KR20120013196A - Room temperature curable organopolysiloxane composition, and automobile oil seal - Google Patents

Abstract

PURPOSE: A room temperature-curable organopolysiloxane composition is provided to have excellent initial hardness, the stability of adhesion as time passed, and drug resistance especially engine oil resistance. CONSTITUTION: A room temperature-curable organopolysiloxane composition comprises: organopolysiloxane in chemical formula 1: HO(SiR^1_2O)_aH; a silane compound and/or there partial hydrololysate thereof having two or more ketooxime group in chemical formula 2: R^3_bSi(ON=CR^2_2)_(4-b) in one molecule; a silane compound in chemical formula 3: R^5_cR^6_dSi(ON=CR^4_2)_(4-c-d), the reactant of the silane compound in chemical formula 4: (XR^7)_eR^8_fSi(ON=CR^4_2)_(4-e-f), partial hydrololysate thereof, or mixtures thereof; and at least one kind of filler.

Description

ROOM TEMPERATURE CURABLE ORGANOPOLYSILOXANE COMPOSITION, AND AUTOMOBILE OIL SEAL

The present invention is an oxime type room temperature curable organopolysiloxane composition which is excellent in initial curing property and adhesiveness over time, excellent in chemical resistance (particularly, engine oil resistance), and mainly used in automobile FIPG (Formed In). It relates to a room temperature-curable organopolysiloxane composition excellent in adhesion known to be useful as a place gaskets material and an automotive oil seal obtained by curing the composition.

Oil-resistant gaskets and packing materials made of cork, organic rubber, asbestos, etc. are conventionally used for sealing around engines for automobiles, but these are inconvenient that inventory management and work processes are complicated. There is also a drawback that there is no reliability. Therefore, the FIPG system using the room temperature hardening type organopolysiloxane composition was used for this kind of use, and high evaluation is obtained from workability, sealing property, and heat resistance.

The condensation-curable room temperature fast-curable organopolysiloxane composition is a one-component type in which the crosslinking agent is reduced to the maximum by reducing the crosslinking agent to an extreme relative to both terminal hydroxyorganopolysiloxanes which are conventional base polymers, and the base polymer. It is known that it is a two-component type which packs both phosphorus terminal hydroxyorganopolysiloxane and a crosslinking agent separately, and mixes at the time of use.

The known oxime type room temperature hardening organopolysiloxane composition uses the oxime silane which has an oxime group as a hardening | curing agent, and the dealcohol type silane coupling agent which has an alkoxy group as an adhesion | attachment adjuvant.

However, in the composition as described above, the oxime group of the curing agent and the alkoxy group of the adhesion assistant cause a transesterification reaction, change into a curing agent or an adhesion assistant in which the oxime-alkoxy group is mixed, and as a result, an initial stage exhibited at the initial stage of production. There exists a problem that sclerosis | hardenability and adhesiveness change with time. In particular, Japanese Patent No. 3818365, Japanese Patent Publication No. 2002-309219, Japanese Patent Publication No. 2003-535152, Japanese Patent Publication No. 2005-298558, Japanese Patent Publication No. 2007-204575 (Patent Documents) FIPG materials for hard-adhesive materials reported in 1 to 5), two-liquid mixed type and jailbreak type room temperature hardening type reported in Japanese Patent No. 3916403 and Japanese Patent No. 3970484 (Patent Documents 6 and 7). In the kanopolysiloxane composition, since the addition amount of the adhesion | attachment adjuvant needs to be large, there existed a problem that the initial stage curability and adhesiveness exhibited initially at the time of manufacture fall as a result.

Japanese Patent No. 3818365 Japanese Patent Laid-Open No. 2002-309219 Japanese Patent Publication No. 2003-535152 Japanese Patent Laid-Open No. 2005-298558 Japanese Patent Laid-Open No. 2007-204575 Japanese Patent No. 3916403 Japanese Patent No. 3970484

This invention is made | formed in view of the said situation, The oxime type room temperature hardenable organopolysiloxane composition which is excellent in initial hardenability and adhesiveness exhibited at the time of manufacture, and excellent in chemical resistance, especially engine oil resistance, and It is an object to provide an automotive oil seal obtained by curing the composition.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, the present inventors changed and added the silane coupling agent which has the alkoxy group normally used as an adhesive adjuvant into the silane coupling agent which has an oxime group, and accordingly, The oxime type room temperature curable organopolysiloxane which suppresses and inhibits the transesterification reaction and is excellent in initial curing stability and adhesiveness over time as a result, and has excellent chemical resistance, particularly engine oil resistance. It was found that the composition was obtained, and came to complete the present invention.

Therefore, this invention provides the room temperature curable organopolysiloxane composition and automotive oil seal shown below.

[Claim 1]

(A) 100 parts by mass of the organopolysiloxane represented by the following formula (1),

(Wherein R ¹ is an unsubstituted or halogen atom substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R ¹ may be the same as or different from each other, and a is an integer of 10 or more)

(B) 0.1 to 30 parts by mass of a silane compound having two or more ketooxime groups represented by the following formula (2) and / or partial hydrolyzate thereof,

(Wherein R ² is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R ³ is a methyl group and / or a vinyl group, b is 0, 1 or 2)

(C) 0.1 to 10 parts by mass of a reactant of a silane compound represented by the following formula (3), a silane compound represented by the following formula (3) and a silane compound represented by the following formula (4), a partial hydrolyzate thereof, or a mixture thereof:

(In formula, R <^4> is a C1-C10 unsubstituted or substituted monovalent hydrocarbon group independently, R <^5> is carbon number containing 1 type (s) or 2 or more types independently selected from a nitrogen atom, a sulfur atom, and an oxygen atom. A 1 to 10 unsubstituted or substituted monovalent hydrocarbon group, R ⁶ is an unsubstituted or halogen atom substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, c is 1 or 2, d is 0 or 1, c + d is 1 or 2)

(Wherein R ⁴ and R ⁶ are the same as described above, R ⁷ is independently an unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, X is a chlorine atom, a bromine atom or a (meth) acryl group, and e is 1 or 2, f is 0 or 1, and e + f is 1 or 2)

(D) 1 to 300 parts by mass of at least one filler

Room-temperature curable organopolysiloxane composition containing the above.

[Claim 2]

The room temperature curable organopolysiloxane composition according to claim 1, wherein component (C) is selected from compounds represented by the following formulas (5) to (8).

(Wherein R ⁴ , R ⁶ , R ⁷ , d, f are the same as above)

[Claim 3]

(E) The mass ratio of the said (C) component and the (E) component is 0.70 <= (C) component of the (E) silane coupling agent and / or its partial hydrolyzate which are represented by following formula (9) / [(C) component + (E) component] <room temperature curable organopolysiloxane composition containing further in the range which becomes <1.0.

(In formula, R <^8> is a C1-C6 monovalent hydrocarbon group independently, R <^9> is C1-C10 which contains 1 type (s) or 2 or more types independently selected from a nitrogen atom, a sulfur atom, and an oxygen atom. An unsubstituted or substituted monovalent hydrocarbon group, R ¹⁰ is an unsubstituted or halogen atom substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, g is 1 or 2, h is 0 or 1, and g + h is 1 or 2)

[Claim 4]

An automobile oil seal obtained by curing the composition according to any one of claims 1 to 3.

According to the present invention, it is possible to suppress and inhibit the phenomenon that the original curability and adhesiveness of the original composition in the conventional composition decreases with time, and is excellent in chemical resistance (especially engine oil resistance). Polysiloxane compositions can be obtained. The composition of the present invention can be expected to be used in the industry where initial curing retention is required, and is particularly effective for automotive applications.

Hereinafter, the present invention will be described in more detail, (A) component of the room temperature curable organopolysiloxane composition of the present invention is an organopolysiloxane represented by the following formula (1).

<Formula 1>

In Formula 1, R ¹ is an unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, jade Alkyl groups such as a methyl group; Cycloalkyl groups such as cyclohexyl group; Alkenyl groups such as vinyl group, allyl group, propenyl group, butenyl group and hexenyl group; Aryl groups, such as a phenyl group and a tolyl group; Aralkyl groups such as benzyl and phenylethyl groups, or groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as chlorine, fluorine and bromine, for example, chloropropyl group and trifluoropropyl group. have. Among these, a methyl group and a phenyl group are preferable and a methyl group is especially preferable. This R ¹ may be the same group or may be a heterogeneous group.

In addition, a in General formula (1) is an integer of 10 or more, It is preferable that the viscosity in 23 degreeC of this organopolysiloxane becomes the number which becomes the range of 25-500,000 mPa * s, especially the range of 500-100,000 mPa * s. In addition, in this invention, a viscosity is the value measured by the rotational viscometer in 23 degreeC.

Subsequently, component (B) is a silane compound having two or more ketooxime groups represented by the following formula (2) in one molecule and / or partial hydrolyzate thereof.

<Formula 2>

Wherein R ² is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, R ³ is a methyl group and / or a vinyl group, and b is 0, 1 or 2 )

In said Formula (2), the same thing as what was illustrated by said R <^1> can be illustrated as R <^2> , Preferably it is a methyl group, an ethyl group, and an isobutyl group.

Specific examples of the silane compound represented by the formula (2) include methyltris (dimethylketooxime) silane, methyltris (methylethylketooxime) silane, methyltris (methylisobutylketooxime) silane and vinyltris (methylethylketooxime) silane Ketooxime silanes, such as a vinyl tris (dimethyl keto oxime) silane and a vinyl tris (methyl isobutyl keto oxime) silane, are illustrated.

(B) A component can be used individually by 1 type or in combination of 2 or more types.

The silane compound of the said (B) component and its partial hydrolyzate are 0.1-30 mass parts with respect to 100 mass parts of organopolysiloxane of (A) component, Preferably it is used in the range of 1-15 mass parts, and a compounding quantity When too small, sufficient crosslinking will not be obtained, and it will not become the composition which has the target rubber elasticity, and when too much compounding quantity, mechanical property will deteriorate.

Subsequently, component (C) is a silane compound having two or more ketooxime groups represented by the following formula (3) and / or partial hydrolyzate thereof, or a ketooxime group represented by the following silane compound and the following formula (4): It is a reactant of the silane compound which has two or more in a molecule | numerator, and / or its partial hydrolyzate, and it is an essential component for suppressing and suppressing the change with sclerosis | hardenability with time in this composition, and expressing favorable adhesiveness.

<Formula 3>

Wherein R ⁴ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and R ⁵ is independently one selected from a nitrogen atom, a sulfur atom, an oxygen atom, or An unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms containing two or more species, R ⁶ is an unsubstituted or halogen atom substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, c is 1 or 2, and d is 0 or 1, c + d is 1 or 2)

<Formula 4>

(Wherein R ⁴ and R ⁶ are the same as described above, R ⁷ is independently an unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, X is a chlorine atom, a bromine atom or a (meth) acryl group, and e is 1 or 2, f is 0 or 1, and e + f is 1 or 2)

In Formulas (3) and (4), R ⁴ may exemplify the same as R ² described above, and preferably methyl, ethyl or isobutyl.

In Formula 3, R ⁵ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, including one or two or more selected from nitrogen, sulfur, and oxygen atoms. An amino group containing group, an amide group containing group, a mercapto group containing group, an isocyanate group containing group, an epoxy group containing group, a (meth) acryl group containing group, etc. are illustrated. Examples of R ⁵ include -R ⁷ NH ₂ , -R ⁷ NHR ⁷ NH ₂ , -R ⁷ NHCONH ₂ , -R ⁷ SH, -R ⁷ NCO, and -R ⁷ OR ⁷ CH (O) CH ₂ . Among them, amino group-containing monovalent hydrocarbon groups such as -R ⁷ NH ₂ and -R ⁷ NHR ⁷ NH ₂ (R ⁷ is an unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms), specifically, an aminoethyl group, An aminopropyl group, 3- (2-aminoethylamino) propyl group, etc. can be illustrated.

In Formulas 3 and 4, R ⁶ is an unsubstituted or halogen atom-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and as R ⁶ , the same as those exemplified for R ¹ may be exemplified. It is preferably a methyl group.

In said Formula (4), X is a chlorine atom, a bromine atom, an acryl group, or a methacryl group, and a chlorine atom, an acryl group, and a methacryl group are preferable.

R ⁷ is an unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, for example, methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, 1,1-dimethyl Alkylene groups, such as a tetramethylene group, a butylene group, and an octylene group, etc. are mentioned, Preferably they are a methylene group, ethylene group, and a propylene group.

Although many silane compounds can be illustrated as a specific example of the silane compound represented by General formula (3), It is preferable that it is a silane compound which contains the monovalent hydrocarbon group which contains a nitrogen atom in a molecule as a functional group especially.

In particular, when the compound represented by the following general formulas (5) to (8) is used as the component (C), it is possible to obtain suppression and suppression of change over time of the curability in the present composition, and good adhesion.

<Formula 5>

<Formula 6>

<Formula 7>

<Formula 8>

(Wherein R ⁴ , R ⁶ , R ⁷ , d, f are the same as above)

Among these, the silane compound represented by General formula (5) is especially preferable.

As a compound represented by the said Formula (5-8), the compound specifically, shown below can be illustrated.

(C) component is not limited to 1 type, You may use 2 or more types simultaneously.

The component (C) is used in the range of 0.1 to 10 parts by mass, preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the organopolysiloxane of the component (A). On the contrary, if the blending amount is too large, the mechanical properties of the rubber obtained are deteriorated, which is disadvantageous in terms of cost.

At least one filler as the component (D) is a reinforcing and non-reinforcing filler for imparting good chemical resistance to the composition and imparting rubber physical properties. Examples of the filler include surface-treated and untreated fumed silica, precipitated silica, wet silica, carbon powder, talc, bentonite, heavy calcium carbonate, colloidal calcium carbonate, zinc carbonate, magnesium carbonate, surface treatment, untreated calcium oxide, and zinc oxide. Magnesium oxide, aluminum oxide, aluminum hydroxide, etc. are illustrated.

The compounding quantity of (D) component is used in the range of 1-300 mass parts with respect to 100 mass parts of (A) component, Preferably it is used in the range of 5-200 mass parts. If it is less than 1 mass part, sufficient chemical-resistance and rubber strength will not be obtained. If it exceeds 300 mass parts, not only the mixing property of a composition will deteriorate but the mechanical properties of the rubber property obtained will also fall.

Moreover, in order to further improve adhesiveness, the composition of this invention can mix | blend the silane coupling agent represented by following formula (9) and / or its partial hydrolyzate.

<Formula 9>

Wherein R ⁸ is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, particularly preferably 1 to 2 carbon atoms, and R ⁹ is independently selected from a nitrogen atom, a sulfur atom and an oxygen atom An unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 7 carbon atoms, and R ¹⁰ is unsubstituted carbon atoms having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, or Halogen atom substituted monovalent hydrocarbon group, g is 1 or 2, h is 0 or 1, g + h is 1 or 2)

In said Formula (9), a methyl group, an ethyl group, a propyl group, a butyl group etc. can be illustrated as R <^8> , Preferably it is a methyl group and an ethyl group.

In addition, R ⁹ can illustrate the same thing as R ⁵ mentioned above. R <^10> can illustrate the same thing as R <^6> mentioned above.

As a specific example of the silane coupling agent of (E) component, many silane coupling agents can be illustrated, A well-known thing is used suitably as such a silane coupling agent, A (meth) acrylsilane coupling agent, an epoxysilane coupling agent, an aminosilane coupler A ring agent, a mercaptosilane coupling agent, etc. are illustrated, Specifically, epoxy group containing silane coupling agents, such as 3-glycidoxy propyl trimethoxysilane and 3-glycidoxy propyl triethoxysilane, 3-methacryloxypropyl tri (Meth) acryl-group containing silane coupling agents, such as methoxysilane, 3-methacryloxypropyl triethoxysilane, and 3-acryloxypropyl trimethoxysilane, N- (2-aminoethyl) -3-aminopropyl tri Amino group-containing silane coupling agents, such as methoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane, 3-urea Ureido group-containing silane coupling agents such as dopropyltriethoxysilane, mercapto group-containing silane coupling agents such as 3-mercaptopropyltrimethoxysilane, and isocyanate group-containing silane coupling agents such as 3-isocyanatepropyltriethoxysilane Can be mentioned.

When mix | blending (E) component (E) component is not limited to 1 type, You may use 2 or more types simultaneously.

The compounding quantity at the time of mix | blending the silane coupling agent of (E) component and its partial hydrolyzate is 0.70 <= (C) component / ((C) component + (E) with the existing mass ratio of (C) component and (E) component. Component] <1.0, It is preferable to make it into the range of 0.8 <= (C) component / [(C) component + (E) component] <1.0 especially. If it is in this range, while the adhesiveness of a composition improves more, a change with time is suppressed and suppressed, and curability does not fall.

The composition of the present invention may be used in addition to the above components in a range that does not impair the object of the present invention, additives known in the room temperature curable organopolysiloxane composition. Examples of the additive include a curing catalyst such as an organic tin compound and an organic titanium compound, a polyether as a thixotropy enhancer, a silicone oil as a plasticizer, isoparaffin, a network polysiloxane containing trimethylsiloxy units as a crosslinking density enhancer and SiO ₂ units, and the like. If necessary, colorants such as pigments, dyes, fluorescent brighteners, bioactive additives such as antibacterial agents, antibacterial agents and marine repellents, phenylsilicone oils as bleeding oils, fluorosilicone oils, silicone and incompatible organic liquids, etc. And surface modifiers, toluene, xylene, solvent gasoline, cyclohexane, methylcyclohexane, and low boiling isoparaffin can also be added.

The room temperature curable organopolysiloxane composition of this invention is obtained by mixing the said (A)-(D) component and (E) component and various additives in the state which interrupted moisture as needed. The obtained composition is stored in a sealed container as it is, and cured into a rubbery elastomer by mixing with other components in a so-called 1 package type room temperature curable organopolysiloxane composition which is cured into a rubbery elastomer by exposure to moisture in the air when in use. It can be used as a so-called 2 package type room temperature curable organopolysiloxane composition.

Moreover, the room temperature curable organopolysiloxane composition obtained by this invention can expect application in the industry which requires initial stage curable fats and oils. Among them, it is particularly effective for automotive oil seal applications.

[Example]

Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to the following Example.

Example 1

(A) 10 parts by mass of fumed silica, the surface of which was treated with dimethyldichlorosilane (100 parts) of 100 parts by mass of polydimethylsiloxane sealed at the end of silanol group at a viscosity of 20,000 mPa · s at 23 ° C, and heavy calcium carbonate 100 After adding mass parts and mixing with a mixer, (B) 10 parts by mass of vinyl tris (methylethylketooxime) silane was added and mixed thoroughly under reduced pressure, and (C) 3-aminopropyltris (methylethylketooxime) silane 2 Mass part, 0.8 mass part of (E) 3-aminopropyl trimethoxysilane, and 0.1 mass part of dioctyl tin versatate were further added, and it mixed thoroughly under reduced pressure, and obtained sample 1 (here, (C) component / ((C ) Component + (E) component] = 0.71 (mass ratio).

[Example 2]

(A) 10 parts by mass of fumed silica, the surface of which was treated with dimethyldichlorosilane (100 parts) of 100 parts by mass of polydimethylsiloxane sealed at the end of silanol group at a viscosity of 20,000 mPa · s at 23 ° C, and heavy calcium carbonate 100 After adding mass parts and mixing with a mixer, (B) 10 parts by mass of vinyl tris (methylethylketooxime) silane was added and mixed thoroughly under reduced pressure, and (C) 3-aminopropyltris (methylethylketooxime) silane 2 Mass part and 0.1 mass part of dioctyl tin versatate were further added, and it mixed thoroughly under reduced pressure, and sample 2 was obtained (where (C) component / [(C) component + (E) component] = 1.0 (mass ratio)). .

Example 3

(A) 10 parts by mass of fumed silica, the surface of which was treated with dimethyldichlorosilane (100 parts) of 100 parts by mass of polydimethylsiloxane sealed at the end of silanol group at a viscosity of 20,000 mPa · s at 23 ° C, and heavy calcium carbonate 100 After mass parts were added and mixed with a mixer, (B) 10 parts by mass of vinyltris (methylethylketooxime) silane was added and mixed thoroughly under reduced pressure, and (C) 3- (2-aminoethylamino) propyltris (methyl 2 parts by mass of ethyl ketooxime) silane, 0.5 parts by mass of (E) 3- (2-aminoethylamino) propyltrimethoxysilane, and 0.1 parts by mass of dioctyl tin versatate were further added, followed by complete mixing under reduced pressure, thereby preparing Sample 3. (C (component) / [(C) component + (E) component] = 0.80 (mass ratio) here).

Example 4

(A) 10 parts by mass of fumed silica, the surface of which was treated with dimethyldichlorosilane (100 parts) of 100 parts by mass of polydimethylsiloxane sealed at the end of silanol group at a viscosity of 20,000 mPa · s at 23 ° C, and heavy calcium carbonate 100 After adding mass parts and mixing with a mixer, 10 parts by mass of (B) vinyltris (methylethylketooxime) silane was added and mixed thoroughly under reduced pressure, and (C) N- (2-aminoethyl) -3-aminopropyl 2 parts by mass of the reaction product of tris (methylethylketooxime) silane and chloropropyltris (methylethylketooxime) silane, (E) 0.5 parts by mass of 3-aminopropyltrimethoxysilane, and 0.1 parts by mass of dioctyl tin versatate, The mixture was mixed under reduced pressure completely to obtain Sample 4 (wherein (C) component / [(C) component + (E) component] = 0.80 (mass ratio)).

Example 5

(A) 10 parts by mass of fumed silica, the surface of which was treated with dimethyldichlorosilane (100 parts) of 100 parts by mass of polydimethylsiloxane sealed at the end of silanol group at a viscosity of 20,000 mPa · s at 23 ° C, and heavy calcium carbonate 100 10 parts by mass of (B) vinyltris (methylethylketooxime) silane was added and mixed thoroughly under a reduced pressure, and (C) 3-methacryloxypropyltris (methylethylketooxime) was added thoroughly. 2 parts by mass of a reactant of silane and N- (2-aminoethyl) -3-aminopropyltris (methylethylketooxime) silane, 0.5 part by mass of (E) 3-aminopropyltrimethoxysilane, dioctyl tin versatate 0.1 mass part was added and it mixed completely under reduced pressure, and sample 5 was obtained (wherein (C) component / [(C) component + (E) component] = 0.80 (mass ratio)).

[Example 6]

Sample 6 was obtained under the same conditions except that 6 parts by mass of (B) methyltris (methylethylketooxime) silane was blended in place of (B) vinyltris (methylethylketooxime) silane in Example 1 (wherein (C) component / [(C) component + (E) component] = 0.71 (mass ratio).

Comparative Example 1

Prepared under the same conditions except that (C) 3-aminopropyltris (methylethylketooxime) silane was not blended in Example 1 and the addition amount of (E) 3-aminopropyltrimethoxysilane was changed to 2.8 parts by mass. To obtain sample 8 (wherein (C) component / [(C) component + (E) component] = 0 (mass ratio)).

Using the samples obtained in the above examples and comparative examples (room temperature curable organopolysiloxane composition), the tack free time, slump property, curing rate, initial sealing property, rubber properties (hardness, elongation at break) , Tensile strength), shear adhesion, storage degradation test, and chemical resistance test. These results are shown in Table 1.

[Test Methods]

Tack free time (touch drying time) was measured in accordance with the method specified in JIS A 5758. The slump test was measured according to JIS A 5758.

In the curing rate test, the sample was filled into a glass petri dish having an inner diameter of 10 mm, and the cured thickness was measured from a portion which came in contact with air after 23 ° C and 50% RH × 1 day.

The initial sealability test was carried out a pressure resistance test using a pressure vessel similar to the flange pressure vessel for the internal pressure test specified in JIS K 6820 as a test apparatus. The pressure vessel consists of an upper vessel having an upper flange having an inner diameter of 58 mm, an outer diameter of 80 mm, and a height of 10 mm, and a lower vessel having a lower flange having the same dimensions as the upper flange. An annular notch of 3 mm in width and 3 mm in depth is provided along the circumference. The sealing surface of this lower flange was wash | cleaned with toluene. Then, the said sample was apply | coated in the shape of bead to the center part of the lower sealing surface. Immediately after application, the upper container was placed in the lower container so that the sealing surface of the upper flange and the lower flange contacted each other, and a steel spacer of 20.50 mm was installed to bond four fastening bolts together. The spacer had a gap of 0.5 mm between the sealing surfaces, which is a so-called accelerated test that makes the pressure resistance test more severe. After hardening for 30 minutes at 23 degreeC and 50% RH, gas was inserted from the upper pressurization port, and the gas pressure which a sealing agent can bear was made into sealing strength.

The sample was introduced into a 2 mm mold and cured at 23 ° C. and 50% RH for 4 days to obtain a 2 mm thick rubber sheet. The rubber properties were measured from a 2 mm thick rubber sheet in accordance with JIS K 6249.

Using this sample and a 25 mm wide and 100 mm long adherend (aluminum, iron), curing was carried out at 23 ° C. and 50% RH for 4 days to prepare a shear adhesion test specimen having an adhesion area of 2.5 mm ² and an adhesion thickness of 1 mm. And the shear adhesive force was measured according to JISK6249.

In the storage deterioration test, the sample was allowed to stand at 70 ° C for 7 days in an uncured state under sealing conditions, and then the performance deterioration was confirmed by performing the same test as the initial stage of manufacture. In addition, the sealing strength ratio after the storage deterioration with respect to the manufacture initial stage compared with the initial stage of manufacture and the sealing strength after storage deterioration in an initial sealability test is shown in Table 1 as retention ratio. The composition whose value becomes 60% or more is good initial stage sealing property.

In addition, in order to confirm the chemical-resistance performance of the sample hardened | cured material, the obtained 2 mm-thick rubber sheet and shear adhesion test body were immersed in engine oil for 10 days at 120 degreeC, and chemical resistance was confirmed by performing the same test as the initial stage of manufacture after that. .

Claims (4)

(A) 100 parts by mass of the organopolysiloxane represented by the following formula (1),
<Formula 1>

(Wherein R ¹ is an unsubstituted or halogen atom substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R ¹ may be the same as or different from each other, and a is an integer of 10 or more)
(B) 0.1 to 30 parts by mass of a silane compound having two or more ketooxime groups represented by the following formula (2) and / or partial hydrolyzate thereof,
<Formula 2>

(Wherein R ² is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R ³ is a methyl group and / or a vinyl group, b is 0, 1 or 2)
(C) 0.1 to 10 parts by mass of a reactant of a silane compound represented by the following formula (3), a silane compound represented by the following formula (3) and a silane compound represented by the following formula (4), a partial hydrolyzate thereof, or a mixture thereof:
<Formula 3>

(In formula, R <^4> is a C1-C10 unsubstituted or substituted monovalent hydrocarbon group independently, R <^5> is carbon number containing 1 type (s) or 2 or more types independently selected from a nitrogen atom, a sulfur atom, and an oxygen atom. A 1 to 10 unsubstituted or substituted monovalent hydrocarbon group, R ⁶ is an unsubstituted or halogen atom substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, c is 1 or 2, d is 0 or 1, c + d is 1 or 2)
<Formula 4>

(Wherein R ⁴ and R ⁶ are the same as described above, R ⁷ is independently an unsubstituted divalent hydrocarbon group having 1 to 10 carbon atoms, X is a chlorine atom, a bromine atom or a (meth) acryl group, and e is 1 or 2, f is 0 or 1, and e + f is 1 or 2)
(D) 1 to 300 parts by mass of at least one filler
Room-temperature curable organopolysiloxane composition containing the above. The room temperature curable organopolysiloxane composition according to claim 1, wherein component (C) is selected from compounds represented by the following formulas (5) to (8).
<Formula 5>

<Formula 6>

<Formula 7>

(8)

(Wherein R ⁴ , R ⁶ , R ⁷ , d, f are the same as above) The silane coupling agent represented by the following general formula (9) and / or partial hydrolyzate thereof (E) has a mass ratio of 0.70 ≦ (C) component / [(C The room temperature curable organopolysiloxane composition further containing in the range which becomes)) component + (E) component] <1.0.
&Lt; Formula 9 >

(In formula, R <^8> is a C1-C6 monovalent hydrocarbon group independently, R <^9> is C1-C10 which contains 1 type (s) or 2 or more types independently selected from a nitrogen atom, a sulfur atom, and an oxygen atom. An unsubstituted or substituted monovalent hydrocarbon group, R ¹⁰ is an unsubstituted or halogen atom substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, g is 1 or 2, h is 0 or 1, and g + h is 1 or 2) An automobile oil seal obtained by curing the composition according to any one of claims 1 to 3.