JP6131918B2 - Method for producing low-foaming room temperature curable organopolysiloxane composition and method for producing automobile oil seal - Google Patents

Description

The present invention relates to a method for producing a low-foaming room temperature-curing organopolysiloxane composition that is suitably used for automobile oil seals, and in particular, has low foaming properties even when dispersed or dissolved in a continuously variable transmission oil or an automatic transmission oil. The present invention relates to a method for producing the organopolysiloxane composition capable of providing a composition and a method for producing an automobile oil seal comprising the step of curing the composition produced by this method.

  Conventionally, oil-resistant solid gaskets and packing materials made of cork, organic rubber, asbestos, and the like have been used for various oil seals for automobile engines. These materials have the disadvantage that inventory management and work processes are complex, and further have the disadvantage that their sealing performance is unreliable.

  Therefore, a sealing method called a FIPG (Formed In Place Gaskets) method using a room temperature curable silicone rubber composition has been adopted instead of a conventional solid gasket. This is a one-part room temperature curable organopolysiloxane composition applied to the engine block seal surface when the engine is assembled, and the seal surfaces are bonded together and bolted while the composition is uncured. is there. This method has been highly evaluated in terms of workability, sealing performance and heat resistance.

  An engine assembled while applying an oil seal according to the FIPG method is usually subjected to a start test by injecting various oils immediately after the assembly. However, the room temperature curable organopolysiloxane composition requires a relatively long time for curing. If it is not sufficiently cured during the starting test, a part of the room temperature curable organopolysiloxane composition is dispersed or dissolved in the oil. In particular, when dispersed or dissolved in continuously variable transmission oil (CVT) and automatic transmission oil (ATF), the structure of the transmission itself is complicated. Oil may erupt. Therefore, even if the FIPG method is used for sealing engine oil and gear oil in a manual vehicle, the continuous variable transmission oil and automatic transmission oil seal in an automatic vehicle cannot be employed unless measures against foaming are taken. For this reason, there is a demand for a one-pack room temperature curable organopolysiloxane composition that has low foaming properties even when used in the transmission oil seal.

  Various investigations and researches have been conducted on countermeasures against foaming. For example, a method of adding an isocyanate silane to a room temperature curable organopolysiloxane composition (Japanese Patent Laid-Open No. 08-73745: Patent Document 1) or an aminosiloxane is added. Have been proposed (Japanese Patent Laid-Open No. 02-215862, Japanese Patent Publication No. 06-41561: Patent Documents 2 and 3), both of which are used for suppressing foaming by eluting additive components into oil. Although there was concern about the effect on the oil to be used, foaming was effective, but sufficient oil resistance was not obtained. Furthermore, a method of adding an alkoxysilane and aluminum stearate to a room temperature curable organopolysiloxane composition (Japanese Patent Laid-Open No. 03-17157: Patent Document 4), a method of adding a specific silane coupling agent (Japanese Patent Laid-Open No. 09). -124946 gazette: Patent Document 5) has been proposed, but there is almost no influence on the oil used, but the effect on foaming is insufficient, and sufficient oil resistance has not been obtained.

  In recent years, techniques for obtaining a low-foaming room-temperature-curable organopolysiloxane composition by a method using a siloxane that does not contain a hydroxyl group (Patent Nos. 5110287 and 2010-180382: Patent Documents 6 and 7) Although low foaming is achieved, it is necessary to use an organopolysiloxane with a hydroxyl group blocked beforehand, which increases costs and reduces price competition. Was unsuitable.

Japanese Patent Laid-Open No. 08-73745 Japanese Patent Laid-Open No. 02-215862 Japanese Patent Publication No. 06-41561 Japanese Patent Laid-Open No. 03-17157 Japanese Patent Laid-Open No. 09-124946 Japanese Patent No. 5110287 JP 2010-180382 A

The present invention has been made in view of the above circumstances, and is suitably used for automobile oil seals. In particular, the present invention provides a low-elasticity composition that provides a composition having low foaming properties even when dispersed or dissolved in a continuously variable transmission oil or an automatic transmission oil. It is an object of the present invention to provide a method for producing a foamable room temperature curable organopolysiloxane composition, and a method for producing an automobile oil seal comprising a step of curing the composition produced by this method.

  As a result of various studies to achieve the above object, the present inventors have found that an organopolysiloxane having a hydroxyl group, a specific ketene silyl acetal type compound, 2-methyl dialkoxysilyl propionic acid ester, and partial hydrolysates thereof. A room temperature-curable organopolysiloxane produced by a method of reacting at least one compound selected from the group consisting of an organic compound having at least one guanidine skeleton in the molecule and then adding a ketoxime silane compound It has been found that the composition has excellent chemical resistance, can dramatically reduce the above-mentioned foaming property, and has the same curability as the oxime type, and has led to the present invention.

（式中、Ｒ⁸は上記の通りであり、Ｒ⁹は炭素数１〜１０の非置換一価炭化水素基であり、Ｒ¹⁰は炭素数１〜１０の二価炭化水素基であり、Ｒ¹¹は芳香環を含む炭素数７〜１０の二価炭化水素基であり、ｐは１〜３の整数である。但し、ＮＨ基及びＮＨ₂基の少なくとも一方はＲ¹¹の芳香環に直結していない。）
で示されるシラン化合物であることを特徴とする〔１〕〜〔４〕のいずれかに記載の低起泡性室温硬化型オルガノポリシロキサン組成物の製造方法。
〔６〕
前記（Ａ）成分及び（Ｂ）成分を混合し、これに（Ｃ）成分を減圧下に混合し、更に（Ｄ）成分を減圧下に混合、反応させるか、又は（Ａ）成分及び（Ｂ）成分を混合した後、これに（Ｃ）成分及び（Ｄ）成分を加え、減圧下に混合、反応させることによって、（Ａ）成分の末端シラノール基を（Ｃ）成分のアルコキシ基によって少なくとも部分的にアルコキシシリル化した後、次いで（Ｅ）成分を減圧下で混合することによって（Ａ）成分中の残余の未反応シラノール基を（Ｅ）成分のアルコキシ基と反応させ、その後、（Ｆ）成分、（Ｇ）成分及び（Ｈ）成分を減圧下で混合する〔１〕〜〔５〕のいずれかに記載の低起泡性室温硬化型オルガノポリシロキサン組成物の製造方法。
〔７〕
〔１〕〜〔６〕のいずれかに記載の方法により製造された低起泡性室温硬化型オルガノポリシロキサン組成物を硬化させる工程を含んでなる自動車オイルシールの製造方法。 Accordingly, the present invention provides the following method for producing a low-foaming room temperature curable organopolysiloxane composition and a method for producing an automobile oil seal.
[1]
(A) 100 parts by mass of an organopolysiloxane represented by the following general formula (1),
HO (SiR ¹ ₂ O) _a H (1)
(Wherein R ¹ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ¹ may be the same or different from each other. A is an integer of 10 or more. is there.)
(B) 1 to 500 parts by mass of at least one inorganic filler,
(C) At least one selected from ketene silyl acetal type compounds represented by the following general formula (2), 2-methyl dialkoxysilyl propionic acid esters represented by the following general formula (3), and partial hydrolysates thereof: 0.1-20 parts by weight of compound,
(R ² O) ₂ Si (R ³ ) OC (OR ³ ) = CHCH ₃ (2)
(R ² O) ₂ Si (CH ₃ ) CH (CH ₃ ) COOR ³ (3)
(Wherein R ² is an alkyl group having 1 to 4 carbon atoms, R ³ is an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms, and R ² and R ³ may be the same or different from each other. It may be a group of
(D) 0.01 to 20 parts by mass of a non-silicon organic compound and / or an organosilicon compound having at least one guanidine skeleton in the molecule;
(E) 0.2-5 parts by mass of a partially hydrolyzed condensate of a silane compound represented by the following general formula (4)
R ⁴ _b Si (X) _4-b (4)
(In the formula, R ⁴ is a methyl group or a vinyl group, X is an alkoxy group, and b is 0 or 1.)
(F) 1-30 parts by mass of a silane compound having three or more ketoxime groups represented by the following general formula (5) in one molecule;
R ⁵ _d Si (ON = CR ⁶ ₂ ) _4-d (5)
(Wherein R ⁵ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ⁶ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms. d is 0 or 1.)
(G) 0.05 to 10 parts by mass of a silane coupling agent represented by the following general formula (6) and / or a partial hydrolysis condensate thereof,
R ⁷ _e Si (OR ⁸ ) _4-e (6)
(In the formula, R ⁷ is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain an atom selected from a nitrogen atom, a sulfur atom and an oxygen atom other than R ⁴ , and is at least one of R ^7. Is a monovalent hydrocarbon group having 1 to 20 carbon atoms and containing at least one atom selected from a nitrogen atom, a sulfur atom and an oxygen atom, and R ⁸ is an unsubstituted or substituted monovalent carbon atom having 1 to 10 carbon atoms. A hydrogen group, and e is 1, 2 or 3.)
(H) Curing catalyst In the manufacturing method of the organopolysiloxane composition containing 0.001 to 10 parts by mass as an essential component, before the step of adding and mixing the component (F) in the composition, the component (C) and (D) The manufacturing method of the low-foaming room temperature curing organopolysiloxane composition characterized by including the process of adding and disperse-mixing a component.
[2]
The low-foaming room-temperature-curing organo described in [1], wherein at least one inorganic filler as the component (B) is selected from calcium carbonate, fumed silica, precipitated silica, and aluminum oxide. A method for producing a polysiloxane composition.
[3]
(C) component is a mixture of a 2-methyl dialkoxysilyl propionic acid ester represented by the above general formula (3) and a ketene silyl acetal type compound represented by the above general formula (2) which is a structural isomer thereof, Or the manufacturing method of the low foaming room temperature curing organopolysiloxane composition of [1] or [2] which is the partial hydrolyzate.
[4]
(E) The component according to any one of [1] to [3], wherein the alkoxy group of the component is a methoxy group and the specific gravity at 23 ° C. is in the range of 1.04 to 1.25. A method for producing a foamable room temperature curable organopolysiloxane composition.
[5]
The silane coupling agent of component (G) is represented by the following general formula (7)

(Wherein R ⁸ is as described above, R ⁹ is an unsubstituted monovalent hydrocarbon group having 1 to ¹⁰ carbon atoms, R ¹⁰ is a divalent hydrocarbon group having 1 to ¹⁰ carbon atoms, ¹¹ is a divalent hydrocarbon group having 7 to 10 carbon atoms including an aromatic ring, and p is an integer of 1 to 3, provided that at least one of the NH group and the NH ₂ group is directly connected to the aromatic ring of R ^11. Not.)
The method for producing a low-foaming room temperature-curable organopolysiloxane composition according to any one of [1] to [4], wherein the silane compound is represented by the formula:
[6]
The component (A) and the component (B) are mixed, the component (C) is mixed under reduced pressure, and the component (D) is further mixed and reacted under reduced pressure, or the components (A) and (B (C) component and (D) component are added to this, and then mixed and reacted under reduced pressure, so that the terminal silanol group of (A) component is at least partially formed by the alkoxy group of (C) component. After the alkoxysilylation, the remaining unreacted silanol group in the component (A) is reacted with the alkoxy group in the component (E) by mixing the component (E) under reduced pressure, and then (F) The method for producing a low-foaming room temperature-curable organopolysiloxane composition according to any one of [1] to [5], wherein the component, the component (G) and the component (H) are mixed under reduced pressure.
[7]
[1] to a method of manufacturing method of an automobile oil seal comprising the step of curing the low foaming room temperature curing organopolysiloxane compositions prepared by according to any one of [6].

  According to the method for producing a low-foaming room-temperature-curable organopolysiloxane composition of the present invention, a target composition can be obtained at low cost, and the curability equivalent to that of an oxime type that has been conventionally used. Even when dispersed or dissolved in a continuously variable transmission oil and automatic transmission oil for automobiles, it is less likely to promote foaming. Useful as a sealing material.

Hereinafter, the present invention will be described in more detail.
The component (A) of the room temperature curable organopolysiloxane composition used in the present invention is represented by the following general formula (1), the main chain is composed of repeating diorganosiloxane units, and both ends of the molecular chain are silicon atoms. It is a linear diorganopolysiloxane blocked with a bonded hydroxyl group (silanol group) and acts as the main agent (base polymer) of the composition of the present invention.
HO (SiR ¹ ₂ O) _a H (1)
(Wherein R ¹ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ¹ may be the same or different from each other. A is an integer of 10 or more. is there.)

In the above formula (1), R ¹ is from 1 to 10 carbon atoms, in particular unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms, such as methyl group, ethyl group, propyl group, butyl group, Alkyl groups such as hexyl group and octyl 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 phenyl group and tolyl group; benzyl group, Examples include aralkyl groups such as phenylethyl groups, or groups in which the hydrogen atoms of these groups are partially substituted with halogen atoms such as chlorine, fluorine, bromine, etc., such as trifluoropropyl groups. A methyl group is preferable, and a methyl group is particularly preferable. R ¹ may be the same group or a different group.

In the formula (1), a is an integer of 10 or more (usually 10 to 2,000), preferably 20 to 1,000, more preferably about 50 to 500, and the organopolysiloxane at 23 ° C. The viscosity is preferably in the range of 1,000 to 500,000 mPa · s, particularly preferably in the range of 5,000 to 100,000 mPa · s. In the present invention, the viscosity is a value measured by a rotational viscometer (for example, BL type, BH type, BS type, cone plate type, etc.). In the present invention, the degree of polymerization (or molecular weight) is, for example, a polystyrene-reduced weight average degree of polymerization (or weight average molecular weight) in gel permeation chromatography (GPC) analysis using toluene, tetrahydrofuran (THF) or the like as a developing solvent. And so on.
(A) The organopolysiloxane of a component may be 1 type and may use 2 or more types together.

Next, the at least one inorganic filler as the component (B) is a reinforcing or non-reinforcing filler for imparting rubber physical properties to the composition. As this filler, silica-based fillers such as surface-treated or untreated dry silica such as calcined silica and fumed silica, wet silica such as precipitated silica and sol-gel silica, carbon powder, talc and bentonite , Surface treated or untreated calcium carbonate, zinc carbonate, magnesium carbonate, surface treated or untreated calcium oxide, zinc oxide, magnesium oxide, aluminum oxide, aluminum hydroxide, etc., among which calcium carbonate, fumed silica Precipitating silica and aluminum oxide are preferable, and calcium carbonate, fumed silica, precipitating silica, and aluminum oxide are more preferable because the surface of the inorganic filler is hydrophobized and has a low water content.
The type, amount and treatment method of the surface treatment agent are not particularly limited, but typically, organosilicon compounds such as chlorosilane, alkoxysilane, organosilazane, fatty acid, paraffin, silane coupling agent, Treatment agents such as titanium coupling agents can be applied.

(B) The compounding quantity of a component is the range of 1-500 mass parts with respect to 100 mass parts of organopolysiloxane of (A) component, Preferably it is the range of 20-300 mass parts. If it is less than 1 part by mass, sufficient rubber strength cannot be obtained, so that there is a problem that it is not suitable for the intended use. If it exceeds 500 parts by mass, the dischargeability from the cartridge is deteriorated and the storage stability is reduced. The mechanical properties of the rubber properties are also reduced.
(B) The inorganic filler of a component may be 1 type and may use 2 or more types together.

Next, the ketene silyl acetal type compound represented by the following general formula (2) of the component (C), the 2-methyl dialkoxysilyl propionic acid ester represented by the following general formula (3), or a partial hydrolyzate thereof, In the present composition, it is an essential component for alkoxylating (alkoxysilylation) both ends (silanol groups) of the component (A). Here, it is essential that the component (C) is added to the component (A) before the component (F) together with the component (D) described later, and dispersed and mixed until it becomes sufficiently uniform.
(R ² O) ₂ Si (R ³ ) OC (OR ³ ) = CHCH ₃ (2)
(R ² O) ₂ Si (CH ₃ ) CH (CH ₃ ) COOR ³ (3)
(Wherein R ² is an alkyl group having 1 to 4 carbon atoms, R ³ is an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms, and R ² and R ³ may be the same or different from each other. It may be a group of

In the above formulas (2) and (3), the alkyl group having 1 to 4 carbon atoms of R ² may be any of linear, cyclic and branched, for example, methyl group, ethyl group, propyl group, n -A butyl group, an isopropyl group, a tert-butyl group, a sec-butyl group, and an isobutyl group are mentioned. R ² is preferably a methyl group or an ethyl group, and more preferably a methyl group. R ² may be the same or different.

In addition, the unsubstituted or substituted alkyl group having 1 to 12 carbon atoms, particularly 1 to 8 carbon atoms of R ³ may be any of linear, cyclic and branched, for example, methyl group, ethyl group, propyl Group, n-butyl group, hexyl group, heptyl group, octyl group, nonyl group, linear alkyl group such as decyl group, cyclic alkyl group such as cyclohexyl group, and tert-butyl group, 2-ethylhexyl group, etc. Branched alkyl groups of these groups, halogen-substituted alkyl groups such as chloromethyl groups, bromoethyl groups, trifluoropropyl groups, etc., in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as chlorine, fluorine, bromine, etc. Can be mentioned. R ³ is preferably a methyl group, an ethyl group, an n-butyl group, or a 2-ethylhexyl group, and more preferably a 2-ethylhexyl group. R ³ may be the same or different.

The (K) component ketene silyl acetal type compound, 2-methyl dialkoxysilyl propionic acid ester or partial hydrolyzate thereof can be used alone or in combination of two or more.
Note that the ketene silyl acetal type compound represented by the general formula (2) and the 2-methyl dialkoxysilyl propionic acid ester represented by the general formula (3) are in a structural isomer relationship with each other. , Present as a mixture of these.

  The component (C) is used in an amount of 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, based on 100 parts by mass of the organopolysiloxane of the component (A). If the blending amount of the component (C) is too small, both ends (silanol groups) of the component (A) cannot be alkoxylated (alkoxysilylated), so the storage stability and appearance of the composition deteriorates, The viscosity of the composition increases. On the other hand, if the amount of component (C) is too large, the curing time is delayed, the mechanical properties of the resulting rubber are inferior, and the cost is disadvantageous.

  Next, the non-silicon-based organic compound having at least one guanidine skeleton in the molecule of the component (D) and / or the organosilicon compound such as organosilane and organopolysiloxane are the components (A) and (C). Is an essential component as a catalyst for efficiently modifying the terminal in a short time. When the component (D) is blended into the composition, the component (C) and the component (D) are always added to the component (A) before the step of adding the component (F) and are sufficiently uniform. It is essential to disperse and mix until.

（式中、Ｍｅはメチル基である。） Here, the guanidine skeleton is represented by the following general formula (8).

(In the formula, Me is a methyl group.)

  Specific examples of the non-silicon organic compound and the organosilicon compound having at least one guanidine skeleton in the molecule of component (D) include inorganic guanidines such as guanidine hydrochloride, guanidine carbonate, guanidine nitrate, guanidine sulfate, and guanidine phosphate. , Aminoguanidine, 1,1,3,3-tetramethylguanidine, n-dodecylguanidine, methylolguanidine, dimethylolguanidine, 1-phenylguanidine, 1,3-diphenylguanidine, 1,3-di-o-tolyl Organic guanidines such as guanidine, triphenylguanidine, 1-benzyl-2,3-dimethyl, cyanoguanidine, 1,1,3,3-tetramethyl-2- [3- (trimethoxysilyl) propyl] guanidine, etc. Alkoxysilanes and their hydrolysis condensates (siloxa S), and the like. Among these, organic guanidines are preferably used, and among them, 1,1,3,3-tetramethyl-2- [3- (trimethoxysilyl) propyl] guanidine and its hydrolysis condensate are particularly used. preferable.

The non-silicon-based organic compound and / or organosilicon compound having at least one guanidine skeleton in the molecule is 0.01 to 20 parts by weight, preferably 100 parts by weight of the organopolysiloxane of component (A), preferably It is used in the range of 0.1 to 10 parts by mass. If the blending amount is too small, both ends (silanol groups) of the component (A) are sufficiently alkoxylated (alkoxysilylation) with the component (C). If the amount is too large, the odor and storage stability deteriorate.
As the component (D), the guanidine skeleton-containing non-silicon-based organic compound and / or the organosilicon compound may be used singly or in combination of two or more.

Next, the partially hydrolyzed condensate of the (organo) silane compound represented by the following general formula (4), which is the component (E), improves the crosslink density of the composition and has good chemical resistance (particularly, It is an essential component as a crosslinking agent for imparting engine oil resistance, ATF resistance, and LLC resistance.
R ⁴ _b Si (X) _4-b (4)
(In the formula, R ⁴ is a methyl group or a vinyl group, X is an alkoxy group, and b is 0 or 1.)

  In the above formula (4), examples of the alkoxy group of X include C1-C6, particularly C1-C4 alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and a methoxy group is preferable. .

  The component (E) is a partially hydrolyzed condensate of (organo) alkoxysilane having 3 or 4 alkoxy groups in a molecule as a hydrolyzable group, and the alkoxy group is more preferably a methoxy group. . This is because the ketoxime group, acetoxy group, and isopropenoxy group are too hydrolyzable with moisture, causing gelation and viscosity increase during the production of this composition. When a part of the alkoxy group slowly undergoes a transesterification reaction with the oxime group of the component (F), the alkoxy group and the oxime group are interchanged to achieve quick curability, and the alkoxy group is a methoxy group. When the room temperature curable organopolysiloxane composition is crosslinked, the component (E) can be quickly introduced as a crosslinking point, so that excellent chemical resistance can be imparted.

Component (E) preferably has a specific gravity at 23 ° C. in the range of 1.04 to 1.25, more preferably in the range of 1.06 to 1.10. If the specific gravity at 25 ° C. is less than 1.04, sufficient fast curability and chemical resistance cannot be imparted, and the composition having the desired rubber elasticity may not be obtained. On the other hand, if the specific gravity at 23 ° C. exceeds 1.25, the number of cross-linking points increases, so that the mechanical properties of the obtained rubber properties may be deteriorated. Specific gravity can be measured by a buoyancy method.
In the present invention, the partially hydrolyzed condensate means a hydrolyzable group remaining in the molecule (alkoxy in the case of the component (E)) produced by partially hydrolyzing and condensing a hydrolyzable silane compound. Means a siloxane oligomer having at least 2, preferably 3 or more groups. Moreover, although there is no upper limit in particular in the number of remaining hydrolysable groups, in the case of (E) component, it is preferable that the specific gravity of a partial hydrolysis condensate satisfies the said range.

The component (E) is used in the range of 0.2 to 5 parts by mass, preferably in the range of 1 to 3 parts by mass, with respect to 100 parts by mass of the organopolysiloxane of the component (A). Is. If the amount of the component (E) is too small, good chemical resistance cannot be obtained. If the amount is too large, the crosslinking density becomes too high, and the mechanical properties of the cured product (silicone rubber) are deteriorated.
(E) The partial hydrolysis-condensation product of the (organo) silane compound of a component may be 1 type, and may use 2 or more types together.

Next, the (organo) silane compound having 3 or more ketoxime groups represented by the following general formula (5), which is the component (F), is good in the resulting composition under hermetic conditions. It is a component generally called a curing agent for imparting excellent storage stability and reacting with moisture in the air after opening to make it rubber. Here, it is essential that the component (F) is added to the component (A) after the component (C) and the component (D).
R ⁵ _d Si (ON = CR ⁶ ₂ ) _4-d (5)
(Wherein R ⁵ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ⁶ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms. d is 0 or 1.)

In the above formula (5), R ⁵ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and is the same as R ^{1 in} the above formula (1). In particular, a methyl group, a vinyl group, and a phenyl group are preferable.
Further, R ⁶ is from 1 to 10 carbon atoms, preferably an unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms, the same as R ¹ of formula (1) above in the same manner as R ⁵ In particular, those selected from a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group are preferable.
R ⁵ and R ⁶ may be the same group or different groups.

  Specific examples of the component (F) silane compound include methyltris (dimethylketoxime) silane, methyltris (methylethylketoxime) silane, methyltris (methylisobutylketoxime) silane, methyltris (methylpropylketoxime) silane, methyltris (methylbutyl). Ketoxime) silane, vinyltris (methylethylketoxime) silane, vinyltris (dimethylketoxime) silane, vinyltris (methylisobutylketoxime) silane, vinyltris (methylpropylketoxime) silane, vinyltris (methylbutylketoxime) silane, tetra (methylethylketo) Examples include ketoxime silanes such as oxime) silane and tetra (methyl isobutyl ketoxime) silane. It may be used in combination of two or more.

The (organo) silane compound as the component (F) is used in an amount of 1 to 30 parts by weight, preferably 3 to 20 parts by weight, based on 100 parts by weight of the organopolysiloxane of the component (A). If the amount is less than 1 part by mass, sufficient crosslinking cannot be obtained, and the composition does not have the desired rubber elasticity. If the amount exceeds 30 parts by mass, the mechanical properties of the obtained rubber properties are deteriorated.
As the component (F), the (organo) silane compound may be used alone or in combination of two or more.

Next, the component (G) is a silane coupling agent represented by the following general formula (6) and / or a partial hydrolysis condensate thereof, and is an essential component for causing the composition to exhibit good adhesiveness. is there.
R ⁷ _e Si (OR ⁸ ) _4-e (6)
(In the formula, R ⁷ is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain an atom selected from a nitrogen atom, a sulfur atom and an oxygen atom other than R ⁴ , and is at least one of R ^7. Is a monovalent hydrocarbon group having 1 to 20 carbon atoms and containing at least one atom selected from a nitrogen atom, a sulfur atom and an oxygen atom, and R ⁸ is an unsubstituted or substituted monovalent carbon atom having 1 to 10 carbon atoms. A hydrogen group, and e is 1, 2 or 3.)

In the above formula (6), R ⁷ is a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain an atom selected from a nitrogen atom, a sulfur atom and an oxygen atom other than R ⁴ described above. Is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group or a hexyl group; a cycloalkyl group such as a cyclohexyl group; an alkenyl group such as a vinyl group, an allyl group, a propenyl group, a butenyl group or a hexenyl group; Aryl groups such as tolyl group and p-styryl group; unsubstituted monovalent hydrocarbon groups having 1 to 10 carbon atoms, such as aralkyl groups such as benzyl group and phenylethyl group, particularly 1 to 6 carbon atoms, β- (2 , 3-epoxycyclohexyl) ethyl group, β- (3,4-epoxycyclohexyl) ethyl group, γ-glycidoxypropyl group, γ- (meth) acryloxypropyl group, γ-acryloxypro Group, N-β (aminoethyl) -γ-aminopropyl group, γ-aminopropyl group, N-phenyl-γ-aminopropyl group, γ-ureidopropyl group, γ-mercaptopropyl group, γ-isocyanatopropyl group And a monovalent hydrocarbon group having 3 to 20 carbon atoms, particularly 8 to 14 carbon atoms, containing at least one atom selected from a nitrogen atom, a sulfur atom, and an oxygen atom. Incidentally, at least one of R ⁷ is a nitrogen atom, a monovalent hydrocarbon group having 1 to 20 carbon atoms containing at least one atom selected from a sulfur atom and an oxygen atom.

R ⁸ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, and examples thereof are the same as those for R ^{1 in} the above formula (1). Group, ethyl group, propyl group and isopropyl group are preferred.

（式中、Ｒ⁸は上記の通りであり、Ｒ⁹は炭素数１〜１０の非置換一価炭化水素基であり、Ｒ¹⁰は炭素数１〜１０の二価炭化水素基であり、Ｒ¹¹は芳香環を含む炭素数７〜１０の二価炭化水素基であり、ｐは１〜３の整数である。但し、ＮＨ基及びＮＨ₂基の少なくとも一方はＲ¹¹の芳香環に直結していない。） As specific examples of the hydrolyzable silane coupling agent of component (G), a large number of silane coupling agents can be exemplified, and among these, at least an atom selected from a nitrogen atom, a sulfur atom and an oxygen atom It is preferable that it is a silane compound containing one C1-C20 monovalent hydrocarbon group containing one, Among these, especially the silane compound or its partial hydrolysis-condensation product shown by following General formula (7) is shown. When used, the adhesion and chemical resistance are further improved.

(Wherein R ⁸ is as described above, R ⁹ is an unsubstituted monovalent hydrocarbon group having 1 to ¹⁰ carbon atoms, R ¹⁰ is a divalent hydrocarbon group having 1 to ¹⁰ carbon atoms, ¹¹ is a divalent hydrocarbon group having 7 to 10 carbon atoms including an aromatic ring, and p is an integer of 1 to 3, provided that at least one of the NH group and the NH ₂ group is directly connected to the aromatic ring of R ^11. Not.)

The silane compound represented by the formula (7) has an NH group (imino group) and an NH ₂ group (amino group), includes an aromatic ring between the NH group and the NH ₂ group, and further includes an NH group This is an alkoxysilane compound in which at least one of the NH ₂ groups is not directly connected to the carbon atom constituting the aromatic ring, and is described in detail in JP-A-5-105689.

In the formula (7), R ⁸ is the same as R ⁸ in formula (6) described above, the same ones can be exemplified, it is preferable that among them methyl group or an ethyl group.
In addition, examples of the unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms of R ⁹ include alkyl groups such as methyl group, ethyl group, propyl group, butyl group, and hexyl group; cyclohexyl group and the like Cycloalkyl groups; vinyl groups, allyl groups, propenyl groups, butenyl groups, hexenyl groups and other alkenyl groups; phenyl groups, tolyl groups and other aryl groups; benzyl groups, phenylethyl groups and other aralkyl groups, and the like. Groups are preferred.

Examples of the divalent hydrocarbon group having 1 to ¹⁰ carbon atoms of R ¹⁰ include methylene group, ethylene group, propylene group, tetramethylene group, hexamethylene group, octamethylene group, decamethylene group, and 2-methylpropylene group. Examples thereof include an arylene group such as an alkylene group and a phenylene group, and a group in which the alkylene group and the arylene group are bonded, and a methylene group, an ethylene group, and a propylene group are preferable, and a propylene group is particularly preferable.

As the divalent hydrocarbon group having 7 to 10 carbon atoms containing an aromatic ring of R ^11, a group phenylene group and an alkylene group are bonded are preferred, include, for example, those represented by the following formula.
—C ₆ H ₄ —CH ₂ —
_{-C 6 H 4 -CH 2 -CH 2} -
_{-C 6 H 4 -CH 2 -CH 2} -CH 2 -
—CH ₂ —C ₆ H ₄ —
—CH ₂ —C ₆ H ₄ —CH ₂ —
—CH ₂ —C ₆ H ₄ —CH ₂ —CH ₂ —
_{-CH 2 -C 6 H 4 -CH 2} -CH 2 -CH 2 -
—CH ₂ —CH ₂ —C ₆ H ₄ —
—CH ₂ —CH ₂ —C ₆ H ₄ —CH ₂ —
_{-CH 2 -CH 2 -C 6 H 4} -CH 2 -CH 2 -
—CH ₂ —CH ₂ —CH ₂ —C ₆ H ₄ —
_{-CH 2 -CH 2 -CH 2 -C 6} H 4 -CH 2 -
Of these, —CH ₂ —C ₆ H ₄ —CH ₂ — is particularly preferred.

In this case, the alkylene group bonded to the right side of the phenylene group (NH ₂ side in Formula (7)) (when there is no alkylene group, it is —NH ₂ group) may be in the ortho position, meta position, or para position. Good.

The following are illustrated as a silane compound shown by the said General formula (7).

The blending amount of the component (G) is 0.05 to 10 parts by weight, preferably 0.07 to 5 parts by weight, particularly preferably 0 with respect to 100 parts by weight of the organopolysiloxane of the component (A). 0.1 to 3 parts by mass. If it is less than 0.05 part by mass, the cured product will not exhibit sufficient adhesion performance, and if it exceeds 10 parts by mass, the rubber strength after curing will decrease and it will be difficult to obtain the desired rubber elastic body. Disadvantageous.
As the component (G), the silane coupling agent and / or the partial hydrolysis condensate thereof may be used alone or in combination of two or more.

  Next, the curing catalyst of component (H) is generally called a curing catalyst, which is used to promote the hydrolysis reaction between the present composition and moisture in the air. It is preferable to use components similar to those used in silicone resin compositions that cure in the presence of moisture, well known in the art.

  Examples of the component (H) include a tin-based catalyst, a bismuth-based catalyst, and a titanium-based catalyst, and it is more preferable to use a tin-based catalyst and a bismuth-based catalyst. Specific examples of tin-based catalysts include tin naphthenate, tin caprylate, dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltin diacetate, diphenyltin diacetate, dibutyltin oxide, dibutyltin dimethoxide, dibutylbis (triethoxysiloxy) ) Tin, dibutyltin benzyl malate, dioctyltin diversate, etc. Specific examples of bismuth-based catalysts include bismuth tris (2-ethylhexanoate) or bismuth tris (neodecanoate) Can do. Specific examples of titanium-based catalysts include tetraisopropoxytitanium, tetra-n-butoxytitanium, tetrabis (2-ethylhexoxy) titanium, dipropoxybis (acetylacetona) titanium, and titanium isopropoxyoctylene glycol. And titanium chelate compounds.

The amount of the curing catalyst used may be a very small amount of catalyst, and is in the range of 0.001 to 10 parts by mass, preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the organopolysiloxane of component (A). When the amount is less than 0.001 part by mass, good curability cannot be obtained, and therefore, there is a problem in that time is extended until, for example, engine oil is injected at the time of manufacturing an automobile or the like. On the other hand, if the amount exceeds 10 parts by mass, the curability of the composition is too fast, so that the allowable range of the time for adhering the adherend after application of the composition is shortened or the mechanical properties of the resulting rubber are reduced.
(H) The curing catalyst of a component may be 1 type and may use 2 or more types together.

  Moreover, in the composition used for this invention, you may use the additive generally known besides the said component in the range which does not impair the objective of this invention. Additives include polyethers as thixotropic agents, silicone oils as plasticizers, isoparaffins, etc., if necessary, colorants such as pigments, dyes, fluorescent brighteners, fungicides, antibacterial agents , Bioactive additives such as marine organism repellent, phenyl silicone oil as bleed oil, fluorosilicone oil, surface modifiers such as organic liquid incompatible with silicone, toluene, xylene, solvent volatile oil, cyclohexane, methyl Solvents such as cyclohexane and low boiling point isoparaffin can also be added.

[Manufacturing process]
In order to obtain a low-foaming room-temperature-curing organopolysiloxane composition having the same curability as the oxime type and excellent in chemical resistance as described above, the component (C) and the component (D) must be ) It is essential to add to the composition prior to the addition of the component and disperse and mix until it is sufficiently uniform. That is, in the production process of the composition, the component (F) is added and mixed into the composition. Before the step of performing, the step (C) and the component (D) are added to the component containing the component (A) and dispersed and mixed until sufficiently uniform.

  This is because the terminal hydroxyl group (silanol group) of organopolysiloxane (A) is reacted to some extent with the alkoxysilane compound (C) and the terminal is alkoxylated to reduce the terminal reactivity. This is because the reaction with components contained in oil and automatic transmission oil can be suppressed. The component (C) and the component (D) added before the component (F) may be added individually or jointly (simultaneously) in the component containing the component (A), and after the addition, It is essential to disperse and mix until uniform.

  Here, ideally, dispersion means that the internally added components are preferably dispersed uniformly, but a method for confirming this takes time. Therefore, mixing the internally added components added in an appropriate mixer at a certain rotation speed (rpm) for a certain period of time was defined as “dispersion”. The dispersion (number of rotations) is preferably mixed for about 1 minute or more at a rotational speed of 2 rpm or more, more preferably mixed for about 5 minutes or more at a rotational speed of 5 rpm or more.

  The essential components other than the (C) component, the (D) component, and the (F) component are not particularly limited in the order of addition. For example, the (A) component and the (B) component are mixed, The component (C) is mixed under reduced pressure and the component (D) is further mixed and reacted under reduced pressure, or the components (A) and (B) are mixed, and then the components (C) and (C) are mixed. Add component D, mix and react under reduced pressure to at least partially alkoxysilylate the terminal silanol group of component (A) with the alkoxy group of component (C), then reduce component (E) under reduced pressure The remaining unreacted silanol group in the component (A) is reacted with the alkoxy group in the component (E) by mixing below, and then the components (F), (G) and (H) are reduced under reduced pressure. A method of mixing is preferred. In this case, the reduced pressure can be about -0.01 to -0.1 MPa.

  The room temperature curable organopolysiloxane composition of the present invention can be obtained by mixing the above components (A) to (H) and various additives as necessary in a state where moisture is blocked. The obtained composition is stored as it is in a sealed container, and is cured into a rubber-like elastic body by being exposed to moisture in the air at the time of use. Application to and use in a so-called one-packaging room temperature curable organopolysiloxane composition It can be used as a so-called two-packaging room temperature curable organopolysiloxane composition that is sometimes cured with a rubber-like elastic body by mixing with other components.

  The room temperature curable organopolysiloxane composition produced by this production method is suitably used as an automobile oil seal. The automobile oil seal is provided as a structure sealed or bonded with a cured product of the room temperature curable organopolysiloxane composition, and examples of such a structure include transport equipment such as automobiles. Moreover, FIPG (Formed In Place Gaskets) etc. are mentioned as a form of a seal | sticker or adhesion | attachment.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In all of the examples and comparative examples, a planetary mixer (manufactured by Inoue Seisakusho Co., Ltd.) was used as an appropriate mixer. In addition, physical properties such as viscosity (measured by a rotational viscometer) not particularly described in the following examples are values at 23 ° C.

[Example 1]
(A) To 100 parts by mass of polydimethylsiloxane whose end at 25 ° C. has a viscosity of 5,000 mPa · s blocked with a silanol group, (B) heavy calcium carbonate with no surface treatment (trade name; Whiteon SSB, Shiroishi 140 parts by mass of calcium (made by Co., Ltd.), (B) 40 parts by mass of colloidal calcium carbonate whose surface is treated with fatty acid (trade name; Shiraka Hana CC-R, produced by Shiraishi Calcium Co., Ltd.), and (B) After adding 8 parts by mass of fumed silica whose surface was treated with dimethyldichlorosilane and mixing, (C) 2-ethylhexyl 2-methyldimethoxysilylpropionate, which is a reaction product of 2-ethylhexyl acrylate and dimethoxymethylsilane, and its 4 parts by mass of a mixture with a ketene silyl acetal type isomer (trade name: OCMS-2, manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and the mixture was subjected to reduced pressure. 0.05 MPa or less, the same shall apply hereinafter) and (D) 0.1 part by mass of (D) 1,1,3,3-tetramethyl-2- [3- (trimethoxysilyl) propyl] guanidine was added. After mixing and reacting under reduced pressure, 2 parts by mass of (E) methyltrimethoxysilane partially hydrolyzed condensate (trade name; KC-89E, manufactured by Shin-Etsu Chemical Co., Ltd., specific gravity: 1.08) In addition, they were mixed and reacted under reduced pressure. Thereafter, (F) 9 parts by mass of vinyltris (methylethylketoxime) silane and (G) a compound obtained by dehydrochlorination reaction of xylylenediamine and 3-chloropropyltrimethoxysilane (trade name; CF-73, Shin-Etsu Chemical Co., Ltd.) (Made by Co., Ltd.) 0.3 parts by mass and (H) dioctyltin diversate 0.08 parts by mass were added and mixed thoroughly under reduced pressure to obtain Composition 1. ((C) component, (D) component added alone, added and dispersed before (F) component)

[Example 2]
(A) To 100 parts by mass of polydimethylsiloxane whose end at 25 ° C. has a viscosity of 5,000 mPa · s blocked with a silanol group, (B) heavy calcium carbonate with no surface treatment (trade name; Whiteon SSB, Shiroishi 140 parts by mass of calcium (made by Co., Ltd.), (B) 40 parts by mass of colloidal calcium carbonate whose surface is treated with fatty acid (trade name; Shiraka Hana CC-R, produced by Shiraishi Calcium Co., Ltd.), and (B) After adding 8 parts by mass of fumed silica whose surface was treated with dimethyldichlorosilane and mixing, (C) 2-ethylhexyl 2-methyldimethoxysilylpropionate, which is a reaction product of 2-ethylhexyl acrylate and dimethoxymethylsilane, and its 4 parts by mass of a mixture with a ketene silyl acetal type isomer (trade name: OCMS-2, manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and the mixture was subjected to reduced pressure. After thoroughly mixing, 0.1 parts by mass of (D) 1,1,3,3-tetramethyl-2- [3- (trimethoxysilyl) propyl] guanidine was added, and the mixture was reacted under reduced pressure. (E) 2 parts by mass of methyltrimethoxysilane partially hydrolyzed condensate (trade name: KC-89E, manufactured by Shin-Etsu Chemical Co., Ltd., specific gravity: 1.08), and mixed and reacted under reduced pressure. . Then, 9 parts by mass of (F) vinyltris (methylethylketoxime) silane, 0.3 part by mass of (G) 3-aminopropyltrimethoxysilane, and 0.08 part by mass of (H) dioctyltin diversate are added, Mixing was completed under reduced pressure to obtain Composition 2. ((C) component, (D) component added alone, added and dispersed before (F) component)

[Example 3]
(A) To 100 parts by mass of polydimethylsiloxane whose end at 25 ° C. has a viscosity of 5,000 mPa · s blocked with a silanol group, (B) heavy calcium carbonate with no surface treatment (trade name; Whiteon SSB, Shiroishi 140 parts by mass of calcium (made by Co., Ltd.), (B) 40 parts by mass of colloidal calcium carbonate whose surface is treated with fatty acid (trade name; Shiraka Hana CC-R, produced by Shiraishi Calcium Co., Ltd.), and (B) After adding 8 parts by mass of fumed silica whose surface was treated with dimethyldichlorosilane and mixing, (C) 2-ethylhexyl 2-methyldimethoxysilylpropionate, which is a reaction product of 2-ethylhexyl acrylate and dimethoxymethylsilane, and its 4 parts by mass of a mixture with a ketene silyl acetal type isomer (trade name; OCMS-2, manufactured by Shin-Etsu Chemical Co., Ltd.), (D) 1, , 3,3-tetramethyl-2- [3- (trimethoxysilyl) propyl] guanidine 0.1 part by weight was added and allowed to be mixed under a reduced pressure reaction. Next, 2 parts by mass of (E) methyltrimethoxysilane partially hydrolyzed condensate (trade name; KC-89E, Shin-Etsu Chemical Co., Ltd., specific gravity: 1.08) was added, and the mixture was reacted under reduced pressure. Thereafter, (F) 9 parts by mass of vinyltris (methylethylketoxime) silane and (G) a compound obtained by dehydrochlorination reaction of xylylenediamine and 3-chloropropyltrimethoxysilane (trade name; CF-73, Shin-Etsu Chemical Co., Ltd.) (Made by Co., Ltd.) 0.3 parts by mass and (H) dioctyltin diversate 0.08 parts by mass were added and mixed thoroughly under reduced pressure to obtain composition 3. ((C) component and (D) component added together, added before (F) component and dispersed)

[Example 4]
(A) To 100 parts by mass of polydimethylsiloxane whose end at 25 ° C. has a viscosity of 5,000 mPa · s blocked with a silanol group, (B) heavy calcium carbonate with no surface treatment (trade name; Whiteon SSB, Shiroishi 140 parts by mass of calcium (made by Co., Ltd.), (B) 40 parts by mass of colloidal calcium carbonate whose surface is treated with fatty acid (trade name; Shiraka Hana CC-R, produced by Shiraishi Calcium Co., Ltd.), and (B) After adding 8 parts by mass of fumed silica whose surface was treated with dimethyldichlorosilane and mixing, (C) 2-ethylhexyl 2-methyldimethoxysilylpropionate, which is a reaction product of 2-ethylhexyl acrylate and dimethoxymethylsilane, and its 4 parts by mass of a mixture with a ketene silyl acetal type isomer (trade name: OCMS-2, manufactured by Shin-Etsu Chemical Co., Ltd.) was added, and the mixture was subjected to reduced pressure. Thoroughly mixed, further (D) 1,1,3,3-tetramethyl-2- [3- (trimethoxysilyl) propyl] guanidine 0.1 part by weight was added and allowed to be mixed under a reduced pressure reaction. Next, 2 parts by mass of (E) methyltrimethoxysilane partially hydrolyzed condensate (trade name; KC-89E, Shin-Etsu Chemical Co., Ltd., specific gravity: 1.08) was added, and the mixture was reacted under reduced pressure. Thereafter, (F) 9 parts by mass of vinyltris (methylethylketoxime) silane and (G) a compound obtained by dehydrochlorination reaction of xylylenediamine and 3-chloropropyltrimethoxysilane (trade name; CF-73, Shin-Etsu Chemical Co., Ltd.) (Made by Co., Ltd.) 0.3 parts by mass and (H) bismuth tris (neodecanoate) 0.08 parts by mass were added and thoroughly mixed under reduced pressure to obtain Composition 4. ((C) component, (D) component added alone, added and dispersed before (F) component)

[Comparative Example 1]
(A) To 100 parts by mass of polydimethylsiloxane whose end at 25 ° C. has a viscosity of 5,000 mPa · s blocked with a silanol group, (B) heavy calcium carbonate with no surface treatment (trade name; Whiteon SSB, Shiroishi 140 parts by mass of calcium (made by Co., Ltd.), (B) 40 parts by mass of colloidal calcium carbonate whose surface is treated with fatty acid (trade name; Shiraka Hana CC-R, produced by Shiraishi Calcium Co., Ltd.), and (B) After adding 8 parts by mass of fumed silica whose surface was treated with dimethyldichlorosilane and mixing, 9 parts by mass of (F) vinyltris (methylethylketoxime) silane was added, and the mixture was reacted under reduced pressure. Next, (C) a mixture of 2-ethylhexyl 2-methyldimethoxysilylpropionate, which is a reaction product of 2-ethylhexyl acrylate and dimethoxymethylsilane, and its ketene silyl acetal isomer (trade name; OCMS-2, Shin-Etsu) 4 parts by mass of Chemical Industry Co., Ltd.) was added and mixed under reduced pressure. Further, (D) 1,1,3,3-tetramethyl-2- [3- (trimethoxysilyl) propyl] guanidine 0 After adding 1 part by mass and mixing and reacting under reduced pressure, (E) a partially hydrolyzed condensate of methyltrimethoxysilane (trade name: KC-89E, manufactured by Shin-Etsu Chemical Co., Ltd., specific gravity; 08) Add 2 parts by mass, mix and react under reduced pressure, and (G) Compound obtained by dehydrochlorination reaction of xylylenediamine and 3-chloropropyltrimethoxysilane (trade name) CF-73, manufactured by Shin-Etsu Chemical Co.) and 0.3 part by weight, (H) and dioctyltin versatate 0.08 parts by weight was added to obtain a composition 5 was mixed thoroughly under reduced pressure. ((F) component added before (C) component, (D) component and dispersed)

[Comparative Example 2]
(A) To 100 parts by mass of polydimethylsiloxane whose end at 25 ° C. has a viscosity of 5,000 mPa · s blocked with a silanol group, (B) heavy calcium carbonate with no surface treatment (trade name; Whiteon SSB, Shiroishi 140 parts by mass of calcium (made by Co., Ltd.), (B) 40 parts by mass of colloidal calcium carbonate whose surface is treated with fatty acid (trade name; Shiraka Hana CC-R, produced by Shiraishi Calcium Co., Ltd.), and (B) After adding 8 parts by mass of fumed silica whose surface was treated with dimethyldichlorosilane and mixing, (F) 9 parts by mass of vinyltris (methylethylketoxime) silane and (C) a reaction product of 2-ethylhexyl acrylate and dimethoxymethylsilane A mixture of 2-ethylhexyl 2-methyldimethoxysilylpropionate and its ketene silyl acetal isomer (quotient Name: OCMS-2, manufactured by Shin-Etsu Chemical Co., Ltd.) 4 parts by mass, thoroughly mixed under reduced pressure, and (D) 1,1,3,3-tetramethyl-2- [3- (tri Methoxysilyl) propyl] guanidine (0.1 part by mass) was added, and the mixture was reacted under reduced pressure. Subsequently, (E) methyltrimethoxysilane partially hydrolyzed condensate (trade name: KC-89E, manufactured by Shin-Etsu Chemical Co., Ltd., specific gravity: 1.08) 2 parts by mass is added, and the mixture is reacted under reduced pressure. (G) 0.3 parts by mass of a compound (trade name; CF-73, manufactured by Shin-Etsu Chemical Co., Ltd.) obtained by dehydrochlorination reaction of xylylenediamine and 3-chloropropyltrimethoxysilane; H) Dioctyltin diversate 0.08 parts by mass was added and mixed thoroughly under reduced pressure to obtain Composition 6. ((F) component and (C) component are added together and dispersed)

[Comparative Example 3]
(A) To 100 parts by mass of polydimethylsiloxane whose end at 25 ° C. has a viscosity of 5,000 mPa · s blocked with a silanol group, (B) heavy calcium carbonate with no surface treatment (trade name; Whiteon SSB, Shiroishi 140 parts by mass of calcium (made by Co., Ltd.), (B) 40 parts by mass of colloidal calcium carbonate whose surface is treated with fatty acid (trade name; Shiraka Hana CC-R, produced by Shiraishi Calcium Co., Ltd.), and (B) After adding 8 parts by mass of fumed silica whose surface was treated with dimethyldichlorosilane and mixing, (F) 9 parts by mass of vinyltris (methylethylketoxime) silane and (C) a reaction product of 2-ethylhexyl acrylate and dimethoxymethylsilane A mixture of 2-ethylhexyl 2-methyldimethoxysilylpropionate and its ketene silyl acetal isomer (quotient Name: OCMS-2, manufactured by Shin-Etsu Chemical Co., Ltd.) 4 parts by mass and (D) 1,1,3,3-tetramethyl-2- [3- (trimethoxysilyl) propyl] guanidine 0.1 mass Part was added and mixed under reduced pressure to react. Subsequently, (E) methyltrimethoxysilane partially hydrolyzed condensate (trade name: KC-89E, manufactured by Shin-Etsu Chemical Co., Ltd., specific gravity: 1.08) 2 parts by mass is added, and the mixture is reacted under reduced pressure. (G) 0.3 parts by mass of a compound (trade name; CF-73, manufactured by Shin-Etsu Chemical Co., Ltd.) obtained by dehydrochlorination reaction of xylylenediamine and 3-chloropropyltrimethoxysilane; H) 0.08 part by mass of dioctyltin diversate was added and thoroughly mixed under reduced pressure to obtain composition 7. ((F) component, (C) component, (D) component are added together and dispersed)

[Comparative Example 4]
(A) To 100 parts by mass of polydimethylsiloxane whose end at 25 ° C. has a viscosity of 5,000 mPa · s blocked with a silanol group, (B) heavy calcium carbonate with no surface treatment (trade name; Whiteon SSB, Shiroishi 140 parts by mass of calcium (made by Co., Ltd.), (B) 40 parts by mass of colloidal calcium carbonate whose surface is treated with fatty acid (trade name; Shiraka Hana CC-R, produced by Shiraishi Calcium Co., Ltd.), and (B) After 8 parts by mass of fumed silica whose surface was treated with dimethyldichlorosilane was added and mixed, (F) 9 parts by mass of vinyltris (methylethylketoxime) silane and (D) 1,1,3,3-tetramethyl-2- 0.1 part by mass of [3- (trimethoxysilyl) propyl] guanidine was added, and the mixture was reacted under reduced pressure. Next, (C) a mixture of 2-ethylhexyl 2-methyldimethoxysilylpropionate, which is a reaction product of 2-ethylhexyl acrylate and dimethoxymethylsilane, and its ketene silyl acetal isomer (trade name; OCMS-2, Shin-Etsu) (Chemical Industry Co., Ltd.) 4 parts by mass, mixed and reacted under reduced pressure, (E) methyltrimethoxysilane partially hydrolyzed condensate (trade name; KC-89E, Shin-Etsu Chemical Co., Ltd.) Manufactured, specific gravity: 1.08) 2 parts by mass is added, mixed and reacted under reduced pressure, and (G) a compound obtained by dehydrochlorination reaction of xylylenediamine and 3-chloropropyltrimethoxysilane (trade name; (CF-73, manufactured by Shin-Etsu Chemical Co., Ltd.) 0.3 parts by mass and (H) dioctyltin diversate 0.08 parts by mass are added and mixed thoroughly under reduced pressure. 8 was obtained. ((F) component and (D) component are added together and dispersed)

[Comparative Example 5]
In Example 1, preparation was carried out under the same conditions except that (E) methyltrimethoxysilane (specific gravity; 0.95) was used instead of the partially hydrolyzed condensate of methyltrimethoxysilane (specific gravity; 1.08). Thus, a composition 9 was obtained.

[Comparative Example 6]
A composition 10 was obtained in the same manner as in Example 1 except that (D) 1,1,3,3-tetramethyl-2- [3- (trimethoxysilyl) propyl] guanidine was omitted. It was.

[Comparative Example 7]
The same procedure as in Example 1 except that (C) the mixture of 2-ethylhexyl 2-methyldimethoxysilylpropionate, which is a reaction product of 2-ethylhexyl acrylate and dimethoxymethylsilane, and its ketene silyl acetal isomer was removed. The composition 11 was obtained under the conditions described above.

[Comparative Example 8]
A composition 12 was obtained in the same manner as in Example 1 except that (E) the partially hydrolyzed condensate of methyltrimethoxysilane was removed.

[Comparative Example 9]
A composition 13 was obtained in the same manner as in Example 1 except that (F) vinyltris (methylethylketoxime) silane was removed.

[Comparative Example 10]
In Example 1, it prepared in the same conditions except remove | excluding the compound obtained by the dehydrochlorination reaction of (G) xylylene diamine and 3-chloropropyl trimethoxysilane, and the composition 14 was obtained.

[Comparative Example 11]
A composition 15 was obtained in the same manner as in Example 1 except that (H) dioctyltin diversate was removed.

[Test method]
The room temperature curable organopolysiloxane composition (silicone rubber composition) prepared in the above examples and comparative examples was poured into a 2 mm mold and cured at 23 ° C. and 50% RH for 7 days to obtain a 2 mm thick rubber sheet. Obtained. The tack free time (touch drying time) is measured according to the method specified in JIS A 5758, and the rubber properties (hardness, elongation at break, tensile strength) from the 2 mm thick sheet according to the method specified in JIS K 6249. ) Was measured.
Further, from this composition, a shear adhesion test body having an adhesion area of 2.5 mm ² and an adhesion thickness of 1 mm was prepared using aluminum having a width of 25 mm and a length of 100 mm, and was cured at 23 ° C. and 50% RH for 7 days. Using this specimen, the shear adhesive strength and the cohesive failure rate were measured according to the method specified in JIS K 6249, and the acceptable value of the cohesive failure rate was set to 100%.
The non-fluidity (slump property) confirmation test was conducted by filling the obtained liquid composition into an aluminum channel having a width of 20 × length of 150 × depth of 10 mm, and immediately leaning vertically to flow the liquid composition. Was measured and 0 mm was determined to be acceptable.
In the curing rate test method, a glass petri dish having an inner diameter of 10 mm was filled with the composition, and the cured thickness was measured from the part exposed to air after 23 ° C. and 50% RH × 1 day.

  As a test method for the initial sealability, a pressure test was performed using a pressure vessel similar to a flange pressure vessel for pressure test specified in JIS K 6820 as a test apparatus. The pressure vessel comprises 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 of the same size as the upper flange, and the inner side of the seal surface of the lower flange An annular cutout having a width of 3 mm and a depth of 3 mm is provided along the circumference of the edge. The sealing surface of the lower flange was washed with toluene. Thereafter, the composition was applied in an application amount sufficient to fill the seal surface, and applied in a bead shape to the central portion of the lower seal surface. Immediately after application, the upper container was placed on the lower container so that the sealing surfaces of the upper flange and the lower flange were in contact with each other, and a 20.50 mm iron spacer was installed and four fastening bolts were assembled. The spacer causes a gap of 0.5 mm between the seal surfaces, which is a so-called accelerated test that makes the pressure test more severe. After curing at 23 ° C. and 50% RH for 60 minutes, a gas was inserted from the upper pressure port, and the gas pressure that could be withstood by the sealant was taken as the seal strength.

  In the foaming property test, 0.63 g of the obtained composition was dissolved in 8 ml of xylene, mixed with 250 ml of continuously variable transmission oil [trade name: Honda Multi Magic Fluid], mixed and then measured according to JIS K 2518. An amount of 100 ml or less was determined to be acceptable.

  In the storage deterioration test, the obtained composition was allowed to stand at 70 ° C. for 7 days in an uncured state under sealing conditions, and then the same test as in the initial stage of production was performed to confirm performance deterioration.

  Moreover, in order to confirm the chemical resistance (CVTF resistance) ability, the obtained rubber sheet was immersed in a continuously variable transmission oil [trade name: Honda Multi Magic Fluid] and deteriorated at 150 ° C. for 7 days. The chemical resistance was confirmed by performing the same test as in the initial stage of manufacture. In addition, the thing whose change rate of the aluminum shearing adhesive force after chemical resistance which is the cause of oil leakage is within ± 20% was determined to be acceptable.

  The results of Examples 1 to 4 are shown in Table 1, the results of Comparative Examples 1 to 6 are shown in Table 2, and the results of Comparative Examples 7 to 11 are shown in Table 3.

As can be seen from Tables 1 to 3, the compositions prepared in Examples 1 to 4 are excellent in initial curability, low foamability, storage stability, and chemical resistance. On the other hand, in the compositions prepared in Comparative Examples 1 to 4, the (F) component was added before or simultaneously with the (C) component and the (D) component, and Comparative Examples 6 and 7 were further added. In (2), since the essential components (C) and (D) are not added, the alkoxylation of the hydroxyl group contained in the organopolysiloxane (A) is insufficient or not, resulting in low foaming. Sex is impaired. Here, in Comparative Example 7, since the component (C) is not added, the component (A) and the component (E) react in the presence of the component (D), and the non-fluidity and the storage stability deteriorate. doing. Further, in Comparative Examples 5 and 8, since the partially hydrolyzed silane compound (E) is not added, the CVTF resistance is impaired. In Comparative Example 9, since the oxime silane which is the component (F) is not added, the crosslinking proceeds with moisture contained in the component (B), and the non-fluidity and the storage stability are deteriorated. . In Comparative Example 10, since the silane coupling agent as component (G) is not added, the cohesive failure rate with respect to aluminum is reduced. In Comparative Example 11, since the curing catalyst as the component (H) has not been added, a decrease in the initial sealability, which is an index of initial curability, is confirmed.
Therefore, it can be confirmed that the method for producing a low-foaming room temperature-curable organopolysiloxane composition excellent in chemical resistance according to the present invention is effective.

Claims (7)

(A) 100 parts by mass of an organopolysiloxane represented by the following general formula (1),
HO (SiR ¹ ₂ O) _a H (1)
(Wherein R ¹ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ¹ may be the same or different from each other. A is an integer of 10 or more. is there.)
(B) 1 to 500 parts by mass of at least one inorganic filler,
(C) At least one selected from ketene silyl acetal type compounds represented by the following general formula (2), 2-methyl dialkoxysilyl propionic acid esters represented by the following general formula (3), and partial hydrolysates thereof: 0.1-20 parts by weight of compound,
(R ² O) ₂ Si (R ³ ) OC (OR ³ ) = CHCH ₃ (2)
(R ² O) ₂ Si (CH ₃ ) CH (CH ₃ ) COOR ³ (3)
(Wherein R ² is an alkyl group having 1 to 4 carbon atoms, R ³ is an unsubstituted or substituted alkyl group having 1 to 12 carbon atoms, and R ² and R ³ may be the same or different from each other. It may be a group of
(D) 0.01 to 20 parts by mass of a non-silicon organic compound and / or an organosilicon compound having at least one guanidine skeleton in the molecule;
(E) 0.2-5 parts by mass of a partially hydrolyzed condensate of a silane compound represented by the following general formula (4)
R ⁴ _b Si (X) _4-b (4)
(In the formula, R ⁴ is a methyl group or a vinyl group, X is an alkoxy group, and b is 0 or 1.)
(F) 1-30 parts by mass of a silane compound having three or more ketoxime groups represented by the following general formula (5) in one molecule;
R ⁵ _d Si (ON = CR ⁶ ₂ ) _4-d (5)
(Wherein R ⁵ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ⁶ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms. d is 0 or 1.)
(G) 0.05 to 10 parts by mass of a silane coupling agent represented by the following general formula (6) and / or a partial hydrolysis condensate thereof,
R ⁷ _e Si (OR ⁸ ) _4-e (6)
(In the formula, R ⁷ is independently a monovalent hydrocarbon group having 1 to 20 carbon atoms which may contain an atom selected from a nitrogen atom, a sulfur atom and an oxygen atom other than R ⁴ , and is at least one of R ^7. Is a monovalent hydrocarbon group having 1 to 20 carbon atoms and containing at least one atom selected from a nitrogen atom, a sulfur atom and an oxygen atom, and R ⁸ is an unsubstituted or substituted monovalent carbon atom having 1 to 10 carbon atoms. A hydrogen group, and e is 1, 2 or 3.)
(H) Curing catalyst In the manufacturing method of the organopolysiloxane composition containing 0.001 to 10 parts by mass as an essential component, before the step of adding and mixing the component (F) in the composition, the component (C) and (D) The manufacturing method of the low-foaming room temperature curing organopolysiloxane composition characterized by including the process of adding and disperse-mixing a component.   The low-foaming room-temperature-curing organo according to claim 1, wherein at least one inorganic filler as component (B) is selected from calcium carbonate, fumed silica, precipitated silica, and aluminum oxide. A method for producing a polysiloxane composition.   (C) component is a mixture of a 2-methyl dialkoxysilyl propionic acid ester represented by the above general formula (3) and a ketene silyl acetal type compound represented by the above general formula (2) which is a structural isomer thereof, Or a method for producing a low-foaming room-temperature-curable organopolysiloxane composition according to claim 1 or 2, which is a partially hydrolyzed product thereof.   (E) The alkoxy group of a component is a methoxy group, and the specific gravity in 23 degreeC is the range of 1.04-1.25, The low of any one of Claims 1-3 characterized by the above-mentioned. A method for producing a foamable room temperature curable organopolysiloxane composition. The silane coupling agent of component (G) is represented by the following general formula (7)

(Wherein R ⁸ is as described above, R ⁹ is an unsubstituted monovalent hydrocarbon group having 1 to ¹⁰ carbon atoms, R ¹⁰ is a divalent hydrocarbon group having 1 to ¹⁰ carbon atoms, ¹¹ is a divalent hydrocarbon group having 7 to 10 carbon atoms including an aromatic ring, and p is an integer of 1 to 3, provided that at least one of the NH group and the NH ₂ group is directly connected to the aromatic ring of R ^11. Not.)
The method for producing a low-foaming room temperature-curable organopolysiloxane composition according to any one of claims 1 to 4, wherein the silane compound is represented by the formula: The component (A) and the component (B) are mixed, the component (C) is mixed under reduced pressure, and the component (D) is further mixed and reacted under reduced pressure, or the components (A) and (B (C) component and (D) component are added to this, and then mixed and reacted under reduced pressure, so that the terminal silanol group of (A) component is at least partially formed by the alkoxy group of (C) component. After the alkoxysilylation, the remaining unreacted silanol group in the component (A) is reacted with the alkoxy group in the component (E) by mixing the component (E) under reduced pressure, and then (F) The method for producing a low-foaming room temperature-curable organopolysiloxane composition according to any one of claims 1 to 5, wherein the component, the component (G) and the component (H) are mixed under reduced pressure. The manufacturing method of the automobile oil seal which comprises the process of hardening the low-foaming room temperature curing type organopolysiloxane composition manufactured by the method of any one of Claims 1-6.