JP6004107B2 - Room temperature curable organopolysiloxane composition - Google Patents

Description

  The present invention relates to a room temperature curable (RTV) organopolysiloxane composition used for adhesion / fixation of electric / electronic parts and transportation equipment parts.

  Room temperature curable (RTV) organopolysiloxane compositions that crosslink with moisture are excellent in heat resistance, adhesiveness, electrical properties, etc. in addition to their ease of handling. It is used in various fields such as drugs.

It is known that the addition of a silane coupling agent having an unshared electron pair (for example, a nitrogen atom or a sulfur atom) is effective for imparting adhesion to a room temperature curable (RTV) organopolysiloxane composition. Yes.
However, conventionally used silane coupling agents such as 3-aminopropyltriethoxysilane have a weak interaction with metals and often do not satisfy adhesiveness or storage stability. For example, adhesiveness can be expressed by increasing the amount of silane coupling agent added, but there are problems such as deterioration in storage stability of the RTV organopolysiloxane composition itself. Moreover, although the silane coupling agent which has thiol selectively adhere | attaches on copper, adhesiveness does not express in another metal. Further, such a compound may be difficult to be blended into the RTV organopolysiloxane composition due to odor problems. In view of the above points, there is a need for a silane coupling agent that enables adhesion to various metals with a smaller amount of addition.

In order to strengthen the interaction with the metal, it is necessary to take a stronger bond form (for example, a covalent bond) between the silicone composition and the metal. There are various kinds of organic compounds that form σ bonds with metals, and well-known examples include salen. This compound acts as a ligand that forms chelates on various metals, and has been actively studied as a catalyst in various catalytic asymmetric synthesis reactions, oxidation reactions, and the like (Non-Patent Documents 1 to 4). . Especially, asymmetric epoxidation reaction using Mn complex is famous. A typical synthesis example of salen is a synthesis example in which the corresponding salicylaldehyde and primary amine are reacted in the presence of magnesium sulfate and at room temperature. According to this method, salen can be easily prepared.
However, there has never been an example of blending such a salen compound into a room temperature curable (RTV) organopolysiloxane composition.

Larrow, F et.al (R, R) -N, N'-Bis (3,5-di-tert-butylsalicylidene) -1,2-Cyclohexanediamine manganese (III) Chloride, a Highly Enantioselective Epoxidation Catalyst (Org. Synth (Col. Vol. 10, p.96) Jacobsen, E.N. et.al Highly Enantioselective Epoxidation Catalysts Derived from 1,2-diaminecyclohexane (J. Am. Chem. Soc., 113, 7063) Jacobsen, E.N. et.al Highly Enantioselective Ring Opening of Epoxides Catalyzed by Chiral (salen) Cr (III) Complexes (J. Am. Chem. Soc., 117, 5897) T. Katsuki et.al Highly Enantioselective Cyclopropanation of Styrene Derivatives Using Co (III) -salen Complex as a Catalyst (Tetrahedron, 53, 7201)

  An object of the present invention is to provide a room temperature curable (RTV) organopolysiloxane composition having excellent adhesion to metal.

  As a result of intensive studies to achieve the above object, the present inventor has improved adhesion to various metals by using an organosilicon compound represented by the following general formula (4) as an adhesion aid. It was found that a room temperature curable (RTV) organopolysiloxane composition was obtained, and the present invention was completed.

That is, the present invention provides the following room temperature curable (RTV) organopolysiloxane composition.
<1> (A) The following general formula (1)

(In the formula, each R ¹ is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n is a number with a kinematic viscosity at 25 ° C. in the range of 25 to 500,000 mm ² / s. And / or the following general formula (2)

Wherein R ² is each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, Z ¹ is each independently an alkoxy group having 1 to 4 carbon atoms, and X is each Independently an alkylene group having 1 to 4 carbon atoms or an oxygen atom, n is a number having a kinematic viscosity in the range of 25 to 500,000 mm ² / s at 25 ° C., and a is an integer of 0 or 1 each independently is there)
An organopolysiloxane represented by
(B) The following general formula (3)
R ³ _4-b SiZ ² _b (3)
(Wherein R ³ is a methyl group, an ethyl group, a propyl group, a vinyl group or a phenyl group, Z ² is independently a hydrolyzable group, and b is 3 or 4)
A silane compound and / or a partial hydrolysis condensate thereof : 0.1 to 30 parts by mass with respect to 100 parts by mass of the component (A) ,
(C) The following general formula (4)

(Wherein R ⁴ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, Y is a hydrogen atom, halogen atom, alkoxy group, aryloxy group, alkylthio group, arylthio group, amino group, nitro group, A group, a hydroxyl group, a carboxyl group, a mercapto group, a cyano group or a linear, branched or cyclic alkyl, alkenyl or aryl group having 1 to 10 carbon atoms which may contain a hetero atom, and Z ³ is independently A hydrolyzable group, m is an integer of 1 to 3, and c is an integer of 0 or 1. ) (A) 0.1 to 3 with respect to 100 parts by mass of component 0.0 part by mass ,
(D) Basic compound : 0.8 to 1.2 equivalents relative to 1 mol of component (C) and (E) Curing catalyst : 0.1 to 10 parts by weight per 100 parts by weight of component (A) > A room temperature curable organopolysiloxane composition comprising:

<2> The composition according to <1>, wherein the hydrolyzable group of the component (B) is at least one selected from a ketoxime group, an alkoxy group, and an isopropenoxy group .

<3> The composition according to <1> or <2>, wherein the hydrolyzable group of the component (C) is at least one selected from a methoxy group and an ethoxy group.

The room temperature curable organopolysiloxane composition of the present invention is excellent in adhesion to metal.
Therefore, it is useful for adhesion / fixation of electrical / electronic parts and transportation equipment parts.

The present invention will be described in detail below.
[(A) component]
The component (A) of the organopolysiloxane composition of the present invention is represented by the following general formulas (1) and (2).

In the above formulas (1) and (2), R ¹ and R ² are each an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group, etc. A cycloalkyl group such as a cyclohexyl group; an alkenyl group such as a vinyl group and an allyl group; an aryl group such as a phenyl group and a tolyl group; and a part or all of hydrogen atoms of these groups are substituted with a halogen atom or the like Group such as 3,3,3-trifluoropropyl group. Among these, a methyl group is particularly preferable.

A plurality of R ¹ and R ² in the formulas (1) and (2) may be the same group or different groups, and n is an integer of 10 or more. Is an integer having a kinematic viscosity at 25 ° C. in the range of 25 to 500,000 mm ² / s, preferably in the range of 500 to 100,000 mm ² / s. The kinematic viscosity can be measured with an Ostwald viscometer (hereinafter the same).

In the above formula (2), two Xs are each independently an oxygen atom or an alkylene group having 1 to 4 carbon atoms, specifically, an oxygen atom, a methylene group, an ethylene group, a propylene group, a trimethylene group, tetramethylene. Group, etc. are mentioned, Preferably they are an oxygen atom, a methylene group, and a propylene group.
Moreover, several Z < ¹ > in Formula (2) is respectively independently a C1-C4 alkoxy group, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group etc. are illustrated, a methoxy group, an ethoxy Group is preferred, and methoxy group is particularly preferred. a is independently 0 or 1. (A) A component may be used individually by 1 type, or may use 2 or more types together.

[(B) component]
The component (B) is represented by the following general formula (3).
R ³ _4-b SiZ ² _b (3)
(Wherein R ³ is a methyl group, an ethyl group, a propyl group, a vinyl group or a phenyl group, Z ² is independently a hydrolyzable group, and b is 3 or 4)
That, (B) component, a hydrolyzable group Z ² bonded to a silicon atom having 3 or more in a molecule, and the remaining bound to a silicon atom an organic group is a methyl group, an ethyl group, a propyl group, It is a silane compound selected from a vinyl group and a phenyl group and / or a partial hydrolysis condensate thereof, and acts as a crosslinking agent in the composition of the present invention.

  The hydrolyzable group possessed by the component (B) silane compound and its partially hydrolyzed condensate is, for example, an alkoxy group having 1 to 4 carbon atoms, particularly 1 or 2 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. C2-C4 such as methoxyethoxy group, especially 3 or 4 alkoxy-substituted alkoxy group, dimethyl ketoxime group, ethylmethyl ketoxime group etc. C3-C6, especially 3 or 4 ketoxime group, isopropenoxy group C2-C4 alkenyloxy group, acyloxy group such as acetoxy group, dialkylaminoxy group such as dimethylaminoxy group, and the like. Among them, ketoxime group, alkoxyl group, isopropenoxy group are preferable, alkoxyl group An isopropenoxy group is particularly preferred.

Specific examples of the component (B) include methyltris (dimethylketoxime) silane, methyltris (methylethylketoxime) silane, ethyltris (methylethylketoxime) silane, methyltris (methylisobutylketoxime) silane, propyltri (methylethylketoxime) silane, tetra (Methyl ethyl ketoxime) silane, vinyl tris (methyl ethyl ketoxime) silane, phenyl tris (methyl ethyl ketoxime) silane, methyl tri (methyl isopropyl ketoxime) silane, methyl tri (cyclohexanoxime) silane and other ketoxime silanes, ethyl silicate, propyl silicate, methyl Trimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, Alkoxy silanes such as vinyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, alkoxy-substituted alkoxysilanes such as methyltris (methoxyethoxy) silane, vinyltris (methoxyethoxy) silane, methyltriisopropenoxysilane, ethyltriisopropenoxysilane , Isopropenoxy group-containing silanes such as vinyl triisopropenoxy silane, phenyl triisopropenoxy silane, acetoxy silanes such as methyl triacetoxy silane, ethyl triacetoxy silane, vinyl triacetoxy silane, and partial hydrolysis condensates of these silane Can be mentioned. (B) A component may be used individually by 1 type, or may use 2 or more types together.
(B) The compounding quantity of a component is 0.1-30 mass parts with respect to 100 mass parts of (A) component, Preferably it is 0.5-20 mass parts, Most preferably, it is the range of 1-15 mass parts. If the amount is less than 0.1 parts by mass, sufficient crosslinkability cannot be obtained, and it is difficult to obtain a desired composition having rubber elasticity. Moreover, when it exceeds 30 mass parts, the hardened | cured material obtained will fall easily for a mechanical characteristic.

[(C) component]
Component (C) is a compound that exhibits an important effect as an adhesion-imparting agent, and is represented by the following general formula (4).

Wherein R ⁴ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, Y is a hydrogen atom, halogen atom, alkoxy group, aryloxy group, alkylthio group, arylthio group, amino group, nitro group , A hydroxyl group, a carboxyl group, a mercapto group, a cyano group, or a linear, branched or cyclic alkyl, alkenyl or aryl group having 1 to 10 carbon atoms which may contain a hetero atom, and Z ³ is independently A hydrolyzable group, m is an integer of 1 to 3, and c is an integer of 0 or 1.)
In the general formula (4), as R ⁴ , for example, an alkyl group such as a methyl group, an ethyl group, or a propyl group; a cycloalkyl group such as a cyclohexyl group; an alkenyl group such as a vinyl group or an allyl group; a phenyl group, a tolyl group, or the like And a group in which part or all of the hydrogen atoms of these groups are substituted with a halogen atom, for example, a 3,3,3-trifluoropropyl group. Among these, a methyl group is particularly preferable. c is 0 or 1.
Y is, for example, a linear alkyl group such as a methyl group, an ethyl group, or a propyl group; a cycloalkyl group such as a cyclohexyl group; an alkenyl group such as a vinyl group or an allyl group; an aryl group such as a phenyl group or a tolyl group; Groups, alkoxy groups such as ethoxy groups, propoxy groups, etc .; and groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms, such as 3,3,3-trifluoropropyl groups; hydrogen, halogen atoms Atoms such as alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, amino groups, nitro groups, hydroxyl groups, carboxyl groups, mercapto groups, and cyano groups.
The orientation of Y may be any of ortho, meta, and para with respect to the phenolic hydroxyl group.
Z ³ in formula (4) is a hydrolyzable group, preferably an alkoxy group having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. An ethoxy group is preferable, and a methoxy group is particularly preferable.
Since this silane compound has an imine at the ortho position of the phenolic hydroxyl group, it can form a strong 6-membered chelate (salen complex) with various metal atoms. Furthermore, by having a hydrolyzable group Z ³ , it is incorporated into the crosslinking of the room temperature curable organopolysiloxane.
This compound can be prepared by reacting the corresponding salicylaldehyde with a primary amine, and specific synthesis examples are described in Org. Synth. Coll. Vol. 10, p.96.
(C) The compounding quantity of component is 0.1-3.0 mass parts with respect to 100 mass parts of (A) component, Preferably it is 0.1-2.0 mass parts, Most preferably, it is the range of 0.1-1.5 mass parts. If it is less than 0.1 parts by mass, good adhesiveness may not be exhibited, and if it exceeds 3.0 parts by mass, curability may be lowered, which is not preferable.

[Component (D)]
(D) A component is a basic compound required in order to produce | generate the phenoxide anion of the said Formula (4), and to form a bond with various metals. Such basic compounds include 1,8-diazabicyclo [5,4,0] -7-undecene (DBU), 1,5-diazabicyclo [4,3,0] -5-nonene (DBN), 1 , 1,3,3-tetramethylguanidine and other organic bases having an amine functional group, and DBU having a high basicity is particularly preferable.
Component (D) is preferably 0.8 to 1.2 equivalents (eq.), Particularly preferably 0.9 to 1.1 eq, relative to 1 mol of component (C). Below 0.8 eq., The phenoxide anion necessary to form a sigma bond with the metal may not be generated, and above 1.2 eq., There are drawbacks such as bleeding from a room temperature curable organopolysiloxane composition.

[(E) component]
As the curing catalyst for component (E), one kind may be used alone, or two or more kinds may be used as a mixture. Specific examples of the component (E) include tetraisopropoxy titanium, tetra-n-butoxy titanium, tetrakis (2-ethylhexoxy) titanium, diisopropoxy titanium bis (ethyl acetoacetate), diisopropoxy bis (acetylacetonate) titanium. , Titanic acid esters or titanium chelate compounds such as titanium isopropoxyoctylene glycol; aluminum isopropylate, aluminum sec-butylate, aluminum ethylate, ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum Aluminum alcoholate or aluminum chelate compound such as diisopropylate; tetramethylguanidylpropyltrimethoxysilane, Silanes or siloxanes containing guanidyl groups such as tramethylguanidylpropylmethyldimethoxysilane, tetramethylguanidylpropyltris (trimethylsiloxy) silane; and the like, such as lead octylate and other acidic or basic catalysts Known catalysts are exemplified. In particular, a titanium chelate compound is preferable, and diisopropoxy titanium bis (ethyl acetoacetate) is particularly preferable.
Component (E) is 0.1 to 10 parts by weight, preferably 0.1 to 8 parts by weight, particularly preferably 0.5 to 5 parts by weight, based on 100 parts by weight of component (A). If it is less than 0.1 part by weight, sufficient crosslinkability cannot be obtained. If it exceeds 10 parts by weight, there are disadvantages such as a disadvantage in price and a decrease in the curing rate.

[Other ingredients]
Moreover, you may mix | blend well-known crosslinking agents and additives other than (B) component in this invention in addition to the said component. Examples of known crosslinking agents other than the component (B) include ketoxime silanes such as 3,3,3-trifluoropropyl (methyl ethyl ketoxime) silane and 3-chloropropyl tri (methyl ethyl ketoxime) silane, and the ketoximes. Examples include alkoxysilane, acetoxysilane, and isopropenoxysilane corresponding to silane.

You may add a well-known additive in the range which does not impair the objective of this invention. For example, polyether as wetter and thixotropy improver, non-reactive dimethyl silicone oil as plasticizer, isoparaffin, trimethylsiloxy unit ((CH ₃ ) ₃ SiO _1/2 unit) and SiO ₂ unit as crosslink density improver In addition, as necessary, colorants such as pigments, dyes, and optical brighteners, fungicides, antibacterial agents, non-reactive phenyl silicone oils as bleed oil, fluorosilicones Oils, surface modifiers such as organic liquids incompatible with silicone, solvents such as toluene, xylene, solvent volatile oil, cyclohexane, methylcyclohexane, and low-boiling isoparaffins may also be added.

  The room temperature curable organopolysiloxane composition of the present invention can be produced by mixing each of the above components according to a conventional method, stored in an atmosphere avoiding moisture, and allowed to stand at room temperature, thereby allowing moisture in the air. It usually cures in the presence of 5 minutes to 1 week.

EXAMPLES Hereinafter, examples and comparative examples for specifically explaining the present invention will be shown, but the present invention is not limited to the following examples. “Me” represents a methyl group.
[Example 1]
100 parts by weight of dimethylsiloxane having a molecular weight at both ends of a trimethoxysilyl group and a viscosity of 20,000 mm ² / s at 25 ° C, 5 parts by weight of fumed silica, and 100 parts by weight of heavy calcium carbonate under reduced pressure for 40 minutes Mixed. After mixing under reduced pressure, 8 parts by weight of vinyltrimethoxysilane, 0.25 parts by weight of an organosilicon compound represented by the following formula (5) and 0.14 parts by weight of DBU (1.05 eq. Of the following formula (5)) are added, and 10 minutes under normal pressure Mixed. Thereafter, 1.5 parts by weight of diisopropoxytitanium bis (ethyl acetoacetate) was added and mixed for 15 minutes under reduced pressure to obtain Composition 1.

[Example 2]
100 parts by weight of dimethylsiloxane having a molecular weight at both ends of a trimethoxysilyl group and a viscosity of 20,000 mm ² / s at 25 ° C, 5 parts by weight of fumed silica, and 100 parts by weight of heavy calcium carbonate under reduced pressure for 40 minutes Mixed. After mixing under reduced pressure, 8 parts by weight of vinyltrimethoxysilane, 0.32 parts by weight of an organosilicon compound represented by the following formula (6) and 0.14 parts by weight of DBU (1.05 eq. Of the following formula (6)) were added, and 10 minutes under normal pressure Mixed. Thereafter, 1.5 parts by weight of diisopropoxytitanium bis (ethylacetoacetate) was added and mixed for 15 minutes under reduced pressure to obtain Composition 2.

[Example 3]
100 parts by weight of dimethylsiloxane having a molecular weight at both ends of a trimethoxysilyl group and a viscosity of 20,000 mm ² / s at 25 ° C, 5 parts by weight of fumed silica, and 100 parts by weight of heavy calcium carbonate under reduced pressure for 40 minutes Mixed. After mixing under reduced pressure, 8 parts by weight of vinyltrimethoxysilane, 0.28 parts by weight of an organosilicon compound represented by the following formula (7) and 0.14 parts by weight of DBU (1.05 eq. Of the following formula (7)) were added, and 10 minutes under normal pressure Mixed. Thereafter, 1.5 parts by weight of diisopropoxytitanium bis (ethylacetoacetate) was added and mixed for 15 minutes under reduced pressure to obtain Composition 3.

[Comparative Example 1]
100 parts by weight of dimethylsiloxane having a molecular weight at both ends of a trimethoxysilyl group and a viscosity of 20,000 mm ² / s at 25 ° C, 5 parts by weight of fumed silica, and 100 parts by weight of heavy calcium carbonate under reduced pressure for 40 minutes Mixed. After mixing under reduced pressure, 8 parts by weight of vinyltrimethoxysilane and 0.25 parts by weight of the organosilicon compound represented by the above formula (5) were added and mixed for 10 minutes under normal pressure. Thereafter, 1.5 parts by weight of diisopropoxytitanium bis (ethylacetoacetate) was added and mixed for 15 minutes under reduced pressure to obtain Composition 4.

[Comparative Example 2]
100 parts by weight of dimethylsiloxane having a molecular weight at both ends of a trimethoxysilyl group and a viscosity of 20,000 mm ² / s at 25 ° C, 5 parts by weight of fumed silica, and 100 parts by weight of heavy calcium carbonate under reduced pressure for 40 minutes Mixed. After mixing under reduced pressure, 8 parts by weight of vinyltrimethoxysilane and 0.32 parts by weight of the organosilicon compound represented by the above formula (6) were added and mixed for 10 minutes under normal pressure. Thereafter, 1.5 parts by weight of diisopropoxytitanium bis (ethylacetoacetate) was added and mixed for 15 minutes under reduced pressure to obtain Composition 5.

[Comparative Example 3]
100 parts by weight of dimethylsiloxane having a molecular weight at both ends of a trimethoxysilyl group and a viscosity of 20,000 mm ² / s at 25 ° C, 5 parts by weight of fumed silica, and 100 parts by weight of heavy calcium carbonate under reduced pressure for 40 minutes Mixed. After mixing under reduced pressure, 8 parts by weight of vinyltrimethoxysilane and 0.28 parts by weight of the organosilicon compound represented by the above formula (7) were added and mixed for 10 minutes under normal pressure. Thereafter, 1.5 parts by weight of diisopropoxytitanium bis (ethylacetoacetate) was added and mixed for 15 minutes under reduced pressure to obtain Composition 6.

[Comparative Example 4]
100 parts by weight of dimethylsiloxane having a molecular weight at both ends of a trimethoxysilyl group and a viscosity of 20,000 mm ² / s at 25 ° C, 5 parts by weight of fumed silica, and 100 parts by weight of heavy calcium carbonate under reduced pressure for 40 minutes Mixed. After mixing under reduced pressure, 8 parts by weight of vinyltrimethoxysilane was added and mixed for 10 minutes under normal pressure. Thereafter, 1.5 parts by weight of diisopropoxytitanium bis (ethylacetoacetate) was added and mixed for 15 minutes under reduced pressure to obtain Composition 7.

[Comparative Example 5]
100 parts by weight of dimethylsiloxane having a molecular weight at both ends of a trimethoxysilyl group and a viscosity of 20,000 mm ² / s at 25 ° C, 5 parts by weight of fumed silica, and 100 parts by weight of heavy calcium carbonate under reduced pressure for 40 minutes Mixed. After mixing under reduced pressure, 8 parts by weight of vinyltrimethoxysilane and 0.14 part by weight of DBU were added and mixed for 10 minutes under normal pressure. Thereafter, 1.5 parts by weight of diisopropoxytitanium bis (ethylacetoacetate) was added and mixed for 15 minutes under reduced pressure to obtain Composition 8.

Using prepared compositions 1 to 8, adhesion to various metals was confirmed as follows.
・ Metal adhesion confirmation method Prepared compositions 1 to 8 were applied to an adherend whose surface had been washed with toluene to a thickness of 3 mm and cured for 7 days in a 23 ° C / 50% RH environment. I let you. Seven days later, the rubber (cured product of the composition) was peeled off from the adherend, the adhesiveness was confirmed, and evaluation was performed according to the following criteria.
○: A cut of about 1 cm is made at the interface between the adherend and the rubber, and the rubber does not peel off from the adherend when pulled in the shear direction by hand. Δ: A cut of about 1 cm is made at the interface between the adherend and the rubber. When the hand is pulled in the shearing direction, the rubber partially peels off from the adherend. ×: A cut of about 1 cm is made at the interface between the adherend and the rubber, and when the hand is pulled in the shearing direction, the rubber adheres to the adherend. Table 1 shows the results obtained from peeling from the film.

  From the above results, the adhesion to various metals was confirmed by blending (C) the organosilicon compound and (D) the basic compound into the room temperature curable silicone rubber. Further, it was found that the adhesiveness was not exhibited only by adding (C) an organosilicon compound or (D) a basic compound alone.

Next, the same confirmation was performed for dimethylsiloxane having both ends of the molecular chain being silanol groups, and will be described below.
[Example 4]
Both ends of the molecular chain are silanol groups, and 100 parts by weight of dimethylsiloxane having a viscosity of 20,000 mm ² / s at 25 ° C., 5 parts by weight of fumed silica, and 100 parts by weight of heavy calcium carbonate were mixed for 40 minutes under reduced pressure. . After mixing under reduced pressure, 8 parts by weight of vinyltrimethoxysilane, 0.25 parts by weight of the organosilicon compound represented by the above formula (5) and 0.14 parts by weight of DBU (1.05 eq. Of the above formula (5)) were added, and 10 minutes under normal pressure Mixed. Thereafter, 0.15 part by weight of dioctyltin dilaurate was added and mixed for 15 minutes under reduced pressure to obtain Composition 9.

[Example 5]
Both ends of the molecular chain are silanol groups, and 100 parts by weight of dimethylsiloxane having a viscosity of 20,000 mm ² / s at 25 ° C., 5 parts by weight of fumed silica, and 100 parts by weight of heavy calcium carbonate were mixed for 40 minutes under reduced pressure. . After mixing under reduced pressure, 8 parts by weight of vinyltrimethoxysilane, 0.32 parts by weight of the organosilicon compound represented by the above formula (6) and 0.14 parts by weight of DBU (1.05 eq. Of the above formula (6)) were added, and 10 minutes under normal pressure Mixed. Thereafter, 0.15 parts by weight of dioctyltin dilaurate was added and mixed for 15 minutes under reduced pressure to obtain Composition 10.

[Example 6]
Both ends of the molecular chain are silanol groups, and 100 parts by weight of dimethylsiloxane having a viscosity of 20,000 mm ² / s at 25 ° C., 5 parts by weight of fumed silica, and 100 parts by weight of heavy calcium carbonate were mixed for 40 minutes under reduced pressure. . After mixing under reduced pressure, 8 parts by weight of vinyltrimethoxysilane, 0.28 parts by weight of the organosilicon compound represented by the above formula (7) and 0.14 parts by weight of DBU (1.05 eq. Of the above formula (7)) were added, and 10 minutes under normal pressure Mixed. Thereafter, 0.15 part by weight of dioctyltin dilaurate was added and mixed for 15 minutes under reduced pressure to obtain Composition 11.

[Comparative Example 6]
Both ends of the molecular chain are silanol groups, and 100 parts by weight of dimethylsiloxane having a viscosity of 20,000 mm ² / s at 25 ° C., 5 parts by weight of fumed silica, and 100 parts by weight of heavy calcium carbonate were mixed for 40 minutes under reduced pressure. . After mixing under reduced pressure, 8 parts by weight of vinyltrimethoxysilane and 0.25 parts by weight of the organosilicon compound represented by the above formula (5) were added and mixed for 10 minutes under normal pressure. Thereafter, 0.15 part by weight of dioctyltin dilaurate was added and mixed for 15 minutes under reduced pressure to obtain Composition 12.

[Comparative Example 7]
Both ends of the molecular chain are silanol groups, and 100 parts by weight of dimethylsiloxane having a viscosity of 20,000 mm ² / s at 25 ° C., 5 parts by weight of fumed silica, and 100 parts by weight of heavy calcium carbonate were mixed for 40 minutes under reduced pressure. . After mixing under reduced pressure, 8 parts by weight of vinyltrimethoxysilane was added and mixed for 10 minutes under normal pressure. Thereafter, 0.15 part by weight of dioctyltin dilaurate was added and mixed under reduced pressure for 15 minutes to obtain a composition 13.

[Comparative Example 8]
Both ends of the molecular chain are silanol groups, and 100 parts by weight of dimethylsiloxane having a viscosity of 20,000 mm ² / s at 25 ° C., 5 parts by weight of fumed silica, and 100 parts by weight of heavy calcium carbonate were mixed for 40 minutes under reduced pressure. . After mixing under reduced pressure, 8 parts by weight of vinyltrimethoxysilane and 0.14 part by weight of DBU were added and mixed for 10 minutes under normal pressure. Thereafter, 0.15 part by weight of dioctyltin dilaurate was added and mixed for 15 minutes under reduced pressure to obtain Composition 14.

Using the prepared compositions 9 to 14, adhesion to various metals was confirmed in the same manner as in Table 1.
The results obtained are shown in Table 2.

  In the results of Examples 4 to 6, adhesion to Ni and SUS was not confirmed, but compared to the results of Comparative Examples 6 to 8, adhesion to Cu, Fe, and brass was developed.

  From the above test results, the adhesion to metal differs depending on the curing catalyst (titanium, tin) used, but by adding (C) organosilicon compound and (D) basic compound to room temperature curable silicone rubber, It has been confirmed that the performance is improved.

Claims (3)

(A) The following general formula (1)
(In the formula, each R ¹ is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, and n is a number having a kinematic viscosity in the range of 25 to 500,000 mm ² / s at 25 ° C. Is)
And / or the following general formula (2)
Wherein R ² is each independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, Z ¹ is each independently an alkoxy group having 1 to 4 carbon atoms, and X is each Independently an alkylene group having 1 to 4 carbon atoms or an oxygen atom, n is a number having a kinematic viscosity in the range of 25 to 500,000 mm ² / s at 25 ° C., and a is an integer of 0 or 1 each independently is there)
An organopolysiloxane represented by
(B) The following general formula (3)
R ³ _4-b SiZ ² _b (3)
(Wherein R ³ is a methyl group, an ethyl group, a propyl group, a vinyl group or a phenyl group, Z ² is independently a hydrolyzable group, and b is 3 or 4)
A silane compound and / or a partial hydrolysis condensate thereof : 0.1 to 30 parts by mass with respect to 100 parts by mass of the component (A) ,
(C) The following general formula (4)
(Wherein R ⁴ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, Y is a hydrogen atom, halogen atom, alkoxy group, aryloxy group, alkylthio group, arylthio group, amino group, nitro group, A group, a hydroxyl group, a carboxyl group, a mercapto group, a cyano group or a linear, branched or cyclic alkyl, alkenyl or aryl group having 1 to 10 carbon atoms which may contain a hetero atom, and Z ³ is independently A hydrolyzable group, m is an integer of 1 to 3, and c is an integer of 0 or 1. ) 0.1 to 0.1 parts by mass of 100 parts by mass of component (A) 3.0 parts by mass ,
(D) Basic compound : 0.8 to 1.2 equivalents relative to 1 mol of component (C) and (E) Curing catalyst : 0.1 to 10 parts by weight per 100 parts by weight of component (A) > A room temperature curable organopolysiloxane composition comprising: The composition according to claim 1, wherein the hydrolyzable group of component (B) is at least one selected from a ketoxime group, an alkoxy group and an isopropenoxy group . The composition according to claim 1 or 2, wherein the hydrolyzable group of component (C) is at least one selected from a methoxy group and an ethoxy group.