR1 2O)nH (1)
In formula, R1Represent the monovalent hydrocarbon of the non-substituted of carbon number 1~10 or substitution, R1Can be with mutually the same, or not
Same group, n is more than 10 integer,
(B) from the ketenes silylacetal type compound represented by following formulas (2), the 2- first represented by following formulas (3)
The mass of compound 0.1~20 of at least a kind selected in base dialkoxy silicyl propionic ester and their partial hydrolystate
Part,
(R2O)2Si(R3)OC(OR3)CHCH3 (2)
(R2O)2Si(CH3)CH(CH3)COOR3 (3)
In formula, R2Represent the alkyl of carbon number 1~4, R3Represent the alkyl of the non-substituted of carbon number 1~12 or substitution, R2、R3
Can with mutually the same, or different group,
(C) intramolecular has the organic compound and/or the mass parts of silane compound 0.01~20 of at least one nitrogen-atoms,
(D) there is silane compound and/or its partial hydrolysis of more than 2 alkoxies by following formulas (4) expression in 1 molecule
The mass parts of condensation product 0.1~30,
R5 mSi(OR4)4-m (4)
In formula, R4Represent the monovalent hydrocarbon of the non-substituted or alkoxy substitution of carbon number 1~4, R5Represent carbon number 1~10
It is non-substituted or substitution monovalent hydrocarbon, m be 0,1 or 2,
2nd composition, is the composition containing following component：
(E) mass parts of organopolysiloxane 150~10 represented by following formulas (5)
HO(SiR1 2O)nH (5)
In formula, R1, n it is same as described above,
(F) mass parts of organotin catalysts 0.01~10,
(G) mass parts of ester compounds 0.1~10 represented by following formulas (6)
R6COCH2COOR6 (6)
In formula, R6It is the alkyl of carbon number 1~5, R6Can with mutually the same, or different group,
Wherein, (A), (E) composition add up to 200 mass parts, (B) contained in the 1st composition~(D) composition and the 2nd combination
The use level of (F), (G) composition contained in thing represents the cooperation of total 200 mass parts relative to (A), (E) composition respectively
Amount.
2. the biliquid mixed type organopolysiloxane composition described in claim 1, wherein, (A) composition is 80~120 mass
Part, (E) composition is 120~80 mass parts, wherein, (A) composition adds up to 200 mass parts with (E) composition.
3. the biliquid mixed type organopolysiloxane composition described in claim 1 or 2, it is by relative to (A) composition, (E)
The mass parts of total amount 200 of composition are that the filler of 2~600 mass parts is matched with above-mentioned 1st composition and/or the 2nd composition
And formed.
4. the biliquid mixed type organopolysiloxane composition described in claim 1 or 2, it is characterised in that by the 1st composition and
2nd composition mixes and solidifies in the case where moisture is blocked.
5. the biliquid mixed type organopolysiloxane composition described in claim 1 or 2, it is automobile component sealant or electricity
Gas electronic component-use sealant.
6. the biliquid mixed type organopolysiloxane composition described in claim 3, it is characterised in that by the 1st composition and the 2nd
Composition mixes and solidifies in the case where moisture is blocked.
7. the biliquid mixed type organopolysiloxane composition described in claim 3, it is automobile component sealant or electrically
Electronic component-use sealant.
8. the biliquid mixed type organopolysiloxane composition described in claim 4, it is automobile component sealant or electrically
Electronic component-use sealant.
9. the biliquid mixed type organopolysiloxane composition described in claim 6, it is automobile component sealant or electrically
Electronic component-use sealant.
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| JP2012075956A JP5644800B2 (en) | 2012-03-29 | 2012-03-29 | Two-component mixed organopolysiloxane composition |
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| JP7327212B2 (en) * | 2019-03-07 | 2023-08-16 | 信越化学工業株式会社 | Two-component room temperature condensation-curable organopolysiloxane composition |
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| JP2006131824A (en) * | 2004-11-09 | 2006-05-25 | Shin Etsu Chem Co Ltd | Room temperature curable organopolysiloxane composition |
| CN1952001A (en) * | 2005-05-13 | 2007-04-25 | 信越化学工业株式会社 | Room temperature curable organopolysiloxane composition |
| CN101993592A (en) * | 2009-08-10 | 2011-03-30 | 信越化学工业株式会社 | Two-part organopolysiloxane composition |
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| JPH0649824B2 (en) * | 1989-09-05 | 1994-06-29 | 信越化学工業株式会社 | Room temperature curable organopolysiloxane composition |
| JP3121188B2 (en) * | 1993-10-26 | 2000-12-25 | 信越化学工業株式会社 | Room temperature fast-curing organopolysiloxane composition excellent in water resistance, curing method thereof, and cured product obtained thereby |
| JP3263331B2 (en) * | 1997-02-04 | 2002-03-04 | 鈴木産業株式会社 | Solvent-free two-part cold curing type liquid polymer composition and its use |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2006131824A (en) * | 2004-11-09 | 2006-05-25 | Shin Etsu Chem Co Ltd | Room temperature curable organopolysiloxane composition |
| CN1952001A (en) * | 2005-05-13 | 2007-04-25 | 信越化学工业株式会社 | Room temperature curable organopolysiloxane composition |
| CN101993592A (en) * | 2009-08-10 | 2011-03-30 | 信越化学工业株式会社 | Two-part organopolysiloxane composition |
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