JP5266788B2 - Oil surface adhesive room temperature curable organopolysiloxane composition and cured product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oily face-adhesive room temperature-curable organopolysiloxane composition capable of producing a cured product having good adhesive strength and cohesion failure even to a substrate with an adhesive interface which is stained by a machine oil, a cutting oil, a turbine oil, an engine oil, a gear oil, a variety of mission oils (an automatic transmission oil, a CVT oil), etc. <P>SOLUTION: This oily face-adhesive room temperature curable organopolysiloxane composition comprises, as essential components, (A) 100 parts of one or more selected from organopolysiloxanes of (i) to (iv) (not shown), (B) 10-150 parts of calcium carbonate whose surface is treated by a fatty acid and/or a paraffine-based treating agent and whose specific surface area by the air permeability method is 0.5-2.5 m<SP>2</SP>/g, (C) 1-30 parts of an oil-absorptive carbon powder, (D) 1-25 parts of a silane represented by formula (6): R<SP>3</SP><SB>4-n</SB>SiK<SB>n</SB>(wherein R<SP>3</SP>is a monovalent hydrocarbon group, K is a hydrolyzable group, and n is 3 or 4) or its partially hydrolyzed product, (E) 0.01-15 parts of a curing catalyst, and (F) 0-10 parts of a silane coupling agent. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a room temperature curable organopolysiloxane composition that provides a cured product having excellent oil surface adhesion, and in particular, a coated product in which machine oil, cutting oil, turbine oil, engine oil, gear oil, etc. are adhered to the adhesive interface. The present invention relates to an oil-surface-adhesive room-temperature-curing organopolysiloxane composition that is useful as an automotive FIPG (Formed In Place Gaskets) material and a cured product thereof, since it exhibits good adhesive strength and cohesive failure even in a body. is there.

  Conventionally, oil-resistant gaskets and packing materials made of cork, organic rubber, asbestos, etc. have been used for the seals around the engine for automobiles, but these require complicated inventory management and work processes. There are disadvantages, and further, there is a disadvantage that the sealing performance is not reliable. For this reason, the FIPG method using a room temperature curable silicone rubber composition has been adopted for this type of application, and has been highly evaluated in terms of workability, sealing property, and heat resistance.

  However, the conventionally known room temperature curable organopolysiloxane composition has a drawback that the formed cured product has insufficient adhesion to the oil surface. For example, machine oil, cutting oil, turbine oil, etc. inevitably adhere when molding or punching engine blocks and oil pans. In addition, engine oil or the like may be injected into the engine block at a stage after the room temperature curable organopolysiloxane composition is applied to the engine block and before it is completely cured. In addition, in missions (ATF (automatic transmission), CVT (continuously variable transmission)), the surface of the adherend may be contaminated with oil after assembly inspection. Therefore, since these oil-like substances are present on the bonding surface between the room temperature curable organopolysiloxane composition and the engine block, there arises a problem that a bonding defect of a cured product that functions as a sealing material occurs. ing. The above problem can be solved to a certain extent by thoroughly cleaning the adhesive interface, but this cleaning process takes a considerable amount of time, and solvent-based degreasing cleaners are not preferred from the environmental and safety aspects. It is difficult to make the assembly process as usual.

  On the other hand, examples of room temperature curable organopolysiloxane compositions having improved adhesion to the oil surface to some extent include JP-A Nos. 05-98160 (Patent Document 1) and JP-A No. 08-176445 (Patent Document 2). ) Has been proposed. However, in the former, oil-absorbing carbon powder is used as a filler, and oil level adhesion, particularly cohesive failure, is difficult to obtain unless it is highly filled, and the viscosity and thixotropy of such a composition is quite high, making it difficult to manufacture. It was. In the latter case, iminoxysilane is used as a crosslinking agent. However, when this curing agent is used, the curing type is limited to a deoxime type, the versatility is inferior, and even if such a curing agent is used, Similar to Japanese Patent Laid-Open No. 05-98160, there was a problem that sufficient oil level adhesion, particularly cohesive failure, was difficult to obtain.

Japanese Patent Laid-Open No. 05-98160 Japanese Patent Laid-Open No. 08-176445

  The present invention has been made in view of the above circumstances, and machine oil, cutting oil, turbine oil, engine oil, gear oil, various transmission oils, automatic transmission oil (ATF), CVT (continuously variable transmission) oil, etc. are present on the bonding interface. It is an object of the present invention to provide an oil surface adhesive room temperature curable organopolysiloxane composition that gives a cured product exhibiting good adhesive strength and cohesive failure to an adherend to be adhered, and a cured product thereof.

  As a result of intensive studies to achieve the above object, the present inventor has obtained one or more of the organopolysiloxanes represented by the following general formula (1) or (2), (3), (5). As a base oil, the component (B) described later as a filler, particularly a composition using a combination of heavy calcium carbonate and oil-absorbing carbon powder, is cured to solve this purpose, and sufficient adhesiveness (particularly cohesive failure). It was found that can be obtained, and the present invention has been made.

（式中、Ｒはメチル基又はエチル基であり、Ｒ¹は炭素原子数１〜１０の置換又は非置換の一価炭化水素基であり、Ｘは１０以上の整数である。Ｙは炭素原子数１〜５のアルキレン基であり、Ｎは独立に０又は１の整数である。）
で示されるオルガノポリシロキサン １００質量部、
（Ｂ）表面がパラフィン系の処理剤で処理されており、かつ空気透過法比表面積が０．５〜２．５ｍ²／ｇである重質炭酸カルシウム １０〜１５０質量部、
（Ｃ）吸油性炭素粉末として、平均粒径が３０〜５０ｎｍの範囲で、ＢＥＴ−Ｎ ₂ 吸着法比表面積が３０〜８０ｍ ² ／ｇであり、かつＤＢＰ吸油量が１３０〜２００ｍｌ／１００ｇの範囲であるアセチレンブラック粉末 ５〜３０質量部、
（Ｄ）下記一般式（６）
Ｒ³ _4-nＳｉＫ_n （６）
（式中、Ｒ³は同一又は異種の炭素数１〜８のアルキル基又はアルケニル基である。また、Ｋは加水分解性基であり、ｎは３又は４の整数である。）
で示されるシラン又はその部分加水分解物 １〜２５質量部、
（Ｅ）硬化触媒 ０．０１〜１５質量部、
（Ｆ）γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルメチルトリエトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシランから選ばれるシランカップリング剤 ０〜１０質量部
からなり、且つコロイダル炭酸カルシウムを含有しないことを特徴とする油面接着性室温硬化型オルガノポリシロキサン組成物、及びその組成物を硬化させてなる硬化物を提供する。
Accordingly, the present invention is (A) under following general formula (1)

(In the formula, R is a methyl group or an ethyl group, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, X is an integer of 10 or more, and Y is a carbon atom. An alkylene group of 1 to 5, and N is independently an integer of 0 or 1.)
Organopolysiloxane down 1 00 parts by mass shown in,
(B) surface Gapa paraffin has been treated with a treating agent based, and 10 to 150 parts by weight of heavy calcium carbonate surface area air permeation method ratio is 0.5 to 2.5 m ² / g,
(C) As the oil-absorbing carbon powder , the average particle diameter is in the range of 30 to 50 nm, the BET-N ₂ adsorption method specific surface area is in the range of 30 to 80 m ² / g, and the DBP oil absorption is in the range of 130 to 200 ml / 100 g. acetylene black powder 5-30 parts by mass is,
(D) The following general formula (6)
R ³ _4-n SiK _n (6)
(In the formula, R ³ is the same or different alkyl group or alkenyl group having 1 to 8 carbon atoms , K is a hydrolyzable group, and n is an integer of 3 or 4.)
1 to 25 parts by mass of a silane or a partial hydrolyzate thereof represented by
(E) Curing catalyst 0.01 to 15 parts by mass,
(F) Silane coupling agent selected from γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 0 to 10 parts by mass
It consists, and provides a colloidal oil surface characterized in that it does not contain calcium carbonate adhesive room temperature curing organopolysiloxane composition, and a cured product obtained by curing the composition.

  According to the room temperature curable organopolysiloxane composition of the present invention, an adherend having machine oil, cutting oil, turbine oil, engine oil, gear oil, various transmission oils (automatic transmission oil, CVT oil) and the like adhered to the adhesive interface. Gives a cured product exhibiting good adhesive strength and cohesive failure.

（式中、Ｒはメチル基又はエチル基であり、Ｒ¹は炭素原子数１〜１０の置換又は非置換の一価炭化水素基であり、Ｘは１０以上の整数である。Ｙは炭素原子数１〜５のアルキレン基であり、Ｎは独立に０又は１の整数である。）
で示されるオルガノポリシロキサン、（ｉｉ）下記一般式（２）

（式中、Ｒ、Ｒ¹、Ｘ、Ｙ、Ｎは上記の通りであり、Ｚは炭素原子数２〜５のアルケニル基である。）
で示されるオルガノポリシロキサン、（ｉｉｉ）下記一般式（３）

〔式中、Ｒ、Ｒ¹、Ｘ、Ｙ、Ｎは上記の通りであり、ｄは１以上１０以下の整数である。また、Ｒ²は下記一般式（４）

（ここで、Ｒ、Ｒ¹、Ｙ、Ｎは上記の通りである。）で示される加水分解性基を含む分岐鎖である。〕
で示されるオルガノポリシロキサン、及び（ｉｖ）下記一般式（５）

（式中、Ｒ、Ｒ¹、Ｘ、Ｙ、Ｚ、Ｎ、ｄは上記の通りである。また、Ｒ²は上記一般式（４）で示される加水分解性基を含む分岐鎖である。）
で示されるオルガノポリシロキサンから選ばれる１種又は２種以上を使用する。 (A) component used for this invention becomes a base polymer of this composition. When preparing a dealcohol-free room temperature curable organopolysiloxane composition, since the storage stability of the uncured composition is a concern, (i) the following general formula (1)

(In the formula, R is a methyl group or an ethyl group, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, X is an integer of 10 or more, and Y is a carbon atom. An alkylene group of 1 to 5, and N is independently an integer of 0 or 1.)
(Ii) the following general formula (2)

(In the formula, R, R ¹ , X, Y and N are as described above, and Z is an alkenyl group having 2 to 5 carbon atoms.)
(Iii) the following general formula (3)

[Wherein, R, R ¹ , X, Y, and N are as defined above, and d is an integer of 1 or more and 10 or less. R ² represents the following general formula (4)

(Wherein R, R ¹ , Y, and N are as described above) are branched chains containing a hydrolyzable group. ]
And (iv) the following general formula (5)

(In the formula, R, R ¹ , X, Y, Z, N, and d are as described above. R ² is a branched chain containing a hydrolyzable group represented by the general formula (4). )
1 type (s) or 2 or more types selected from the organopolysiloxane shown by these are used.

  (A) The preferable viscosity of a component is 1,000-300,000 mPa * s on 25 degreeC conditions. This is because if it is less than 1,000 mPa · s, the cured elastomer may not be able to give excellent physical properties, particularly flexibility and impact resistance, and if it is greater than 300,000 mPa · s. This is because the viscosity of the composition becomes high and the fluidity may be remarkably lowered. Therefore, it is more preferably 5,000 to 100,000 mPa · s. This viscosity is a value measured by a rotational viscometer (hereinafter the same).

In said general formula, R is a methyl group or an ethyl group, and a methyl group is preferable. R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 6 carbon atoms, such as an alkyl group such as a methyl group, an ethyl group or a propyl group, or a cycloalkyl group such as a cyclohexyl group. And a group in which the hydrogen bond of these groups is partially substituted with a halogen atom, for example, 3,3,3-trifluoropropyl group, etc., methyl group, ethyl group, vinyl group, phenyl group, 3, A 3,3-trifluoropropyl group is preferred, and a methyl group is particularly preferred. The plurality of R ¹ in the above general formula may be the same group or different groups.

  Y is an alkylene group having 1 to 5 carbon atoms. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, and the like. Specifically, an ethylene group is preferable.

  Z is an alkenyl group having 2 to 5 carbon atoms, and examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a pentenyl group, and the like. Among these, a vinyl group is most preferable.

  Calcium carbonate, which is the component (B) used in the present invention, is an essential component for giving good workability to the composition and obtaining sufficient oil surface adhesion, particularly good cohesive failure.

Here, it is essential that the component (B) has a surface that is particularly treated with a fatty acid and / or a paraffinic treatment agent, and has an air permeation method specific surface area of 0.5 to 2.5 m ² / g. It is effective for obtaining sufficient oil level adhesion to be within the range. The type of calcium carbonate selected is preferably heavy calcium carbonate. In the case of a composition using colloidal calcium carbonate, sufficient oil level adhesion cannot be obtained, and workability is also improved. It will decline. As such calcium carbonate, a commercial item can be used, for example, Maruo Calcium Co., Ltd. MC coat P-20 etc. can be used.

  (B) Although the addition amount of a component is 10-150 mass parts with respect to 100 mass parts of (A) component, Preferably it is 30-80 mass parts. If the amount is too large, the resin adhesiveness is lowered and the viscosity of the composition is increased, resulting in poor dischargeability during mixing and construction. If the amount is too small, sufficient oil surface adhesion, particularly the cohesive failure rate, is significantly reduced.

The oil-absorbing carbon powder which is the component (C) used in the present invention is an essential component for obtaining good oil surface adhesion, particularly good adhesion strength and cohesive failure in the present composition. Here, specific examples of the oil-absorbing carbon powder as component (C) include porous carbon powders such as activated carbon, carbon blacks such as ketjen black, channel black, furnace black, and acetylene black. These can be used alone or in combination of two or more. Among the above-mentioned carbon blacks, acetylene black powder is more preferred, and among them, the most preferred acetylene black powder is preferably as powdered as possible. Here, when the acetylene black powder that has been pressed is used, the cohesive failure rate of oil surface adhesiveness is lower than that of the powdery material described above. The average particle diameter of the acetylene black powder is in the range of 30 to 50 nm, the BET-N ₂ specific surface area by the adsorption method is in the range of 30 to 80 m ² / g, and the DBP oil absorption is 130 to 200 ml / 100 g. More preferably, the average particle size is in the range of 30 to 40 nm, the specific surface area is in the range of 50 to 80 m ² / g, and the DBP oil absorption is in the range of 150 to 190 ml / 100 g. It is preferable that A commercially available product can also be used as the oil-absorbing carbon powder of component (C), for example, Denka Black manufactured by Denki Kagaku Kogyo Co., Ltd. can be used.

  The addition amount of (C) component is 1-30 mass parts with respect to 100 mass parts of (A) component, Preferably it is 5-20 mass parts. If it is too much, the viscosity of the composition will increase, and the dischargeability at the time of mixing and construction will deteriorate, and if it is too little, sufficient oil level adhesion, especially good adhesive strength and cohesive failure can not be obtained, The thixotropy of the composition itself is also reduced and may flow.

The following general formula (6) of the component (D) used in the present invention:
R ³ _4-n SiK _n (6)
(In the formula, R ³ is the same or different unsubstituted or substituted monovalent hydrocarbon group, K is a hydrolyzable group, and n is an integer of 3 or 4.)
Or a partially hydrolyzed product thereof is one that acts as a crosslinking agent in the composition of the present invention.

R ^{3 in the} general formula (6) is the same or different, preferably an unsubstituted or substituted monovalent hydrocarbon such as an alkyl group, alkenyl group, haloalkyl group or the like having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms. It is a group. K is a hydrolyzable group, and specific examples thereof include alkoxy groups such as methoxy group, ethoxy group and propoxy group, alkenyl oxime groups such as isopropenoxy group and 1-ethyl-2-methylvinyl oxime group, dimethyl keto Axioxy groups such as oxime groups, ketoxime groups such as methyl ethyl ketoxime groups, acetoxy groups, propionoxy groups, butyroyloxy groups, butyloxy groups such as benzoyloxime groups, amino groups such as dimethylamino groups and diethylamino groups, aminoxy groups such as dimethylaminoxy groups and diethylaminoxy groups Examples include amide groups such as a group, N-methylacetamide group, N-ethylacetamide group, and N-methylbenzamide group. n is an integer of 3 or 4.

  Specific examples of the component (D) include ethyl silicate, propyl silicate, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, methyltris (methoxyethoxy) silane, vinyltris (methoxyethoxy) silane. , Methyltripropenoxysilane, methyltriacetoxysilane, vinyltriacetoxysilane, methyltri (butanoxime) silane, vinyltri (butanoxime) silane, phenyltri (butanoxime) silane, propyltri (butanoxime) silane, tetra (butanoxime) silane, 3 , 3,3-trifluoropropyl (butanoxime) silane, 3-chloropropyl (butanoxime) silane, methyltri (propanoxime) silane, methyltri (pentanoxy) Arm) silane, methyl tri (iso-pentanoic) silane, vinyl (cyclopentanoxime) silane, such as methyl tri (cyclohexanoxime) silane, and the partial hydrolyzates and the like are exemplified.

  The crosslinking agent of component (D) may be any of silane and siloxane obtained by partial hydrolysis, and this siloxane may be linear, branched or cyclic, and these are one kind. However, two or more of them may be used.

  The amount of component (D) is 1 to 25 parts by weight, preferably 3 to 15 parts by weight, per 100 parts by weight of component (A). If the component (D) is less than 1 part by mass, this will cause gelation during the production or storage of the composition, or the elastic body obtained from the composition will not exhibit the desired physical properties. If the amount is larger, the shrinkage ratio at the time of curing of the composition is increased, and the elasticity of the cured product is also decreased.

  Next, the curing catalyst of component (E) used in the composition of the present invention is a catalyst for the condensation reaction between the base oil of component (A) and the hydrolyzable crosslinking agent of component (D) in the composition of the present invention. It performs the action. Specifically, organic acid metal salts such as iron octoate, iron naphthenate, cobalt octoate, cobalt naphthenate, tin octoate, tin naphthenate, lead octoate, lead naphthenate, dibutyltin diacetate, dibutyl Alkyl tin ester compounds such as tin dilaurate and dibutyl tin dioctoate, halogenated tin compounds, tin orthoester compounds, metal alcoholates such as tetrabutyl titanate and tetrabutyl zirconate, diisopropoxybis (acetylacetonate) titanium And titanium chelates such as diisopropoxybis (ethylacetoacetate) titanium, and amines such as diethylhydroxylamine, dimethylhydroxylamine, and γ-aminopropyltriethoxysilane.

  The use of the curing catalyst as the component (E) is not limited to one type, and two or more types may be used. The blending amount of the component (E) is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the component (A), and more specifically 0.05 to 5 parts by mass. If it is less than 0.01 parts by mass, it takes a long time to form a tack-free film when the composition is exposed to the air, and its internal curability deteriorates. In addition to the extremely short formation time of several seconds, workability is inferior, and the heat resistance of the cured product is reduced.

  The (F) component silane coupling agent used in the composition of the present invention is a component having an action as an adhesion-imparting component in the room temperature curable organopolysiloxane composition of the present invention. Known silane coupling agents are preferably used, and examples include (meth) acryl silane coupling agents, epoxy silane coupling agents, amino silane coupling agents, mercapto silane coupling agents, and the like. γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyltriethoxysilane, N-β- ( Aminoethyl) γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane and the like are exemplified.

  The compounding quantity of this silane coupling agent is 0-10 mass parts with respect to 100 mass parts of (A) component, Preferably 0.1-5 mass parts is used. When bonding with a filler and an adherend without using a silane coupling agent, the silane coupling agent may not be used. When using, if it exceeds 10 mass parts, it will become disadvantageous in price.

  The room temperature curable organopolysiloxane composition of the present invention preferably contains (G) a non-reactive silicone oil, preferably polydimethylsiloxane having both ends blocked with trimethylsilyl groups. By blending this component, properties such as workability and thread breakage are improved, and rubber properties after curing can be adjusted.

  The viscosity (25 ° C.) is preferably 5 to 50,000 mPa · s, particularly 50 to 5,000 mPa · s. It is preferable that a compounding quantity is 0.1-100 mass parts with respect to 100 mass parts of (A) component, especially 5-80 mass parts.

  In addition to the components (A) to (F) described above, the room temperature curable organopolysiloxane composition of the present invention further improves the flow characteristics before curing, if necessary, to form a rubber-like elastic body after curing. In order to impart necessary mechanical properties, a fine powdery inorganic filler may be added. Inorganic fillers include quartz fine powder, fumed silica, precipitated silica, fumed titanium dioxide, diatomaceous earth, aluminum hydroxide, particulate alumina, magnesia, zinc oxide, zinc carbonate and their silanes, silazanes, and low polymerization. Examples thereof include those that have been surface-treated with siloxanes and organic compounds. Furthermore, an organic solvent, an antifungal agent, a flame retardant, a heat resistance agent, a plasticizer, a thixotropic agent, an adhesion promoter, a curing accelerator, a pigment, and the like are added to the room temperature curable organopolysiloxane composition of the present invention. Can do.

  The room temperature curable organopolysiloxane composition of the present invention can be obtained by mixing the components (A) to (F) and various additives as necessary while blocking moisture. The obtained composition can be used as a so-called one-packaging room temperature curable organopolysiloxane composition that 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 during use.

  The composition of the present invention is particularly effective for automobile use and construction use.

  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 addition, in the following example, a part shows a mass part and a viscosity shows the measured value of the measuring method with a rotational viscometer at 25 degreeC.

[Example 1]
Calcium carbonate (trade name; MC Coat P, whose surface is treated with paraffinic material on 100 parts of dimethylpolysiloxane having a viscosity of 50,000 mPa · s blocked at both ends of the molecular chain with ethylene groups and trimethoxysilyl groups. -20, manufactured by Maruo Calcium Co., Ltd., air permeation method specific surface area: 0.8 to 2.0 m ² / g, heavy calcium carbonate) and acetylene black powder (trade name; Denka black powder, electrochemical industry (Made by Co., Ltd., average particle size 35 nm , BET specific surface area 68 m ² / g, DBP oil absorption 175 ml / 100 g) was dispersed and mixed until uniform, then 5 parts methyltrimethoxysilane, diisopropoxybis ( Acetylacetonate) 2 parts of titanium and 2 parts of γ-glycidoxypropyltrimethoxysilane were added and thoroughly mixed under reduced pressure to obtain a composition. .

[Example 2]
Calcium carbonate (trade name; MC Coat P, whose surface is treated with paraffinic material on 100 parts of dimethylpolysiloxane having a viscosity of 50,000 mPa · s blocked at both ends of the molecular chain with ethylene groups and trimethoxysilyl groups. -20, manufactured by Maruo Calcium Co., Ltd., air permeation specific surface area: 0.8 to 2.0 m ² / g, heavy calcium carbonate 100 parts and acetylene black powder (trade name; Denka black powder, electrochemical industry 10 parts by average particle size 35 nm , BET specific surface area 68 m ² / g, DBP oil absorption 175 ml / 100 g, manufactured by Co., Ltd., were dispersed and mixed until uniform, then 5 parts methyltrimethoxysilane, diisopropoxybis ( Acetylacetonate) 3 parts of titanium and 2 parts of γ-glycidoxypropyltrimethoxysilane were added and mixed thoroughly under reduced pressure to obtain a composition. It was.

[Example 3]
Calcium carbonate (trade name; MC Coat P, whose surface is treated with paraffinic material on 100 parts of dimethylpolysiloxane having a viscosity of 50,000 mPa · s blocked at both ends of the molecular chain with ethylene groups and trimethoxysilyl groups. -20, manufactured by Maruo Calcium Co., Ltd., air permeation method specific surface area: 0.8 to 2.0 m ² / g, heavy calcium carbonate) and acetylene black powder (trade name; Denka black powder, electrochemical industry (Made by Co., Ltd., average particle size 35 nm , BET specific surface area 68 m ² / g, DBP oil absorption 175 ml / 100 g) After 20 parts are dispersed and mixed until uniform, 5 parts of methyltrimethoxysilane, diisopropoxybis ( Acetylacetonate) 2 parts of titanium and 2 parts of γ-glycidoxypropyltrimethoxysilane were added and thoroughly mixed under reduced pressure to obtain a composition. .

[Comparative Example 1]
In Example 1, a composition was prepared in the same manner as in Example 1 except that the surface was treated with paraffinic calcium carbonate.

[Comparative Example 2]
A composition was prepared in the same manner as in Example 1 except that 200 parts of calcium carbonate whose surface was treated with a paraffinic system was used.

[Comparative Example 3]
In Example 1, a composition was prepared in the same manner as in Example 1 except that acetylene black powder was removed.

[Comparative Example 4]
In Example 1, a composition was prepared in the same manner as in Example 1 except that 35 parts of acetylene black powder was used.

[Comparative Example 5]
A composition was prepared in the same manner as in Example 1 except that 200 parts of calcium carbonate whose surface was treated with a paraffinic system and 35 parts of acetylene black powder were used.

[Comparative Example 6]
In Example 1, instead of calcium carbonate whose surface was treated with a paraffinic system, calcium carbonate whose surface was not treated (trade name; Whiten SSB, manufactured by Shiraishi Calcium Co., Ltd., air permeation specific surface area; 1.6 A composition was prepared in the same manner as in Example 1 except that 60 parts (˜1.8 m ² / g, heavy calcium carbonate) were used.

[Comparative Example 7]
In Example 1, instead of calcium carbonate whose surface was treated with a paraffinic system, calcium carbonate whose surface was treated with a special organic acid (trade name: Nanocoat W-25, manufactured by Maruo Calcium Co., Ltd., ratio of air permeation method) A composition was prepared in the same manner as in Example 1 except that 60 parts of a surface area of 2.2 to 2.7 m ² / g, heavy calcium carbonate) was used.

[Comparative Example 8]
In Example 1, instead of calcium carbonate whose surface was treated with a paraffinic system, calcium carbonate whose surface was treated with a fatty acid (trade name; Caltex 5, manufactured by Maruo Calcium Co., Ltd., air permeation specific surface area; A composition was prepared in the same manner as in Example 1 except that 60 parts (7 to 3.5 m ² / g, heavy calcium carbonate) were used.

The room temperature curable organopolysiloxane compositions (silicone rubber compositions) of the above Examples and Comparative Examples were poured into 2 mm molds and cured at 23 ° C. and 50% RH for 7 days to obtain 2 mm thick rubber sheets. The tack free time (touch drying time) and slump property (fluidity) were measured according to the method specified in JIS A5758, and the rubber physical properties were measured from a 2 mm thick sheet according to JIS K6249. In addition, a shear adhesion test specimen having an adhesion area of 2.5 mm ² and an adhesion thickness of 1 mm was prepared from the composition using an adherend having a width of 25 mm and a length of 100 mm. The oil level shearing adhesive strength and cohesive failure rate were determined by applying engine oil on an adherend washed with toluene to 0.1 g / 25 cm ^2, and then applying a room temperature curable organopolysiloxane composition. A 1 mm thick coating was applied to the adherend on which the engine oil was applied to a thickness of 0.1 g / 25 cm ^2, and curing was performed at 23 ° C. and 50% RH for 7 days. The shear adhesive force and the cohesive failure rate were confirmed according to JIS K6850. Moreover, in order to confirm the chemical resistance performance of the obtained rubber sheet, it was immersed in engine oil at 120 ° C. for 10 days, and a chemical resistance test was performed. The results of Examples 1 to 3 are shown in Table 1, and the results of Comparative Examples 1 to 8 are shown in Table 2.

Claims (2)

(A) under following general formula (1)

(In the formula, R is a methyl group or an ethyl group, R ¹ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, X is an integer of 10 or more, and Y is a carbon atom. An alkylene group of 1 to 5, and N is independently an integer of 0 or 1.)
Organopolysiloxane down 1 00 parts by mass shown in,
(B) surface Gapa paraffin has been treated with a treating agent based, and 10 to 150 parts by weight of heavy calcium carbonate surface area air permeation method ratio is 0.5 to 2.5 m ² / g,
(C) As the oil-absorbing carbon powder , the average particle diameter is in the range of 30 to 50 nm, the BET-N ₂ adsorption method specific surface area is in the range of 30 to 80 m ² / g, and the DBP oil absorption is in the range of 130 to 200 ml / 100 g. acetylene black powder 5-30 parts by mass is,
(D) The following general formula (6)
R ³ _4-n SiK _n (6)
(In the formula, R ³ is the same or different alkyl group or alkenyl group having 1 to 8 carbon atoms , K is a hydrolyzable group, and n is an integer of 3 or 4.)
1 to 25 parts by mass of a silane or a partial hydrolyzate thereof represented by
(E) Curing catalyst 0.01 to 15 parts by mass,
(F) Silane coupling agent selected from γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane 0 to 10 parts by mass
From it, and oily surface adhesion, characterized in that it does not contain colloidal calcium carbonate at room temperature curing type organopolysiloxane composition. Hardened | cured material formed by hardening the composition of the said Claim 1 .