JPWO2018055851A1 - Resin adhesive organopolysiloxane composition for oil seal and oil seal for automobile - Google Patents

Abstract

A silane coupling agent having at least one functional group other than an isocyanate group containing a nitrogen atom, a sulfur atom, or an oxygen atom and / or a partial hydrolytic condensate thereof and an isocyanate silane compound and / or a partial hydrolytic condensate thereof The organopolysiloxane composition for resin-adhesive oil sealing using a base oil having a high viscosity and adjusting the amount of the curing agent in combination is also suitably used as an oil seal for automobiles, and in particular, it is an initial pressure resistance by rapid curing. As well as having excellent properties, it improves adhesion to a resin oil pan and adhesion strength, and gives a cured product having good elongation and engine oil resistance.

Description

  The present invention relates to an organopolysiloxane composition for resin adhesive oil seal that is suitably used as an oil seal for automobiles, and in particular, it is excellent in initial curing resistance with quick curing and improves adhesion to resin oil pan and adhesive strength. And an organopolysiloxane composition which gives a cured product having good elongation and engine oil resistance, and an automobile oil seal obtained by curing the composition.

  Conventionally, oil-resistant gaskets and packing materials made of cork, organic rubber, asbestos, etc. are used for seals around automobile engines, but it is said that inventory control and work processes are complicated for these. There is the disadvantage that there is a disadvantage and that their sealing performance is not reliable. Therefore, for this type of application, an FIPG method (Formed In Place Gasket) using a room temperature curable organopolysiloxane composition as a liquid gasket is adopted.

  In recent years, attempts have been made to partially resinify metals used for automobile engines from the viewpoint of improving fuel economy and reducing weight of automobiles. Resins employed as those members are generally selected from resins which have a low rate of change with respect to mechanical properties and durability test against engine oil, that is, resins which are very stable mechanically and chemically. Resins with high chemical stability do not have or have very few active groups, so it is considered difficult to obtain good adhesion and to stably maintain the adhesion. . As a method for improving the adhesion to a resin, a method of adding an oligomer of an aminosilane coupling agent to a room temperature curable organopolysiloxane composition (Japanese Patent No. 3714861: Patent Document 1) is known. When an oligomer of an aminosilane coupling agent was added to a composition for oil seal use, it could not be used because of its poor resistance to engine oil. Also, a method of selecting a filler of a room temperature curable organopolysiloxane composition of dealcoholization type (Japanese Patent Laid-Open No. 2004-292724: Patent Document 2), and a method of selecting a structure of a titanium catalyst used as a curing catalyst ( Although the patent No. 4438937, the patent No. 4530136, the patent No. 4658654, the patent No. 4530177: the patent documents 3-6) are known, these compositions are compositions of a dealcoholization type. Therefore, there is a problem that it takes time to obtain a cured product, and engine oil resistance performance is inferior as compared with FIPG conventionally used. In addition, as a technique for improving adhesion to various adherends, a report that the adhesion of magnesium is improved when a reaction product of isocyanate silane and acetic acid is used as an adhesion promoter (Patent No. 4662056: Patent Document 7), isocyanate silane is used Report that the oil surface adhesion is improved (Japanese Patent Laid-Open No. 2010-037507: Patent No. 8), and the method using isocyanurate silane (Japanese Patent Laid-open No. 2015-021009: Patent No. 9) has been reported. There are no reports of improving the adhesion to resins having high chemical stability.

Patent No. 3714861 gazette Unexamined-Japanese-Patent No. 2004-292724 Patent No. 4438937 Patent No. 4530136 Patent No. 4658654 gazette Patent No. 4530177 gazette Patent No. 4662056 JP, 2010-037507, A Unexamined-Japanese-Patent No. 2015-021019 Japanese Patent Application Laid-Open No. 5-105689

  The present invention has been made in view of the above circumstances, and is suitably used as an oil seal for automobiles, and in particular, it is excellent in initial curing resistance with rapid curing and improves adhesion to resin oil pan and adhesive strength, and An object of the present invention is to provide a resin adhesive oil sealing organopolysiloxane composition which gives a cured product having good elongation and engine oil resistance, and an automotive oil seal obtained by curing the composition.

  As a result of intensive studies to achieve the above object, the present inventors have found that a silane coupling agent having at least one functional group other than a nitrogen atom, a sulfur atom or an isocyanate group containing an oxygen atom and / or the like The cured product obtained by combining the partially hydrolyzed condensate and the hydrolyzable isocyanate silane compound and / or the partially hydrolyzed condensate thereof has good adhesion and oil resistance, and the amount of curing agent It is found that by adjusting a base oil having rapid curing property and high viscosity, it is possible to obtain a resin adhesive oil sealing organopolysiloxane composition in which the resulting cured product achieves high elongation. The present invention has been made.

（式中、Ｒ¹²、Ｒ¹³は、それぞれ独立に、炭素数１〜１０の非置換一価炭化水素基であり、Ｒ¹⁴は炭素数１〜１０の二価炭化水素基であり、ｆは１〜３の整数である。）
（Ｆ）硬化触媒 ０．０１〜０．５質量部
を含有することを特徴とする樹脂接着性オイルシール用オルガノポリシロキサン組成物。
〔２〕
（Ｂ）成分の無機質充填剤が、表面処理剤により処理された、炭酸カルシウム、煙霧質シリカ、沈降性シリカ、カーボンブラック及び酸化アルミニウムから選択される少なくとも１種である〔１〕記載の樹脂接着性オイルシール用オルガノポリシロキサン組成物。
〔３〕
（Ｄ）成分のシランカップリング剤が、下記一般式（４）

（式中、Ｒ⁸、Ｒ⁹は、それぞれ独立に、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、ｅ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。）
で示される加水分解性オルガノシラン化合物及び／又はその部分加水分解縮合物を含有するものである〔１〕又は〔２〕に記載の樹脂接着性オイルシール用オルガノポリシロキサン組成物。
〔４〕
〔１〕〜〔３〕のいずれかに記載の樹脂接着性オイルシール用オルガノポリシロキサン組成物の硬化物からなる自動車用オイルシール。That is, the present invention provides the following organopolysiloxane composition for resin adhesive oil seal and an oil seal for automobile obtained by curing the composition.
[1]
(A) 100 parts by mass of organopolysiloxane having a viscosity of 2,000 mPa · s or more at 23 ° C. 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, R ¹ may be the same as or different from each other, and a is an integer of 100 or more) is there.)
(B) 1 to 500 parts by mass of inorganic filler,
(C) 1 to 30 parts by mass of a hydrolyzable (organo) silane compound having three or more ketooxime groups represented by the following general formula (2) in one molecule,
R ² _b Si (O-N = CR ³ ₂ ) _4-b (2)
(Wherein R ² is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ³ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms. B Is 0 or 1.)
(D) 0.01 to 5 parts by mass of a silane coupling agent represented by the following general formula (3) and / or a partial hydrolysis condensate thereof
R ⁴ R ⁶ _c Si (OR ⁵ ) _3-c (3)
(Wherein, R ⁴ is a monovalent hydrocarbon having 1 to 20 carbon atoms having at least one functional group other than an isocyanate group containing any one or more atoms selected from a nitrogen atom, a sulfur atom and an oxygen atom) R ⁵ and R ⁶ each independently represent an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and c is 0, 1 or 2.)
(E) 0.01 to 3 parts by mass of a hydrolyzable isocyanate silane compound represented by the following general formula (5) and / or a partial hydrolysis condensate thereof

(Wherein, R ¹² and R ¹³ are each independently an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R ¹⁴ is a divalent hydrocarbon group having 1 to 10 carbon atoms, and f is It is an integer of 1 to 3.)
(F) An organopolysiloxane composition for resin adhesive oil seal containing 0.01 to 0.5 parts by mass of a curing catalyst.
[2]
The resin adhesion according to [1], wherein the inorganic filler of component (B) is at least one selected from calcium carbonate, fumed silica, precipitated silica, carbon black and aluminum oxide treated with a surface treatment agent Oil sealing organopolysiloxane composition.
[3]
The silane coupling agent of component (D) is represented by the following general formula (4)

(Wherein, R ⁸ and R ⁹ each independently represent an unsubstituted monovalent hydrocarbon group having 1 to ¹⁰ carbon atoms, R ¹⁰ represents a divalent hydrocarbon group having 1 to ¹⁰ carbon atoms, and R ¹¹ Is an aromatic ring-containing divalent hydrocarbon group having 7 to 10 carbon atoms, and e is an integer of 1 to _3. However, at least one of NH group and NH ₂ group is directly linked to the aromatic ring of R ¹¹ Absent.)
The organopolysiloxane composition for resin adhesive oil seal as described in [1] or [2] which contains the hydrolysable organosilane compound shown by these, and / or the partial hydrolysis-condensation product.
[4]
An automobile oil seal comprising a cured product of the organopolysiloxane composition for resin adhesive oil seal according to any one of [1] to [3].

  According to the present invention, in particular, it is excellent in initial pressure resistance by rapid curing, improves adhesion to a resin oil pan and adhesion strength, and room temperature curability giving a cured product having good elongation and engine oil resistance. The resin-adhesive organopolysiloxane composition of the present invention can be obtained.

Hereinafter, the present invention will be described in more detail.
The component (A) of the organopolysiloxane composition for resin adhesive oil sealing used in the present invention is represented by the following general formula (1), and the main chain consists of repeating diorganosiloxane units, and both molecular chain terminals are A linear diorganopolysiloxane having a viscosity of 2,000 mPa · s or more at 23 ° C. blocked by a hydroxyl group (silanol group) bonded to a silicon atom, which acts as the main component (base polymer) of the composition of the present invention It is
^{_{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, R ¹ may be the same as or different from each other, and a is an integer of 100 or more) is there.)

In the above formula (1), R ¹ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group and hexyl Alkyl group such as octyl group; cycloalkyl group such as cyclohexyl group; alkenyl group such as vinyl group, allyl group, propenyl group, butenyl group and hexenyl group; aryl group such as phenyl group and tolyl group; benzyl group, phenyl group Aralkyl groups such as ethyl group, or groups in which hydrogen atoms of these groups are partially substituted with halogen atoms such as chlorine, fluorine and bromine, such as trifluoropropyl group etc. are mentioned, and methyl group and phenyl group are preferable. And methyl are particularly preferred. The R ^{1 s} may be the same or different groups.

Further, a in the formula (1) is an integer of 100 or more (usually 100 to 2,000), preferably 150 to 1,000, more preferably 200 to 800, and this organopolysiloxane at 23 ° C. The viscosity is 2,000 mPa · s or more, usually in the range of 2,000 to 500,000 mPa · s, preferably in the range of 3,000 to 500,000 mPa · s, in particular 5,000 to 100,000 mPa · s. It is preferable that it becomes a range. 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 polymerization degree (or molecular weight) is, for example, a number average polymerization degree (or number average molecular weight) in terms of polystyrene in gel permeation chromatography (GPC) analysis using toluene, tetrahydrofuran (THF) or the like as a developing solvent. It can be determined as etc.
The organopolysiloxane (A) may be used alone or in combination of two or more.

Next, the inorganic filler which is the component (B) is a reinforcing non-reinforcing filler for imparting rubber physical properties to the present composition. As the filler, silica-based fillers such as surface-treated or non-treated, dry silica such as pyrogenic silica, fumed silica, precipitated silica, wet silica such as sol-gel method silica, carbon black, talc, bentonite And 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 and the like Precipitated silica, carbon black, and aluminum oxide are preferable, and calcium carbonate, fumed silica, precipitated silica, carbon black, and aluminum oxide are more preferable because the surface of the inorganic filler is hydrophobized. In this case, these inorganic fillers preferably have a low water content.
The type and amount of the surface treatment agent and the treatment method are not particularly limited, but typically, organosilicon compounds such as chlorosilanes, alkoxysilanes and organosilazanes, fatty acids, paraffins, and silane coupling agents, Treatment agents such as titanium coupling agents can be applied.

The inorganic filler of component (B) may be used alone or in combination of two or more.
The blending amount of the component (B) is in the range of 1 to 500 parts by mass, preferably in the range of 20 to 300 parts by mass with respect to 100 parts by mass of the organopolysiloxane of the component (A). If the amount is less than 1 part by mass, sufficient rubber strength can not be obtained, which causes the problem of being unsuitable for use. When the amount exceeds 500 parts by mass, the dischargeability from the cartridge is deteriorated and the storage stability is deteriorated. The mechanical properties of the physical properties of the rubber are also reduced.

Next, a hydrolyzable (organo) silane compound having three or more (that is, three or four) ketooxime groups represented by the following general formula (2) which is the component (C) in one molecule is obtained. In the composition, it is a component generally called a curing agent for imparting good storage stability to the composition under closed conditions, and reacting with the moisture in the air to make it rubbery after opening.
R ² _b Si (O-N = CR ³ ₂ ) _4-b (2)
(Wherein R ² is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ³ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms. B Is 0 or 1.)

In the formula (2), R ² is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, can be exemplified the same ones as R ¹ of formula (1) described above, among them 1 to carbon atoms An unsubstituted or substituted monovalent hydrocarbon group of 6 is preferred, and a methyl group, a vinyl group and a phenyl group are particularly preferred.
R ³ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and similar to R ^{2 in the} same manner as R ¹ in the above-mentioned formula (1) can be exemplified. The unsubstituted or substituted monovalent hydrocarbon group of 6 is preferable, and one selected from methyl group, ethyl group, propyl group, butyl group and isobutyl group is particularly preferable.
The above R ² and R ³ may be the same or different groups.

Specific examples of the hydrolyzable (organo) silane compound of component (C) include methyltris (dimethylketoxime) silane, methyltris (methylethylketoxime) silane, methyltris (methylisobutylketoxime) silane and methyltris (methylpropylketoxime) Silane, methyltris (methylbutylketoxime) silane, vinyltris (methylethylketoxime) silane, vinyltris (dimethylketoxime) silane, vinyltris (methylisobutylketoxime) silane, vinyltris (methylpropylketoxime) silane, vinyltris (methylbutylketoxime) silane And ketoxime silanes such as silane, tetra (methylethyl ketoxime) silane and tetra (methyl isobutyl ketoxime) silane are exemplified. These can be used in combination alone, or two or more kinds.
The hydrolyzable (organo) silane compound of the component (C) is a component which does not contain a ketooxime group in the molecule in that the ketoxime group is essentially contained in the molecule. The silane coupling agent and / or the partial hydrolysis condensate thereof, and the hydrolyzable isocyanate silane compound of the component (E) and / or the partial hydrolysis condensate thereof are clearly differentiated.

  The hydrolyzable (organo) silane compound of the component (C) is used in an amount of 1 to 30 parts by mass, preferably 3 to 15 parts by mass, per 100 parts by mass of the organopolysiloxane (A). When the amount is less than 1 part by mass, sufficient crosslinking can not be obtained, and a target composition having rubber elasticity can not be obtained. When the amount exceeds 30 parts by mass, mechanical properties and curability of the obtained rubber physical properties decrease. I will.

Next, the component (D) is a silane coupling agent represented by the following general formula (3) (ie, a hydrolyzable carbon functional organosilane compound having a functional group-containing monovalent hydrocarbon group) and / or its It is a partial hydrolysis condensation product, and is an essential component to develop good adhesion to the present composition.
R ⁴ R ⁶ _c Si (OR ⁵ ) _3-c (3)
(Wherein, R ⁴ is a monovalent hydrocarbon having 1 to 20 carbon atoms having at least one functional group other than an isocyanate group containing any one or more atoms selected from a nitrogen atom, a sulfur atom and an oxygen atom) R ⁵ and R ⁶ each independently represent an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and c is 0, 1 or 2; Preferably it is 0 or 1.)

In the above formula (3), R ⁴ is a functional group other than an isocyanate group containing an atom selected from a nitrogen atom, a sulfur atom and an oxygen atom (eg, unsubstituted or substituted amino group, unsubstituted or substituted imino group, amide group A monovalent hydrocarbon group having 1 to 20 carbon atoms and having at least one of a ureido group, a mercapto group, an epoxy group, a (meth) acryloxy group, etc. Specifically, β- (2,3-epoxycyclohexyl) ) Ethyl group, β- (3,4-epoxycyclohexyl) ethyl group, γ-glycidoxypropyl group, γ- (meth) acryloxypropyl group, γ-acryloxypropyl group, N-β (aminoethyl)- γ-aminopropyl group, γ-aminopropyl group, N-phenyl-γ-aminopropyl group, γ-ureidopropyl group, γ-mercaptopropyl group, γ-isocyanate propy Nitrogen atom such as a group, a sulfur atom and having 3 to 20 carbon atoms other than the isocyanate group containing at least one atom selected from oxygen atom, in particular be mentioned monovalent hydrocarbon group of 8 to 14 carbon atoms.

R ⁵ and R ⁶ each independently represent an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, and is the same as R ^{1 in} the above-mentioned formula (1) In particular, alkyl groups such as methyl, ethyl, propyl and isopropyl are preferred.

（式中、Ｒ⁸、Ｒ⁹は、それぞれ独立に、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、ｅは１〜３の整数、好ましくは２又は３、より好ましくは３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 a specific example of the silane coupling agent of (D) component, it is carbon number 1 which has at least one functional group other than the isocyanate group containing any one or more atoms chosen from a nitrogen atom, a sulfur atom, and an oxygen atom. -20 hydrolyzable silane compounds containing one monovalent hydrocarbon group, and one to three organooxy groups such as alkoxy groups may be used, though (D) component Among these, when using a hydrolyzable organosilane compound represented by the following general formula (4) and / or a partial hydrolytic condensate thereof, adhesion and chemical resistance are further improved.

(Wherein, R ⁸ and R ⁹ each independently represent an unsubstituted monovalent hydrocarbon group having 1 to ¹⁰ carbon atoms, R ¹⁰ represents a divalent hydrocarbon group having 1 to ¹⁰ carbon atoms, and R ¹¹ Is an aromatic ring-containing divalent hydrocarbon group having 7 to 10 carbon atoms, and e is an integer of 1 to 3, preferably 2 or 3, and more preferably 3. However, at least one of NH group and NH ₂ group is One is not directly linked to the aromatic ring of R ^11. )

The silane compound represented by the above formula (4) has an NH group (imino group) and an NH ₂ group (amino group), contains an aromatic ring between the NH group and the NH ₂ group, and further contains an NH group at least one of the NH ₂ group is an alkoxysilane compound which does not directly linked to the carbon atoms constituting the aromatic ring, more details are described in JP-a-5-105689.

In the above formula (4), the unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, represented by R ⁸ and R ⁹ includes methyl, ethyl, propyl, butyl and hexyl groups. Alkyl groups such as cyclohexyl 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, phenylethyl group etc. An aralkyl group etc. are mentioned, A methyl group or an ethyl group is preferable as R ⁸ , A methyl group is preferable as R ⁹ .

As the divalent hydrocarbon group having 1 to 10 carbon atoms R ^10, methylene group, ethylene group, propylene group, tetramethylene group, hexamethylene group, octamethylene group, decamethylene group, such as 2-methyl propylene 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 the like, preferably a methylene group, an ethylene group or a propylene group, and particularly preferably a propylene group.

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 -
Among these, particularly preferred is -CH ₂ -C ₆ H ₄ -CH _2- .

In this case, the alkylene group bonded to the right side of the phenylene group (on the NH ₂ side in Formula (4) (an -NH ₂ group in the absence of an alkylene group) is ortho, meta or para) Good.

As a silane compound shown by the said General formula (4), the following are illustrated.

The silane coupling agent of component (D) and / or its partial hydrolysis condensate may be used alone or in combination of two or more.
In the present invention, the partial hydrolytic condensate is a residual hydrolyzate formed in the molecule by partially hydrolyzing and condensing one or two or more hydrolysable organosilane compounds (silane coupling agents) as raw materials. It means an organopolysiloxane (oligomer) containing at least two, preferably three or more degradable groups (for example, organooxy groups such as unsubstituted or substituted alkoxy groups).
In addition, the silane coupling agent of (D) component and / or its partial hydrolysis-condensation product are things which do not contain an isocyanate group in a molecule, and in the point which has an isocyanate group essentially in a molecule mentioned later The hydrolyzable isocyanate silane compound of component (E) and / or the partial hydrolytic condensate thereof are clearly differentiated.

  The compounding quantity of the said (D) component is 0.01-5 mass parts with respect to 100 mass parts of organopolysiloxane of (A) component, Preferably it is 0.1-3 mass parts. If the amount is less than 0.01 parts by mass, the cured product does not exhibit sufficient adhesive performance, and if it is more than 5 parts by mass, the rubber strength after curing may decrease or the curability may decrease.

（式中、Ｒ¹²、Ｒ¹³は、それぞれ独立に、炭素数１〜１０の非置換一価炭化水素基であり、Ｒ¹⁴は炭素数１〜１０の二価炭化水素基であり、ｆは１〜３の整数、好ましくは２又は３、より好ましくは３である。）Next, the hydrolyzable isocyanate silane compound represented by the following general formula (5), which is the component (E), and / or its partial hydrolysis condensate react with the component (D) during mixing, and good adhesion is obtained. And oil resistance to the composition.

(Wherein, R ¹² and R ¹³ are each independently an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R ¹⁴ is a divalent hydrocarbon group having 1 to 10 carbon atoms, and f is It is an integer of 1 to 3, preferably 2 or 3, more preferably 3.)

In the above formula (5), the unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, having R ¹² and R ¹³ includes a methyl group, an ethyl group, a propyl group, a butyl group and a hexyl group. Alkyl groups such as cyclohexyl 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, phenylethyl group etc. an aralkyl group, as R ¹² is preferably a methyl group or an ethyl group, the R ^13, a methyl group is preferred.

As the divalent hydrocarbon group having 1 to 10 carbon atoms R ^14, methylene group, ethylene group, propylene group, tetramethylene group, hexamethylene group, octamethylene group, decamethylene group, such as 2-methyl propylene 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 the like, preferably a methylene group, an ethylene group or a propylene group, and particularly preferably a propylene group.

  Specific examples of the component (E) include 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-isocyanatepropyltripropoxysilane, 3-isocyanatepropylmethyldimethoxysilane, 3-isocyanatepropyldimethylmethoxysilane, 3-isocyanate propylethyl dimethoxysilane, 4-isocyanate butyl trimethoxysilane, 5-isocyanate pentyl trimethoxysilane, 6-isocyanate hexyl trimethoxysilane, 7-isocyanate heptyl trimethoxysilane, 8-isocyanate octyl trimethoxysilane and parts thereof Although a hydrolysis condensation product can be illustrated, it is not this limitation. Among them, 3-isocyanatepropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane can be suitably used.

  The compounding quantity of (E) component is 0.01-3 mass parts with respect to 100 mass parts of organopolysiloxane of (A) component, Preferably it is 0.1-1.5 mass parts. If the compounding amount is less than the above range, there is a possibility that the adhesiveness and rubber physical properties (mechanical characteristics such as hardness, elongation, strength, etc.) of the target cured product (silicone rubber) may not be obtained. There is a possibility that the increase and the deterioration of the physical properties of the rubber may be caused.

  Next, the curing catalyst of the component (F) is generally called a curing catalyst, which is used to accelerate the hydrolysis reaction of the present composition with the moisture in the air. It is preferred 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 (F) include tin-based catalysts, bismuth-based catalysts, and titanium-based catalysts. It is preferable to use tin-based catalysts and bismuth-based catalysts. Specific examples of tin-based catalysts include tin naphthenate, tin caprylate, dibutyltin diacetate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltin diolate, diphenyltin diacetate, dibutyltin oxide, dibutyltin dimethoxide, dibutylbis (triethoxysiloxy) ) Tin, dibutyltin benzyl malate, dioctyltin diversatate, etc., and specific examples of the bismuth-based catalyst include bismuth tris (2-ethylhexanoate) or bismuth tris (neodecanoate) etc. Can. Specific examples of the titanium-based catalyst include titanate esters such as tetraisopropoxytitanium, tetra-n-butoxytitanium, tetrabis (2-ethylhexoxy) titanium, dipropoxybis (acetylacetona) titanium, titanium isopropoxyoctylene glycol and the like And titanium chelate compounds.

The curing catalyst for the component (F) may be used alone or in combination of two or more.
The compounding amount of the component (F) is in the range of 0.01 to 0.5 parts by mass, preferably in the range of 0.03 to 0.3 parts by mass with respect to 100 parts by mass of the organopolysiloxane of the component (A). It is. If the amount is less than 0.01 parts by mass, good curability can not be obtained, which causes a problem that, for example, time is increased before injection of engine oil at the time of manufacture of an automobile etc. On the other hand, if the amount is more than 0.5 parts by mass, the storage stability of the composition may be deteriorated, and the composition may gel in the container over time.

  Further, in the composition of the present invention, additives generally known in addition to the above components may be used without impairing the object of the present invention. Examples of the additive include polyether as a thixotropic agent, silicone oil as a plasticizer, isoparaffin and the like, and if necessary, pigments, dyes, coloring agents such as fluorescent whitening agents, antifungal agents, 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, low boiling isoparaffins can also be added.

  The organopolysiloxane composition for resin-adhesive oil sealing of the present invention is a composition curable at room temperature, and as the curing conditions, for example, a composition (room-temperature curable organopolysiloxane composition) of 2 mm mold The composition is allowed to stand for 2 days at 23 ° C. and 50% RH for 7 days to obtain a 2 mm thick cured product (silicone rubber sheet).

  In addition, the organopolysiloxane composition for resin adhesive oil seal of the present invention is suitably used as an oil seal for automobiles, and in particular, it is excellent in initial curing resistance with rapid curing and has adhesiveness to resin oil pan and adhesive strength. And provide a cured product having good elongation and engine oil resistance. In particular, it can be suitably used as a sealing material for resin-made oil pans for automobile engines.

  EXAMPLES Hereinafter, the present invention will be specifically described by showing Examples and Comparative Examples, but the present invention is not limited to the following Examples. In all of the examples and comparative examples, a planetary mixer (manufactured by Inoue Seisakusho Co., Ltd.) was used as a suitable mixer. Moreover, physical-property values, such as a viscosity (measurement value by a rotational viscometer) which is not indicated in particular in a following example, show the value in 23 degreeC.

Example 1
(A) Heavy calcium carbonate (trade name: MC) in which (B) the surface is treated with a fatty acid in 100 parts by mass of polydimethylsiloxane in which the end at a viscosity of 50,000 mPa · s at 23 ° C. is blocked with a silanol group. Coat S-20, 40 parts by mass of Maruo Calcium Co., Ltd., and (B) 80 parts by mass of colloidal calcium carbonate (trade name; Carlex 300 manufactured by Maruo Calcium Co., Ltd.), the surface of which is treated with fatty acid And (B) 2 parts by mass of fumed silica whose surface was treated with dimethyldichlorosilane were added and mixed, and then 7 parts by mass of (C) vinyltris (methylethyl ketoxime) silane was added and mixed under reduced pressure. Next, 1 part by mass of a compound (trade name: CF-73, manufactured by Shin-Etsu Chemical Co., Ltd.) obtained by dehydrochlorination reaction of (D) xylylenediamine and 3-chloropropyltrimethoxysilane, (D) 3 -1 part by mass of aminopropyltrimethoxysilane (trade name: KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.), (E) 3-isocyanatopropyltriethoxysilane (trade name: KBE-9007, Shin-Etsu Chemical Co., Ltd. 0.5 parts by mass) and 0.1 parts by mass of (F) dioctyltin diversatate were added and thoroughly mixed under reduced pressure to obtain a composition 1.

Example 2
(A) Heavy calcium carbonate (trade name: MC) in which (B) the surface is treated with a fatty acid in 100 parts by mass of polydimethylsiloxane in which the end at a viscosity of 50,000 mPa · s at 23 ° C. is blocked with a silanol group. Coat S-20, 40 parts by mass of Maruo Calcium Co., Ltd., and (B) 80 parts by mass of colloidal calcium carbonate (trade name; Carlex 300 manufactured by Maruo Calcium Co., Ltd.), the surface of which is treated with fatty acid And (B) 2 parts by mass of fumed silica whose surface was treated with dimethyldichlorosilane were added and mixed, and then 7 parts by mass of (C) vinyltris (methylethyl ketoxime) silane was added and mixed under reduced pressure. Next, (D) 1.5 parts by mass of a compound (trade name; CF-73, manufactured by Shin-Etsu Chemical Co., Ltd.) obtained by the dehydrochlorination reaction of xylylenediamine and 3-chloropropyltrimethoxysilane (E) (E) ) 0.5 parts by mass of 3-isocyanatopropyltriethoxysilane (trade name: KBE-9007, Shin-Etsu Chemical Co., Ltd.) and 0.1 parts by mass of (F) dioctyltin diversatate are added, and the reaction is completely completed under reduced pressure To obtain a composition 2.

[Example 3]
(A) Heavy calcium carbonate (trade name: MC) in which (B) the surface is treated with a fatty acid in 100 parts by mass of polydimethylsiloxane in which the end at a viscosity of 50,000 mPa · s at 23 ° C. is blocked with a silanol group. Coat S-20, 40 parts by mass of Maruo Calcium Co., Ltd., and (B) 80 parts by mass of colloidal calcium carbonate (trade name; Carlex 300 manufactured by Maruo Calcium Co., Ltd.), the surface of which is treated with fatty acid And (B) 2 parts by mass of fumed silica whose surface was treated with dimethyldichlorosilane were added and mixed, and then 7 parts by mass of (C) vinyltris (methylethyl ketoxime) silane was added and mixed under reduced pressure. Next, (D) 1.5 parts by mass of a compound (trade name; CF-73, manufactured by Shin-Etsu Chemical Co., Ltd.) obtained by the dehydrochlorination reaction of xylylenediamine and 3-chloropropyltrimethoxysilane (E) (E) ) 0.5 parts by mass of 3-isocyanatopropyltrimethoxysilane (trade name: KBM-9007, Shin-Etsu Chemical Co., Ltd.) and 0.1 parts by mass of (F) dioctyltin diversatate are added, and the reaction is completely completed under reduced pressure To obtain a composition 3.

Example 4
(A) Heavy calcium carbonate (trade name: MC) in which (B) the surface is treated with a fatty acid in 100 parts by mass of polydimethylsiloxane in which the end at a viscosity of 50,000 mPa · s at 23 ° C. is blocked with a silanol group. Coat S-20, 40 parts by mass of Maruo Calcium Co., Ltd., and (B) 80 parts by mass of colloidal calcium carbonate (trade name; Carlex 300 manufactured by Maruo Calcium Co., Ltd.), the surface of which is treated with fatty acid And (B) 2 parts by mass of fumed silica whose surface was treated with dimethyldichlorosilane were added and mixed, and then 7 parts by mass of (C) vinyltris (methylethyl ketoxime) silane was added and mixed under reduced pressure. Next, (D) 1.5 parts by mass of a compound (trade name; CF-73, manufactured by Shin-Etsu Chemical Co., Ltd.) obtained by the dehydrochlorination reaction of xylylenediamine and 3-chloropropyltrimethoxysilane (E) (E) ) 0.5 parts by mass of 3-isocyanatopropyltriethoxysilane (trade name: KBE-9007, Shin-Etsu Chemical Co., Ltd.) and 0.2 parts by mass of (F) dioctyltin diversatate are added, and the reaction is completely completed under reduced pressure To give a composition 4.

Comparative Example 1
(A) Heavy calcium carbonate (trade name: MC) in which (B) the surface is treated with a fatty acid in 100 parts by mass of polydimethylsiloxane in which the end at a viscosity of 50,000 mPa · s at 23 ° C. is blocked with a silanol group. Coat S-20, 40 parts by mass of Maruo Calcium Co., Ltd., and (B) 80 parts by mass of colloidal calcium carbonate (trade name; Carlex 300 manufactured by Maruo Calcium Co., Ltd.), the surface of which is treated with fatty acid And (B) 2 parts by mass of fumed silica whose surface was treated with dimethyldichlorosilane were added and mixed, and then 7 parts by mass of (C) vinyltris (methylethyl ketoxime) silane was added and mixed under reduced pressure. Next, (D) 1.5 parts by mass of a compound (trade name: CF-73, manufactured by Shin-Etsu Chemical Co., Ltd.) obtained by the dehydrochlorination reaction of xylylenediamine and 3-chloropropyltrimethoxysilane (F) ) 0.1 part by mass of dioctyltin diversatate was added and mixed thoroughly under reduced pressure to obtain a composition 5.

Comparative Example 2
(A) Heavy calcium carbonate (trade name: MC) in which (B) the surface is treated with a fatty acid in 100 parts by mass of polydimethylsiloxane in which the end at a viscosity of 50,000 mPa · s at 23 ° C. is blocked with a silanol group. Coat S-20, 40 parts by mass of Maruo Calcium Co., Ltd., and (B) 80 parts by mass of colloidal calcium carbonate (trade name; Carlex 300 manufactured by Maruo Calcium Co., Ltd.), the surface of which is treated with fatty acid And (B) 2 parts by mass of fumed silica whose surface was treated with dimethyldichlorosilane were added and mixed, and then 7 parts by mass of (C) vinyltris (methylethyl ketoxime) silane was added and mixed under reduced pressure. Next, 1 part by mass of (D) 3-aminopropyltrimethoxysilane (trade name: KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.1 parts by mass of (F) dioctyltin diversatate are added, The mixture was thoroughly mixed to obtain Composition 6.

Comparative Example 3
(A) Heavy calcium carbonate (trade name: MC) in which (B) the surface is treated with a fatty acid in 100 parts by mass of polydimethylsiloxane in which the end at a viscosity of 50,000 mPa · s at 23 ° C. is blocked with a silanol group. Coat S-20, 40 parts by mass of Maruo Calcium Co., Ltd., and (B) 80 parts by mass of colloidal calcium carbonate (trade name; Carlex 300 manufactured by Maruo Calcium Co., Ltd.), the surface of which is treated with fatty acid And (B) 2 parts by mass of fumed silica whose surface was treated with dimethyldichlorosilane were added and mixed, and then 7 parts by mass of (C) vinyltris (methylethyl ketoxime) silane was added and mixed under reduced pressure. Next, 1 part by mass of a compound (trade name: CF-73, manufactured by Shin-Etsu Chemical Co., Ltd.) obtained by dehydrochlorination reaction of (D) xylylenediamine and 3-chloropropyltrimethoxysilane, (D) 3 -1 part by mass of aminopropyltrimethoxysilane (trade name: KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.), (E) 3-isocyanatopropyltriethoxysilane (trade name: KBE-9007, Shin-Etsu Chemical Co., Ltd. 0.5 parts by mass) and 0.001 parts by mass of (F) dioctyltin diversatate were added and thoroughly mixed under reduced pressure to obtain a composition 7.

Comparative Example 4
(A) Heavy calcium carbonate (trade name: MC) in which (B) the surface is treated with a fatty acid in 100 parts by mass of polydimethylsiloxane in which the end at 1,000 mPa · s at 23 ° C. has a viscosity of 1,000 mPa · s. Coat S-20, 40 parts by mass of Maruo Calcium Co., Ltd., and (B) 80 parts by mass of colloidal calcium carbonate (trade name; Carlex 300 manufactured by Maruo Calcium Co., Ltd.), the surface of which is treated with fatty acid And (B) 2 parts by mass of fumed silica whose surface was treated with dimethyldichlorosilane were added and mixed, and then 7 parts by mass of (C) vinyltris (methylethyl ketoxime) silane was added and mixed under reduced pressure. Next, 1 part by mass of a compound (trade name: CF-73, manufactured by Shin-Etsu Chemical Co., Ltd.) obtained by dehydrochlorination reaction of (D) xylylenediamine and 3-chloropropyltrimethoxysilane, (D) 3 -1 part by mass of aminopropyltrimethoxysilane (trade name: KBM-903, manufactured by Shin-Etsu Chemical Co., Ltd.), (E) 3-isocyanatopropyltriethoxysilane (trade name: KBE-9007, Shin-Etsu Chemical Co., Ltd. 0.5 parts by weight) and 0.1 parts by weight of (F) dioctyltin diversatate were added and thoroughly mixed under reduced pressure to obtain a composition 8.

[Test method]
The composition prepared in the above examples and comparative examples (organopolysiloxane composition for resin adhesive oil seal) is poured into a 2 mm mold and aged for 7 days at 23 ° C. and 50% RH to obtain a 2 mm thick rubber sheet I got Tack free time (touch-to-touch time) was measured according to the method defined in JIS A 5758, and rubber physical properties (hardness, elongation at break, tensile strength) were measured from a 2 mm thick sheet according to JIS K 6249.

  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 a portion exposed to air after one day at 23 ° C. and 50% RH.

  The test method of initial stage sealability performed the pressure resistance test using the pressure vessel similar to the flange pressure container for pressure resistance tests prescribed | regulated to JISK6820 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 having the same size as the upper flange, and the inner side of the sealing surface of the lower flange At the edge, an annular notch 3 mm wide and 3 mm deep is provided along the circumference. The sealing surface of the lower flange was washed with toluene. Thereafter, the above composition was applied at a coating amount sufficient to completely fill the sealing surface, and was applied in the form of a bead on the lower central surface of the sealing surface. Immediately after the application, the upper container was placed on the lower container so that the upper flange and the sealing surface of the lower flange were in contact, and a 20.50 mm iron spacer was installed to assemble four tightening bolts. Although a gap of 0.5 mm is generated between the seal surfaces by the spacer, it is a so-called accelerated test which makes the pressure resistance test more severe. After curing for 30 minutes at 23 ° C. and 50% RH, a gas was inserted from the upper pressure port, and the gas pressure which the sealing agent can withstand was taken as the seal strength, and those having 200 kPa or more were judged as pass.

Also, from this composition, aluminum having a width of 25 mm and a length of 100 mm, and nylon 66 (PA 66) considered to be promising as a resin for automobile engines (trade name; Seidel 80G33HS1L, manufactured by DuPont Co., Ltd.), nylon 6 (PA 6) (Trade name: UBE nylon, manufactured by Ube Industries, Ltd.), polybutylene terephthalate (PBT) (trade name: Duranex 3300, manufactured by Polyplastics Co., Ltd.), polyphenylene sulfide (PPS) (trade name: Cersteel GS) A shear adhesion test specimen having a bonding area of 2.5 mm ² and a bonding thickness of 1 mm was prepared using -40, Tosoh Co., Ltd. product, and aged at 23 ° C. and 50% RH for 7 days. The shear adhesion and the cohesive failure rate to aluminum and each resin were measured according to the method defined in JIS K 6249 using this test body, and the cohesive failure rates were compared.

  In addition, in order to confirm the chemical resistance (engine oil resistance) ability, immerse the obtained cured silicone rubber sheet and shear adhesion test body in engine oil [trade name: Toyota Castle Oil SN 0W-20], After 10 days of deterioration at 120 ° C, perform the same tests as in the initial stage of production (rubber physical properties (hardness, elongation at break, tensile strength) and measurement of shear adhesion and cohesive failure to aluminum and each resin) The chemical resistance confirmation test was conducted.

  These results are shown in Table 1 below.

  Examples 1 to 4 exhibited good initial sealability, elongation, physical properties, resin adhesiveness, and oil resistance. On the other hand, in Comparative Examples 1 and 2, the initial resin adhesiveness was poor, and in Comparative Example 3, the initial sealability deteriorated. In Comparative Example 4, the adhesion and oil resistance were good, but the elongation was poor.

  From the above results, it can be seen that the organopolysiloxane composition for resin adhesive oil sealing according to the present invention is effective.

Claims (4)

(A) 100 parts by mass of organopolysiloxane having a viscosity of 2,000 mPa · s or more at 23 ° C. 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, R ¹ may be the same as or different from each other, and a is an integer of 100 or more) is there.)
(B) 1 to 500 parts by mass of inorganic filler,
(C) 1 to 30 parts by mass of a hydrolyzable (organo) silane compound having three or more ketooxime groups represented by the following general formula (2) in one molecule,
R ² _b Si (O-N = CR ³ ₂ ) _4-b (2)
(Wherein R ² is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and R ³ is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms. B Is 0 or 1.)
(D) 0.01 to 5 parts by mass of a silane coupling agent represented by the following general formula (3) and / or a partial hydrolysis condensate thereof
R ⁴ R ⁶ _c Si (OR ⁵ ) _3-c (3)
(Wherein, R ⁴ is a monovalent hydrocarbon having 1 to 20 carbon atoms having at least one functional group other than an isocyanate group containing any one or more atoms selected from a nitrogen atom, a sulfur atom and an oxygen atom) R ⁵ and R ⁶ each independently represent an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and c is 0, 1 or 2.)
(E) 0.01 to 3 parts by mass of a hydrolyzable isocyanate silane compound represented by the following general formula (5) and / or a partial hydrolysis condensate thereof

(Wherein, R ¹² and R ¹³ are each independently an unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R ¹⁴ is a divalent hydrocarbon group having 1 to 10 carbon atoms, and f is It is an integer of 1 to 3.)
(F) An organopolysiloxane composition for resin adhesive oil seal containing 0.01 to 0.5 parts by mass of a curing catalyst.   The resin bonding according to claim 1, wherein the inorganic filler of the component (B) is at least one selected from calcium carbonate, fumed silica, precipitated silica, carbon black and aluminum oxide treated with a surface treatment agent. Oil sealing organopolysiloxane composition. The silane coupling agent of component (D) is represented by the following general formula (4)

(Wherein, R ⁸ and R ⁹ each independently represent an unsubstituted monovalent hydrocarbon group having 1 to ¹⁰ carbon atoms, R ¹⁰ represents a divalent hydrocarbon group having 1 to ¹⁰ carbon atoms, and R ¹¹ Is an aromatic ring-containing divalent hydrocarbon group having 7 to 10 carbon atoms, and e is an integer of 1 to _3. However, at least one of NH group and NH ₂ group is directly linked to the aromatic ring of R ¹¹ Absent.)
3. A resin-adhesive oil-seal organopolysiloxane composition according to claim 1, which comprises the hydrolyzable organosilane compound and / or the partial hydrolytic condensate thereof.   The oil seal for motor vehicles which consists of hardened | cured material of the organopolysiloxane composition for resin adhesive oil sealing of any one of Claims 1-3.