KR101226373B1 - Room Temperature Curable Organopolysiloxane Composition - Google Patents

Abstract

The present invention (A) 100 parts by mass of diorganopolysiloxane having a hydroxyl group at both ends and / or diorganopolysiloxane having an alkoxysilyl group at both ends,

(B) 0.1 to 10 parts by mass of polyoxypropylene-modified silicone,

(C) 1 to 50 parts by mass of wet silica,

(D) 1 to 20 parts by mass of a silane or siloxane having three or more hydrolyzable groups bound to silicon atoms in one molecule

It is related with the room temperature curable organopolysiloxane composition characterized by containing.

The room temperature curable organopolysiloxane composition of the present invention is excellent in non-sag and imparts excellent rubber properties and durability by room temperature curing.

Room temperature curable organopolysiloxane composition

Description

Room temperature curable organopolysiloxane composition

[Patent Document 1] US Patent No. 4,261,758

[Patent Document 2] Japanese Patent Application Laid-Open No. 2-48586

[Patent Document 3] Japanese Patent Application Laid-Open No. 1-245057

[Patent Document 4] Japanese Unexamined Patent Publication No. 61-21158

[Patent Document 5] Japanese Patent Application Laid-Open No. 62-135560

The present invention relates to a room temperature curable organopolysiloxane composition which is excellent in non-sag and is preferably used as a silicone-based sealing agent, an adhesive, or the like, which gives excellent rubber properties, durability by curing at room temperature.

In the construction of various types of concrete, sash joints, glass circumference, etc., the current method of filling with a sealing material such as synthetic rubber is common, this sealing material is silicone, polysulfide, modified silicone, polyurethane, acrylic rubber Although various things, such as SBR type and a butyl rubber type, are known, the condensation hardening type silicone type sealing material is widely used from the viewpoint of adhesiveness, heat resistance, and weather resistance. In that case, the basic performance additionally required in addition to weather resistance is non-flow and fatigue durability.

As for the non-flowability, it is known that the use of non-flow agents such as polyether and the kind of filler greatly contribute. In the general-purpose silicone sealing material currently distributed, treated dry silica and surface-treated colloidal calcium carbonate are the mainstream, and in combination with a non-flow agent, U.S. Patent No. 4,261,758 (Patent Document 1) and Japanese Patent Publication ( [0002] The number of dry silicas and a polyether having a molecular weight of 300 to 200,000 is illustrated in Japanese Patent Application Laid-Open No. 2-48586 (Patent Document 2). In addition, Japanese Patent Laid-Open No. Hei 1-245057 (Patent Document 3) exemplifies a polysiloxane-polyether copolymer having a surface bonded to dry silica and a carboxyl group pretreated with octamethylcyclotetrasiloxane. In addition, Japanese Patent Application Laid-Open No. 61-21158 (Patent Document 4) discloses a polyether and a filler having a hydrolyzable silyl group at both ends of Japanese Patent Application Laid-Open No. 62-135560 (Patent Document 5). Although the combination of the polypropylene glycol which has a ketooxime group at both ends and fumed silica is illustrated, the room temperature hardenable organopolysiloxane composition which is more excellent in nonflow is desired.

It is an object of the present invention to provide a room temperature curable organopolysiloxane composition which is excellent in non-flowability and imparts excellent rubber properties by room temperature curing.

Fillers frequently used in silicone rubbers are wet silicas, but they are not used in condensation-curable silicone rubbers because they are difficult to impart. MEANS TO SOLVE THE PROBLEM The present inventors examined in order to provide a non-flow property to the room temperature curable organopolysiloxane composition used for condensation type silicone sealant etc. which used wet silica, and the specific polyether modified silicone, ie, a polyoxypropylene modified silicone, is non-flowing. The present inventors have found something useful for imparting sex to complete the present invention.

Therefore,

(A) 100 parts by mass of diorganopolysiloxane having hydroxyl groups at both ends and / or diorganopolysiloxane having alkoxysilyl groups at both ends,

(B) 0.1 to 10 parts by mass of polyoxypropylene-modified silicone,

(C) 1 to 50 parts by mass of wet silica,

(D) 1 to 20 parts by mass of a silane or siloxane having three or more hydrolyzable groups bound to silicon atoms in one molecule

It provides a room temperature curable organopolysiloxane composition characterized by containing.

In this case, it is preferable that (B) component is 1 type, or 2 or more types of silicone represented by following Chemical formulas 1-3.

Wherein R is the same or different unsubstituted or substituted monovalent hydrocarbon group, Y is -R ¹ -O- (C ₃ H ₆ O) _j -H, and R ¹ is an alkylene group having 1 to 12 carbon atoms K is an integer of 1 or more, m is an integer of 1 or more, k + m is an integer of 10 or more, n is an integer of 4 or more, j is an integer of 5 or more).

Moreover, it is preferable that the water content of (C) component is 1 mass% or less.

The room temperature curable organopolysiloxane composition of the present invention

(E) 0.01 to 10 parts by mass of a curing catalyst and / or

(F) 0.1 to 20 parts by mass of silane coupling agent

It may further contain. The composition is effectively used as a sealing agent, an adhesive.

BEST MODE FOR CARRYING OUT THE INVENTION [

[(A) component]

Component (A) of the room temperature curable organopolysiloxane composition of the present invention is diorganopolysiloxane having hydroxyl groups at both ends and / or diorganopolysiloxanes having alkoxysilyl groups at both ends, which is used as the base polymer of the present composition. . As this component, what is represented by following formula (4) or (5) can be used.

Wherein R ² is the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, R ³ is the same or different unsubstituted or substituted monovalent hydrocarbon group having 1 to 6 carbon atoms, and X is Is an oxygen atom or an unsubstituted or substituted bivalent hydrocarbon group having 2 to 6 carbon atoms, a is an integer of 10 or more, and n is an integer of 1 to 3.)

Each R ² is independently an alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, hexyl group, cycloalkyl group such as cyclohexyl group, alkenyl group such as vinyl group, allyl group, propenyl group, and aryl such as phenyl group A monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8, such as a group, or a chloromethyl group, 3,3,3-trifluoropropyl group in which part or all of the hydrogen atoms of these groups are substituted with a halogen atom or the like Monovalent substituted hydrocarbon groups, such as these, are mentioned.

R ³ is independently a monovalent hydrocarbon group having 1 to 6 carbon atoms, such as an alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, alkenyl group such as isopropenyl group, or some or all of the hydrogen atoms of these groups Monovalent substituted hydrocarbon groups, such as the chloromethyl group and 3,3,3- trifluoropropyl group which substituted the halogen atom etc. are mentioned. In consideration of reactivity, a methyl group and an ethyl group are particularly preferable.

 X represents an oxygen atom or a divalent hydrocarbon group having 2 to 6 carbon atoms such as an ethylene group, a propylene group, a butylene group, and a 2-methylpropylene group, or a part in which part or all of the hydrogen atoms of these groups are replaced with a halogen atom or the like And optionally substituted hydrocarbon groups.

n is an integer of 1 to 3, but particularly preferably 2 or 3.

Although a is an integer of 10 or more as mentioned above, it is preferable that it is a number which makes the viscosity of diorganopolysiloxane become 100-1,000,000 mPa * s at 20 degreeC, More preferably, it is a number which makes 500-200,000 mPa * s. In addition, this viscosity is the value obtained by the rotational viscometer.

Such polymers are materials known in the art. The polymer of formula (4) can be obtained by equilibrating the corresponding cyclic siloxane in the presence of water or the like. In addition, when X is an oxygen atom in the polymer of Formula (5), it can obtain by condensation reaction of the polymer of Formula (4) and the corresponding alkoxysilane. In the polymer of the formula (5), when X is a divalent hydrocarbon, an organopolysiloxane having an alkenyl group at both ends thereof, a silane having an alkoxy group and a Si—H group, or an organo having a Si—H group at both ends The silane which has an alkoxy group and an alkenoxy group with respect to polysiloxane can be obtained by addition-reacting under transition metal catalysts, such as platinum.

[Component (B)] [

The polyoxypropylene-modified silicone as the component (B) is preferably one or two or more represented by the following general formulas (1) to (3), which act as a non-flow agent of the present invention.

≪ Formula 1 >

<Formula 2>

<Formula 3>

Wherein R is the same or different unsubstituted or substituted monovalent hydrocarbon group, Y is -R ¹ -O- (C ₃ H ₆ O) _j -H, and R ¹ is an alkylene group having 1 to 12 carbon atoms K is an integer greater than or equal to 1, m is an integer greater than or equal to 1, k + m is an integer greater than or equal to 10, n is an integer greater than or equal to 4, j is an integer greater than or equal to 5).

Here, R is preferably an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, and the same groups as those described above for R ² can be given.

In addition, R <^1> is a C1-C12, especially 2-4 alkylene group, and a methylene group, an ethylene group, trimethylene group, tetramethylene group, etc. are illustrated. k is at least 1, preferably 3 to 100, particularly preferably 5 to 50, m is at least 1, preferably 3 to 100, particularly preferably 5 to 50, and k + m is 10 or more, preferably Is 6 to 200, particularly preferably 10 to 100. In addition, n is 4 or more, preferably 4 to 20, particularly preferably 4 to 10, and j is 5 or more, preferably 10 to 200, particularly preferably 20 to 100.

This polyoxypropylene modified silicone is obtained by addition reaction of the siloxane which has a corresponding hydrosilyl group, and the polypropylene glycol which has an alkenyl group at one terminal and a hydroxyl group at one terminal in presence of a platinum catalyst.

The compounding quantity of this polyoxypropylene modified silicone is 0.1-10 mass parts per 100 mass parts of (A) component, Preferably 0.2-5 mass parts is used. If it is less than 0.1 mass part, sufficient nonflow property will not be obtained, and if it exceeds 10 mass parts, it will become disadvantageous in price.

[Component (C)] [

The wet silica as component (C) acts as a filler in the room temperature curable organopolysiloxane composition of the present invention. The method for producing wet silica is a method of neutralizing the aqueous solution to precipitate silica, filtering and drying the silica, using sodium silicate as a raw material, and performing a hydrolysis reaction using an alkoxysilane instead of sodium silicate. Etc. are known. This wet silica has a specific surface area (BET method) of 50 m ² / g or more, preferably 75 m ² / g or more, particularly preferably 100 to 400 m ² / g, and specific surface area (BET method) / Specific surface area (CTAB method) = 1.0-1.3, Preferably it is 1.0-1.2, Especially preferably, it is 1.0-1.1, and moisture content is 1 mass% or less, Preferably it is 0.5 mass% or less. If the specific surface area (BET method) is less than 50 m ² / g, the provision of mechanical strength becomes insufficient. In addition, when the specific surface area (BET method) / specific surface area (CTAB method) is outside the range of 1.0 to 1.3, or when the water content exceeds 1% by mass, the composition gels during kneading. Here, the specific surface area (BET method) is the surface by nitrogen adsorption amount, the specific surface area (CTAB method) is the surface by the adsorption amount of N-cetyl-N, N, N-trimethylammonium bromide, and this ratio is close to 1. The more there is no pores inside, the more moisture is absorbed into the internal pores. Therefore, for example, even if there is much moisture content in external appearance, it becomes easy to remove. This wet silica is available, for example, as Siloa72X (made by Rodea Japan). The water content can also be dried and manufactured to a predetermined amount by a batch drying tank, a continuous ribbon blender, or the like in advance.

The addition amount of the wet silica which is (C) component is 1-50 mass parts with respect to 100 mass parts of (A) component, Preferably it is 5-30 mass parts. If it is less than 1 mass part, the addition amount is too small and a non-flow property is not obtained. If it exceeds 50 mass parts, a viscosity will become high and workability will fall.

[Component (D)] [

Silane or siloxane which has three or more hydrolysable groups couple | bonded with the silicon atom in 1 molecule which is (D) component acts as a storage stabilizer and a crosslinking agent in the room temperature curable organopolysiloxane composition of this invention. As a hydrolysable group which a silane compound and its partial hydrolyzate have, a ketooxime group, an alkoxy group, an acetoxy group, isopropenoxy group etc. are mentioned, for example. Specific examples include tetrakis (methylethylketooxime) silane, methyltris (dimethylketooxime) silane, methyltris (methylethylketooxime) silane, ethyltris (methylethylketooxime) silane and methyltris (methylisobutylketooxime ) Ketooximesilanes, such as a silane and a vinyl tris (methyl ethyl ketooxime) silane, and alkoxysilanes, such as methyl trimethoxysilane, vinyl trimethoxysilane, phenyltrimethoxysilane, and vinyl triethoxysilane, methyl Acetoxysilanes such as triacetoxysilane and vinyltriacetoxysilane, isopropenoxysilanes such as methyltriisopropenoxysilane, vinyltriisopropenoxysilane, and phenyltriisopropenoxysilane, and And partial hydrolysis condensates of these silanes. These may be used independently or may use multiple types together.

(D) component is used in 1-20 mass parts with respect to 100 mass parts of (A) component, Preferably it is used in the range of 5-15 mass parts. If it is less than 1 mass part, sufficient crosslinking will not be obtained, and it will be difficult to obtain the composition which has the target rubber elasticity, and when it exceeds 20 mass parts, it will become disadvantageous in price.

[Component (E)] [

The hardening catalyst which is (E) component acts as a catalyst of hardening reaction by reaction of (A) component and (D) component, and hydrolysis of a composition in the room temperature curable organopolysiloxane composition of this invention. These include tin ester compounds such as dioctate tin, alkyl tin ester compounds such as dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dioctoate, tetraisopropoxycitane, tetra-n-butoxy Titanic esters or titanium chelate compounds such as titanium, tetrakis (2-ethylhexoxy) titanium, dipropoxybis (acetylacetonate) titanium, titanium isopropoxyoctylene glycol, zinc naphthenate, zinc stearate, zinc- Organometallic compounds such as 2-ethyloctoate, iron-2-ethylhexate, cobalt-2-ethylhexate, manganese-2-ethylhexate, cobalt naphthenate, and alkoxyaluminum compounds, 3-aminopropyltriethoxy Aminoalkyl group substituted alkoxysilanes such as silane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, hexylamine, dodecylamine phosphate, tetramethylguanidine, diaza Amine compounds such as cyclononane and salts thereof, quaternary ammonium salts such as benzyltriethylammonium acetate, lower fatty acid salts of alkali metals such as potassium acetate, sodium acetate, lithium oxalate, dimethylhydroxyamine, diethylhydroxylamine and the like Silanes containing guanidyl groups such as dialkylhydroxylamine, tetramethylguanidyl propyltrimethoxysilane, tetramethylguanidyl propylmethyldimethoxysilane, and tetramethylguanidyl propyltris (trimethylsiloxy) silane Or siloxane etc. are illustrated, Especially a tin ester compound and an alkyl tin ester compound are used preferably. These are not limited to one kind thereof, and may be used as a mixture of two or more kinds.

Moreover, as for the compounding quantity of these curing catalysts, 0.01-10 mass parts, especially 0.05-5 mass parts are preferable with respect to 100 mass parts of (A) component.

[(F) component]

The silane coupling agent which is (F) component is a component which has an effect | action as an adhesion provision component in the composition of this invention. As the silane coupling agent, those known in the art are preferably used. It is especially preferable to have an alkoxysilyl group and an alkenoxysilyl group as a hydrolyzable group, and it is a vinyl tris ((beta) -methoxyethoxy) silane, (gamma)-methacryloxypropyl trimethoxysilane, and (beta)-(3, 4- epoxy). Cyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyl methyldiethoxysilane, N-β- (aminoethyl) γ-aminopropyltrimethoxysilane, γ- Aminopropyl triethoxysilane, (gamma)-mercaptopropyl trimethoxysilane, (gamma)-glycidoxy propyl triisopropenyl silane, (gamma)-glycidoxy propyl methyl diisopropenoxy silane, etc. are illustrated. In particular, the use of an amine coupling agent is preferable.

The compounding quantity of this silane coupling agent is 0.1-20 mass parts per 100 mass parts of (A) component, Preferably 0.2-10 mass parts is used. If it is less than 0.1 mass part, sufficient adhesiveness will not be obtained, and if it exceeds 10 mass parts, it may become disadvantageous in price.

[Other Ingredients]

In addition, as long as the effect of the present invention is not impaired, use of an additive generally known in addition to the above components is not impeded. Examples of the additive include silicone oils and isoparaffins as plasticizers. Colorants such as pigments, dyes and fluorescent brighteners, bioactive additives such as antibacterial agents, antibacterial agents, insect repellents and marine organism repellents, and bleed oils may be used as necessary. Surface modifiers such as phenylsilicone oil, fluorosilicone oil, silicone incompatible organic liquids, toluene, xylene, solvent gasoline, cyclohexane, methylcyclohexane, low boiling isoparaffin, and the like may also be added.

The composition of this invention is applicable to the use in existing silicone type sealing agents, such as a building sealing agent, an adhesive for electrical and electronics, and a sealing compound for transports, and an adhesive agent. Furthermore, it can be applied to a building coating agent having thixotropy by diluting with a solvent having a suitable capacity, a coating agent for underwater structures, a bottom paint, a coating agent for outdoor electric structures, a coating agent for electric and electronic products, and the like.

<Examples>

Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited to a following example. In addition, in the following example, Me represents a methyl group.

Example 1

100 parts by mass of dimethylpolysiloxane having a viscosity of 50,000 mPa · s having hydroxyl groups at both ends, 1,3,5,7-tetramethyl-1,3,5,7-tetrahydrotetracyclosiloxane and allyl groups at one end, and other 2 parts by mass of an addition reaction product of polypropylene glycol having a polymerization degree of 9 having a hydroxyl group at one end, 15 parts by mass of wet silica (Siloa72X, manufactured by Rodea Japan) with a water content of 0.8% by mass, 8 parts by mass of vinyltributane oxime silane, 0.15 mass part of dibutyltin dioctoate and 1 mass part of (gamma) -aminopropyl triethoxysilanes were mixed until it became uniform under dry conditions, and the composition 1 was prepared.

[Example 2]

Polypropylene glycol of Example 9 having 1,3,5,7-tetramethyl-1,3,5,7-tetrahydrotetracyclosiloxane, an allyl group at one end and a hydroxyl group at the other end Polypropylene glycol having a degree of polymerization of 23, having 1,3,5,7-tetramethyl-1,3,5,7-tetrahydrotetracyclosiloxane, an allyl group at one end and a hydroxyl group at the other end A composition 2 was prepared in the same manner as in Example 1, except that the addition reactant was used.

[Example 3]

In Example 1, except for using a wet silica (fine seal E70, manufactured by Tokuyama Co., Ltd.) with a water content of 0.5% by mass instead of a wet silica (Siloa72X, manufactured by Rodea Japan) with a water content of 0.8% by mass. Composition 3 was prepared in the same manner.

Comparative Example 1

Polypropylene glycol of Example 9 having 1,3,5,7-tetramethyl-1,3,5,7-tetrahydrotetracyclosiloxane, an allyl group at one end and a hydroxyl group at the other end A composition 4 was prepared in the same manner as in Example 1, except that polypropylene glycol of the polymerization degree 9 having an allyl group at one end and a hydroxyl group at the other end was used instead of the addition reaction product of.

Comparative Example 2

Polypropylene glycol of Example 9 having 1,3,5,7-tetramethyl-1,3,5,7-tetrahydrotetracyclosiloxane, an allyl group at one end and a hydroxyl group at the other end A composition 5 was prepared in the same manner as in Example 1, except that polypropylene glycol having a polymerization degree of 23 having an allyl group at one end and a hydroxyl group at the other end was used instead of the addition reaction product of.

Slump was measured about the composition of these Examples and the comparative example according to JISA-5758. In addition, a sheet having a thickness of 2 mm was prepared, and cured for 7 days in an atmosphere of 23 ± 2 ° C. and 50 ± 5% RH to confirm its rubber properties. The results are shown in Table 1.

 Example 4

Viscosity dimethylpolysiloxane 100 of 50,000 mPa · s mass portion having a hydroxyl group at both terminals, average formula _{(Me 3 SiO 1/2)} 2 (Me 2 SiO) 18 (HMeSiO) group inform the siloxane with one terminal thereof represented by _20, 2 parts by mass of an addition reaction product of polypropylene glycol having a polymerization degree of 9 having a hydroxyl group at the other end, 20 parts by mass of wet silica (Siloa72X, manufactured by Rodea Japan) having a water content of 0.5% by mass, and a trimethylsiloxy group at both ends 25 parts by mass of dimethylpolysiloxane having a viscosity of 100 mPa · s, 8 parts by mass of methyltributane oxime silane, 0.15 parts by mass of dioctyltin dilaurate, and 0.8 parts by mass of γ-ethylenediaminopropyltrimethoxysilane were uniformly dried. Was prepared until the composition 6 was prepared.

[Example 5]

Example 4 In the, average formula _{(Me 3 SiO 1/2)} 2 (Me 2 SiO) 18 (HMeSiO) group inform the siloxane with one terminal thereof represented by _20, the degree of polymerization of 9 Poly having a hydroxyl group at the other end propylene Instead of glycol addition reactions, poly of polymerization degree 23 having a siloxane represented by the average formula (Me ₃ SiO _1/2 ) ₂ (Me ₂ SiO) ₃₁ (HMeSiO) ₇ , an allyl group at one end and a hydroxyl group at the other end A composition 7 was prepared in the same manner as in Example 4, except that the addition reactant of propylene glycol was used.

[Example 6]

Example 4 In the, average formula _{(Me 3 SiO 1/2)} 2 (Me 2 SiO) 18 (HMeSiO) group inform the siloxane with one terminal thereof represented by _20, the degree of polymerization of 9 Poly having a hydroxyl group at the other end propylene instead of addition reaction of the glycol, the average formula _{(HMe 2 SiO 1/2)} 2 (Me 2 SiO) groups notify the siloxane with one terminal represented by _18, the addition of polypropylene glycol with a polymerization degree 23 having a hydroxyl group at the other end A composition 8 was prepared in the same manner as in Example 4, except that the reactants were used.

[Comparative Example 3]

Example 4 In the, average formula _{(Me 3 SiO 1/2)} 2 (Me 2 SiO) 18 (HMeSiO) group inform the siloxane with one terminal thereof represented by _20, the degree of polymerization of 9 Poly having a hydroxyl group at the other end propylene A composition 9 was prepared in the same manner as in Example 4, except that polypropylene glycol having a polymerization degree of 23 having an allyl group at one end and a hydroxyl group at the other end was used instead of the glycol addition reaction product.

[Comparative Example 4]

In Example 4, instead of the wet silica (Siloa72X, manufactured by Rodea Japan Co., Ltd.) with a moisture content of 0.5 mass%, dry silica (Erosil R972, manufactured by Nippon Aerosol Co., Ltd.) with a moisture content of 0.5 mass% was used. Other than this, the composition 10 was manufactured by the same method as Example 4.

The slump was measured according to JIS A-5758 with respect to the compositions of these Examples and Comparative Examples. In addition, a sheet having a thickness of 2 mm was prepared, and cured for 7 days in an atmosphere of 23 ± 2 ° C. and 50 ± 5% RH to confirm its rubber properties. The results are shown in Table 2. In addition, about the composition 6 and the composition 10, the aluminite H type block was manufactured according to JIS A-1439, and the 9030 fatigue durability test was done according to JIS A-5758. The results are shown in Table 2.

[Example 7]

Viscosity dimethylpolysiloxane 100 of 20,000 mPa · s mass portion having a hydroxyl group at both terminals, average formula _{(Me 3 SiO 1/2)} 2 (Me 2 SiO) 18 (HMeSiO) group inform the siloxane with one terminal thereof represented by _20, 2 parts by mass of an addition reaction product of polypropylene glycol having a polymerization degree of 9 having a hydroxyl group at the other end, 20 parts by mass of wet silica (Siloa72X, manufactured by Rodea Japan) with a water content of 0.5% by mass, and 5 parts by mass of vinyltrimethoxysilane , 11 parts by mass of dipropoxybis (acetylacetonate) titanium was mixed until uniform under dry conditions to prepare a composition 11.

[Example 8]

Viscosity dimethylpolysiloxane 100 of 20,000 mPa · s mass portion having a hydroxyl group at both terminals, average formula _{(Me 3 SiO 1/2)} 2 (Me 2 SiO) 18 (HMeSiO) group inform the siloxane with one terminal thereof represented by _20, 2 parts by mass of an addition reaction product of polypropylene glycol having a polymerization degree of 9 having a hydroxyl group at the other end, 20 parts by mass of wet silica (Siloa72X, manufactured by Rodea Japan) with a water content of 0.5% by mass, and vinyltriisopropenoxysilane 5 Mass 12 and 1 mass part of tetramethylguanidylpropyltrimethoxysilane were mixed until they became uniform under dry conditions, to prepare a composition 12.

[Example 9]

100 parts by weight of viscosity 20,000 mPa and having at both ends of a trimethoxysilyl via an oxygen atom s dimethylpolysiloxane, average formula _{(Me 3 SiO 1/2)} 2 (Me 2 SiO) siloxane represented by ₁₈ (HMeSiO) ₂₀ 2 parts by mass of an addition reaction product of polypropylene glycol having a polymerization degree of 9 having an allyl group at one end and a hydroxyl group at the other end, and 23 parts by mass of wet silica (Siloa72X, manufactured by Rodea Japan) having a water content of 0.5% by mass. 25 parts by mass of dimethylpolysiloxane having a viscosity of 100 mPa · s, 5 parts by mass of methyltrimethoxysilane, and 4 parts by mass of dipropoxybis (acetylacetonate) titanium at a terminal are mixed until uniform under dry conditions. Composition 13 was prepared.

[Example 10]

An ethylene group with trimethoxysilyl groups viscosity 30,000 mPa · s polydimethylsiloxane 100 having mass parts on both ends, an average formula _{(Me 3 SiO 1/2)} 2 (Me 2 SiO) siloxane represented by ₁₈ (HMeSiO) ₂₀ and 2 parts by mass of an addition reaction product of polypropylene glycol of polymerization degree 9 having an allyl group at one end and a hydroxyl group at the other end, 23 parts by mass of wet silica (Siloa72X, manufactured by Rodea Japan) having a water content of 0.5% by mass, both ends A composition 14 was prepared by mixing 8 parts by mass of dimethylpolysiloxane having a viscosity of 100 mPa · s, 5 parts by mass of vinyltrimethoxysilane, and 1.5 parts by mass of tetrapropoxytitane to uniformity under dry conditions.

The slump was measured for the composition of these Examples according to JIS A-5758. In addition, a sheet having a thickness of 2 mm was prepared, and cured for 7 days in an atmosphere of 23 ± 2 ° C. and 50 ± 5% RH to confirm its rubber properties. The results are shown in Table 3.

The room temperature curable organopolysiloxane composition of the present invention is excellent in non-flowability and gives excellent rubber physical properties and durability by room temperature curing.

Claims (6)

(A) 100 parts by mass of diorganopolysiloxane having hydroxyl groups at both ends and / or diorganopolysiloxane having alkoxysilyl groups at both ends, (B) 0.1 to 10 parts by mass of polyoxypropylene-modified silicone, (C) Wet surface area (BET method) of 50 m ² / g or more, specific surface area (BET method) / specific surface area (CTAB method) = 1.0 to 1.3, moisture content of 1% by mass or less, surface-treated 1 to 50 parts by mass of silica, (D) Silane or siloxane which has three or more hydrolysable groups couple | bonded with the silicon atom in 1 molecule, tetrakis (methyl ethyl keto oxime) silane, methyl tris (dimethyl keto oxime) silane, and methyl tris (methyl ethyl keto oxime) Silane, ethyltris (methylethylketooxime) silane, methyltris (methylisobutylketooxime) silane, vinyltris (methylethylketooxime) silane, methyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane , Vinyltriethoxysilane, methyltriacetoxysilane, vinyltriacetoxysilane, methyltriisopropenoxysilane, vinyltriisopropenoxysilane, phenyltriisopropenoxysilane, vinyltributane oxime silane, and 1-20 parts by mass selected from partially hydrolyzed condensates of these silanes, (F) A silane coupling agent, vinyl tris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- Glycidoxypropyltrimethoxysilane, γ-glycidoxypropyl methyldiethoxysilane, N-β- (aminoethyl) γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercapto 0-20 parts by mass selected from propyltrimethoxysilane, γ-glycidoxypropyltriisopropenoxysilane, and γ-glycidoxypropylmethyldiisopropenoxysilane Containing, The room temperature curable organopolysiloxane composition, wherein the component (B) is a polyoxypropylene-modified silicone represented by any one of the following Chemical Formulas 1-3. &Lt; Formula 1 >

<Formula 2>

<Formula 3>

Wherein R is the same or different unsubstituted or halogen-substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, Y is -R ¹ -O- (C ₃ H ₆ O) _j -H, and R ¹ is carbon number K is an integer of 1 or more, m is an integer of 1 or more, k + m is an integer of 10 or more, n is an integer of 4 or more, j is an integer of 5 or more.) The composition according to claim 1, further comprising 0.01 to 10 parts by mass of (E) curing catalyst. The composition of Claim 1 or 2 containing 0.1-20 mass parts of (F) silane coupling agents. The composition according to claim 1 or 2, which is for a sealing agent or an adhesive. delete delete