JP2010084062A - Room temperature-curable organopolysiloxane composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dealcoholization type room temperature-curable organopolysiloxane composition excellent in curability, and giving an adhesive rubber with high strength and high modulus, and excellent in moisture resistance and warm water resistance. <P>SOLUTION: This room temperature-curable organopolysiloxane composition comprises (A) 100 pts.wt. of polyorganosiloxane with molecular chain terminals blocked by a hydroxy- or alkoxysilyl-group and having 50-100,000 mPa s viscosity at 23°C; (B) 0.1-20 pts.wt. of a specific silane compound containing a long-chain alkyl group with branched structure; (C) 3-500 pts.wt. of an inorganic filler; and (D) 0.001-10 pts.wt. of a curing catalyst. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention is a dealcohol that becomes an adhesive rubber having excellent curability, high strength, high modulus, and excellent moisture resistance and warm water resistance by blending a specific long-chain alkyl group-containing silane compound. Type room temperature curable organopolysiloxane composition. The room temperature curable organopolysiloxane composition of the present invention is particularly suitably used for a multi-layer glass seal application.

Conventionally composed of organopolysiloxane having a hydroxyl group at the molecular chain end, a reaction product or mixture of aminoalkylalkoxysilane and epoxyalkylalkoxysilane and a curing catalyst, and has adhesiveness to various substrates that are in contact during curing Organopolysiloxane compositions are known (Patent Document 1). However, the silicone rubber obtained by curing this composition has a drawback that its adhesive strength is reduced in a water-resistant adhesive property, particularly in a harsh environment such as hot water immersion in float glass.
Moreover, in order to improve water-resistant adhesion, it has been proposed to blend a disilaalkane compound (Patent Documents 2 and 3) or a specific methoxy group-containing silicon compound (Patent Document 4), but the effect is sufficient. I could not say it.
Japanese Patent Publication No. 63-23226 JP-A 64-60656 JP 2003-221506 A JP 2007-119768 A

  The present invention provides a room temperature curable organopolysiloxane composition that improves the above-mentioned drawbacks of the prior art, has excellent curability, has a relatively high modulus, and is an adhesive rubber excellent in moisture resistance and warm water resistance. With the goal.

As a result of intensive studies to achieve the above object, the present inventors have obtained a room temperature curable organopolysiloxane composition having the above-mentioned excellent characteristics by blending a specific long-chain alkyl group-containing silane compound. The present invention has been completed.
That is, the present invention
(A) 100 parts by weight of a polyorganosiloxane whose molecular chain end is blocked with a hydroxyl group or an alkoxysilyl group, and the viscosity at 23 ° C. is 50 to 100,000 mPas,
(B) 0.1-20 parts by weight of a long-chain alkyl group-containing silane compound represented by the following general formula,
R ¹ R ² _a Si (OR ³ ) _3-a
(Wherein R ¹ represents a branched alkyl group having 5 to 50 carbon atoms, R ² represents a monovalent hydrocarbon, and R ³ represents an alkyl group. A is an integer of 0 or 1. )
(C) 3 to 500 parts by weight of an inorganic filler, and
(D) A room temperature-curable organopolysiloxane composition comprising 0.001 to 10 parts by weight of a curing catalyst.

  The polyorganosiloxane that is the component (A) of the composition of the present invention is a chain polymer that is blocked by blocking both ends with a hydroxyl group or an alkoxy group. Further, the component (A) may contain a branched polymer.

  The component (A) is a polyorganosiloxane whose molecular chain ends are blocked with a hydroxyl group or an alkoxy group, and is a main component of the room temperature curable composition of the embodiment. If the viscosity of the component (A) is too low, the rubber elasticity after curing will be poor, and if it is too high, the workability will be reduced. It is necessary to be in

  The molecular structure of the polyorganosiloxane is preferably a straight chain represented by the following general formula, but may be a structure having a partially branched chain.

In the formula, R ⁴ represents a substituted or unsubstituted monovalent hydrocarbon group which may be the same or different from each other, and R ⁵ represents a monovalent organic group represented by —ZSiR ⁶ _3-p X _p. . Here, Z represents oxygen (oxo group) or a divalent hydrocarbon group, and R ⁶ represents a substituted or unsubstituted monovalent hydrocarbon group which may be the same as or different from each other. X represents a hydroxyl group (hydroxyl group) or an alkoxy group, and p is an integer of 1 to 3. Moreover, n is a number with which the viscosity in 23 degreeC of the said (A) component satisfy | fills 50-1,000,000 mPas.

R ⁴ includes methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, decyl group, alkyl group such as dodecyl group; alkenyl group such as vinyl group and allyl group; phenyl group And aryl groups such as tolyl group and xylyl group; aralkyl groups such as 2-phenylethyl group and 2-phenylpropyl group are exemplified, and some of hydrogen atoms of these hydrocarbon groups may be other atoms or groups. Substituted with, ie, halogenated alkyl groups such as chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group; substituted carbonized groups such as cyanoalkyl group such as 3-cyanopropyl group A hydrogen group is illustrated. It is easy to synthesize, and the component (A) has a low viscosity with respect to the molecular weight, gives good extrudability to the composition before curing, and gives good physical properties to the composition after curing. it from is preferably 85% or more of the total R ⁴ is a methyl group, and more preferably substantially all R ⁴ are methyl groups.

On the other hand, in the case of imparting heat resistance, radiation resistance, cold resistance or transparency to the composition, a necessary amount of phenyl group as a part of R ⁴ , in the case of imparting oil resistance and solvent resistance, When a 3,3,3-trifluoropropyl group or 3-cyanopropyl group is added as a part of R ⁴ or a surface having paintability is applied, a long chain alkyl group or aralkyl is added as a part of R ^4. The group can be arbitrarily selected depending on the purpose, for example, in combination with a methyl group.

The terminal group R ^{5 of the} component (A) is a silicon-functional siloxy unit represented by —ZSiR ⁶ _3-p X _p and having at least one silicon hydroxyl group or alkoxy group X which is a silicon functional group. Therefore, the component (A) of the embodiment has at least one hydroxyl group or alkoxy group X at each end of the molecule.

In the terminal group R ⁵ , R ⁶ bonded to the silicon atom is a substituted or unsubstituted monovalent hydrocarbon group which may be the same as or different from each other and may be the same as or different from R ^4. Materials similar to those in the R ⁴ are exemplified. A methyl group or a vinyl group is preferable because synthesis is easy and the reactivity of the hydrolyzable group X is excellent. Z is a divalent oxygen (oxo group) or divalent hydrocarbon group which may be the same or different from each other. Examples of the divalent hydrocarbon group include a methylene group, an ethylene group and a trimethylene group. An alkylene group; a phenylene group and the like. From the viewpoint of easy synthesis, an oxo group or an ethylene group is preferable, and an oxo group is particularly preferable.

X is a silanol group or an alkoxy group which is a silicon functional group present in at least one of R ⁵ which is a terminal group. Examples of alkoxy groups include alkoxyl groups such as methoxy, ethoxy, propoxy, and butoxy; substituted alkoxyl groups such as 2-methoxyethoxy and 2-ethoxyethoxy; enoxy groups such as isopropenoxy And may be the same as or different from each other. Alkoxyl groups such as methoxy, ethoxy and propoxy groups are preferred because of their ease of synthesis, physical properties of the composition prior to curing, stability during storage, curability, economy, and use in a wide range of applications. .

In the terminal group R ⁵ , the number p of hydroxyl groups or alkoxy groups X which are silicon functional groups is preferably 1 to 3. Such a silicon-functional polydiorganosiloxane is obtained by ring-opening polymerization or ring-opening copolymerization of a cyclic diorganosiloxane low monomer such as octamethylcyclosiloxane in the presence of water with an acidic catalyst or an alkaline catalyst, It can be obtained by introducing a hydroxyl group bonded to a silicon atom into the terminal of the obtained linear polydiorganosiloxane.

The silicon-functional polydiorganosiloxane in which X is a hydrolyzable group can be synthesized, for example, by condensing a silane having two or more arbitrary hydrolyzable groups to a polyorganosiloxane having a hydroxyl group at the terminal. it can. In this case, since one hydrolyzable group possessed by the silane is consumed by the condensation reaction, the number of X in the terminal group R ⁵ of the polyorganosilosan obtained by the reaction is the hydrolyzable group-containing silane used. One less than the number of hydrolyzable groups possessed by.

  Specific examples of the polyorganosiloxane as component (A) include dimethylpolysiloxane, methylethylpolysiloxane, methyloctylpolysiloxane, methylvinylpolysiloxane, methylphenylpolysiloxane, methyl (3,3,3-trimethyl). Fluoropropyl) polysiloxane, a copolymer of dimethylsiloxane and methylphenylsiloxane, a copolymer of dimethylsiloxane and methyl (3,3,3-trifluoropropyl) siloxane, and the like. The molecular chain terminal of this polyorganosiloxane is blocked with a hydroxyl group or a hydrolyzable group (for example, an alkoxyl group). The molecular chain terminal blocked with a hydroxyl group includes a dimethylhydroxysiloxy group, methylphenylhydroxysiloxy group. Examples of the molecular chain end blocked with an alkoxyl group include a vinyldimethoxysiloxy group, a methyldimethoxysiloxy group, a trimethoxysiloxy group, a methyldiethoxysiloxy group, and a triethoxysiloxy group.

  When the present invention is used in the form of other components such as a main agent and a curing agent, the terminal of the component (A) is generally a silanol group, which is preferable from the reaction rate. In the case of providing in a one-component form, an alkoxysilyl group is preferred at the end of the component (A) from the viewpoints of curability, storage stability, and ease in the production process.

  The component (B) used in the present invention is (B) a long-chain alkyl group-containing silane compound represented by the following general formula.

R ¹ R ² _a Si (OR ³ ) _3-a
(Wherein R ¹ represents a branched alkyl group having 5 to 50 carbon atoms, R ² represents a monovalent hydrocarbon, and R ³ represents an alkyl group. A is an integer of 0 or 1. )
R ¹ is a branched alkyl group having 5 to 50 carbon atoms. Among them, an alkyl group having a length of 6 or more is excellent in water resistance, more preferably 8 or more, and particularly preferably 12 or more.

  The carbon number range of the preferred alkyl group is 6 to 48, particularly 12 to 32.

  Further, the number of branched carbons is preferably 2 or more, more preferably 4 or more, and particularly preferably 8 or more, from the viewpoint of water resistance and easy handling of silane.

Examples of R ² include alkyl groups such as a methyl group, an ethyl group, and a propyl group, and monovalent hydrocarbon groups such as a phenyl group and a vinyl group.

As R ³ , an alkyl group such as a methyl group, an ethyl group, and a propyl group can be generally mentioned because of the hydrolyzability of OR ³ . a is an integer of 0 or 1, and is preferably 0.

  Specific examples of the component (B) include 2-ethylhexyltrimethoxysilane, 4-ethyloctylsilane, 3.5-dimethyl-hexyltrimethoxysilane, 3.7.11-trimethyldodecyltrimethoxysilane, 2-octyldodecyltri Examples include methoxysilane and 2-dodecylhexadecyltrimethoxysilane. Alkoxylation of 2-dodecylhexadecyltrichlorosilane {GELEST, Azmax Co., Ltd., commercial product} or 2-ethylhexene, 4-ethyl-1-octene, 3,5-dimethyl-1-hexene, 2- It can be obtained by a hydrosilylation reaction between an alkene compound such as octyl-1-dodecene and Si—H of hydrogen chlorosilane or hydrogen alkoxysilane.

  Of these, 2-octyldodecyltrimethoxysilane and 2-dodecylhexadecyltrimethoxysilane, in which the branched alkyl group has a large number of carbon atoms, are particularly preferred.

  Compared with a linear alkyl group, the larger the branched group, the more sterically hydrophobic it is, and it is more effective in that it can be hydrophobized with a smaller number of alkoxy groups. is there. These may be used alone or in combination of two or more.

  The amount of component (B) is 0.1 to 20 parts by weight per 100 parts by weight of component (A). If the amount is less than 0.1 parts by weight, the crosslinking reaction is not sufficiently performed, and sufficient water resistance cannot be obtained. On the other hand, when the amount exceeds 20 parts by weight, an excessive crosslinking component that is not consumed by the crosslinking reaction adversely affects the properties of the rubber-like elastic body.

  As the component (C) in the present invention, an inorganic filler is blended in view of reinforcing properties. In general, conventionally known fillers can be widely used as inorganic fillers, and specifically, reinforcing fillers such as fumed silica, precipitated silica, anhydrous silicic acid, hydrous silicic acid, and carbon black. Fibrous fillers such as wood, calcium carbonate, magnesium carbonate, diatomaceous earth, calcined clay, clay, talc, titanium oxide, bentonite, organic bentonite, ferric oxide, zinc oxide, activated zinc white, asbestos, glass fiber and filaments Etc. can be illustrated.

Among these, in view of the thixotropy, viscosity, and adhesive properties of the resulting composition, calcium carbonate is preferable, and the addition of colloidal calcium carbonate is more preferable. Further, it is preferable to add colloidal calcium carbonate having a BET specific surface area of 14.0 to 20.0 m ² / g, an average particle size of 0.05 to 0.20 μm, and a particle surface treated. If the average particle size is less than 0.05 μm, the viscosity becomes too high and the workability is practically inferior, and if it exceeds 0.20 μm, excellent mechanical properties cannot be imparted to the cured product. Can not be imparted to excellent mechanical properties in the cured product is less than even 14.0 m ² / g for the BET specific surface area, poor practical workability becomes too high viscosity exceeds 20.0 m ² / g. Furthermore, examples of the surface treatment of calcium carbonate include those treated with a resin acid containing fatty acids and fatty acid salts, fatty acid esters, rosin acid and the like and salts thereof. Those treated with rosin acid or a metal salt thereof are preferred in that they give the hardened rubber with the highest modulus and are excellent in resistance to heat and humidity and water resistance.

  Examples of such calcium carbonate include Homocal D, Homocal DM, Shiraka Hana TDD, Shiraka Hana IGV (trade name, manufactured by Shiroishi Kogyo Co., Ltd.) and MT-100M (trade name, manufactured by Maruo Calcium Co., Ltd.).

  The amount of component (C) is 3 to 500 parts by weight, preferably 5 to 200 parts by weight, per 100 parts by weight of component (A). If the amount is less than 3 parts by weight, excellent mechanical properties cannot be imparted to the cured product. If the amount exceeds 500 parts by weight, the viscosity becomes too high and the workability is practically inferior. Further, heavy calcium carbonate may be blended as long as the mechanical properties and the water resistance are not impaired. The blending of heavy calcium carbonate is effective in improving workability such as viscosity adjustment, and it is preferable that the surface of such heavy calcium carbonate be treated in the same manner as the calcium carbonate carbonate.

  The component (D) curing catalyst serves as a catalyst for accelerating the curing of the composition of the present invention, and includes tin, titanium, zirconium, iron, antimony, bismuth or manganese organic carboxylates, organic titanates, and organic titanium chelates. Compounds and the like. Specific examples of the catalyst used include dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin dilaurate, dibutyltin malate ester, stannous octoate, a reaction product of dibutyltin oxide and phthalate ester; Reactants of dialkyltin oxides with alkoxysilanes such as ethyl silicate and propyl silicate, tin compounds such as dialkyltin (trialkyloxysilicate) compounds such as dioctyltin bis (triethoxysilicate) and their multimers; tetrabutyl Examples thereof include titanium compounds such as titanate, diisopropoxybis (acetylacetonate) titanium, and diisopropoxybis (ethylacetoacetate). Tin compounds that exhibit sufficient curability in small amounts are preferred. Component (D) is added in an amount of 0.001 to 10 parts by weight, preferably 0.01 to 5 parts by weight per 100 parts by weight of component (A). This is because if the amount of the component (D) is too small, the curing rate is too slow to be suitable for practical use. If the amount is too large, the curing rate is too high, and the working time cannot be taken, and the water resistance decreases.

The mixture or reaction mixture of the component (E) aminoalkylalkoxysilane and epoxyalkylalkoxysilane acts as a cross-linking agent for the composition of the present invention, and has adhesion to various substrates that are in contact during curing. It acts to impart, and when used in combination with the component (B), imparts adhesion durability under severe conditions such as warm water immersion to the cured product of the composition of the present invention. Examples of the aminoalkylalkoxysilane constituting the component (E) include aminomethyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) aminomethyltrimethyl. Examples include butoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, and γ-anilinopropyltriethoxysilane. Epoxyalkylorganoalkoxysilanes include γ-glycidoxyprolyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3 , 4-Epoxycyclohexyl) ethylmethyldimethoxysilane. These aminoalkylalkoxysilanes and epoxyalkylalkoxysilanes are mixed in a molar ratio of (1: 1) to (1: 5), preferably (1: 1.5) to (1: 3), and stored at room temperature or heated. By doing so, a reaction mixture can be easily obtained. In addition, when a titanium-based, zirconium-based, or aluminum-based compound is used as the curing catalyst, it is desirable that the ratio of epoxyalkylalkoxysilane is particularly high in view of the influence on the curing catalyst. This is because when the proportion of aminoalkylalkoxysilane is high, the storage stability of the composition may be lowered. The amount of component (E) added is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight per 100 parts by weight of component (A). This is because if the amount of the component (E) is too small, sufficient rubber strength and adhesiveness cannot be obtained, and if it is too large, the curing rate becomes slow, or the cured rubber becomes too hard.
In the composition of the present invention, an alkoxysilane different from the component (B) and the component (E) can be further added as a crosslinking agent in order to adjust the curability and rubber strength after curing. Examples of such alkoxysilanes include tetrafunctional silanes such as tetramethoxysilane, tetraethoxysilane, methyl cellosolve orthosilicate, and n-propyl orthosilicate; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, vinyl Examples thereof include trifunctional alkoxysilanes such as trimethoxysilane, phenyltrimethoxysilane, and methyltrimethoxyethoxysilane, and partial hydrolysates thereof. The amount of alkoxysilane added is 20 parts by weight or less, preferably 10 parts by weight or less, based on 100 parts by weight of component (A). This is because if the amount of alkoxysilane is too small, a sufficient improvement in rubber strength cannot be obtained, and if it is too large, the curing speed will be slow, or the cured rubber will be too hard.

  Furthermore, a cyclic (iso) cyanurate compound can be added as a thing which improves initial adhesive expression and does not impair water resistance. Examples of such compounds include triallyl cyanurate (1,3,5-triallylcyclotricyanurate) and 1,3,5-tris [3- (trimethoxysilyl), which is an adduct of alkoxyhydrogensilane. Propyl] cyclotricyanurate, 1,3,5-tris [3- (methyldimethoxysilyl) propyl] cyclotricyanurate and triallyl isocyanurate (1,3,5-triallylcyclotriisocyanurate), 1,3, Examples include 5-tris [3- (trimethoxysilyl) propyl] cyclotriisocyanurate and 1,3,5-tris [3- (methyldimethoxysilyl) propyl] cyclotriisocyanurate. Among these, a cyclic isocyanurate compound having a carbonyl group is preferable because of its structure. The amount of the cyclic (iso) cyanurate compound added is 20 parts by weight or less, preferably 10 parts by weight or less, based on 100 parts by weight of the component (A). This is because if the amount of the cyclic (iso) cyanurate compound is too small, sufficient adhesiveness cannot be obtained, and if the amount is too large, the curing speed becomes slow, or the rubber after curing becomes too hard.

  Further, the composition of the present invention may contain an organic solvent, a terminal trimethylsilylated diorganopolysiloxane, a flame retardant, a plasticizer, a thixotropic agent, a colorant, a normal adhesion promoter, an antifungal agent, etc. Doing so does not interfere with the object of the present invention.

  The composition of the present invention is a dealcohol-free room temperature curable organopolysiloxane composition which is an adhesive rubber having high strength, high modulus, and excellent moisture resistance and warm water resistance. The room temperature curable organopolysiloxane composition of the present invention is particularly suitably used for multi-layer glass seal applications, but it can be used in either a one-component form or a multi-component form.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In the synthesis examples, examples and comparative examples, all “parts” represent parts by weight.
Synthesis Example A 2-liter four-necked separable flask equipped with a stirrer, a dropping funnel, a reflux tube, a thermometer, a nitrogen gas flow device, and a decompression device was charged with 294 parts (1.05 mol) of 2-octyl-1-dodecene, chloride A platinum acid isopropanol solution was prepared so that the amount of Pt was 30 ppm, stirred at 60 ° C for 1 hour, then 133.5 parts of trichlorosilane was added dropwise from a dropping funnel, and stirring was continued at a temperature of 80 to 90 ° C for 4 hours. It was. The end point of the reaction was determined to be the point at which absorption of 2150 cm ⁻¹ Si—H disappeared by infrared spectroscopic analysis. After cooling to room temperature, 500 parts of N, N-dimethylaniline was added, and 106 parts (3.3 mol) of methanol was added dropwise from a dropping funnel and stirred for 2 hours. The mixture was heated and stirred at a temperature of 60 to 70 ° C. for 8 hours, and the hydrochloride was suction filtered under a nitrogen atmosphere. Thereafter, the unreacted raw material was distilled off under reduced pressure at 150 ° C. (0.13 kPa), and taken out after cooling. In this way, 2-octyldodecyltrimethoxysilane was obtained.
Example 1
Collagen calcium carbonate "Shiraka Hana TDD" surface-treated with rosin acid with BET specific surface area of 16.0m ² / g and average particle size of 0.06μm on 100 parts of polydimethylsiloxane with a viscosity of 5,000mPas, both ends of which are blocked with silanol groups 100 parts (product name, manufactured by Shiroishi Kogyo Co., Ltd.) were mixed until uniform (hereinafter, the obtained mixture is referred to as a base). On the other hand, carbon black (VULCAN XC72, manufactured by CABOT) is uniformly dispersed in α, ω-divinylmethylsiloxane having a viscosity of 1,000 mPas, and then the components shown in Table 1 are mixed and defoamed to obtain a catalyst composition. 1 was obtained. Next, the base and catalyst composition were mixed and defoamed at a ratio of 100: 10 (weight ratio) to obtain the composition of the present invention.
Examples 2-13, Comparative Examples 1-9
A composition was obtained and evaluated in the same manner as in Example 1 except that the type and amount of each component to be blended were changed as shown in Tables 1 and 2. The results are shown in Tables 1 and 2.

Note that “nc” in the table represents “non-cured; not cured”.
Example 14
Collagen calcium carbonate with a BET specific surface area of 17.0m ² / g and an average particle size of 0.07μm and treated with stearic acid with a viscosity of 5,000mPas and sealed with silanol groups at both ends of the molecular chain 100 parts of S ”(trade name, manufactured by Shiroishi Kogyo Co., Ltd.) were mixed until uniform (hereinafter, the obtained mixture is referred to as a base). On the other hand, each component shown in Table 1 was mixed and defoamed to obtain a catalyst composition. Subsequently, the base and the catalyst composition were mixed and defoamed at a ratio of 100: 10 (weight ratio) to obtain the composition 14 of the present invention.
Examples 15-16
Collagen calcium carbonate with a BET specific surface area of 17.0 m ² / g and an average particle size of 0.07 μm surface-treated with rosin acid with a viscosity of 5,000 mPas and sealed with silanol groups at both ends of the molecular chain. 70 parts of "S" (product name, manufactured by Shiroishi Kogyo Co., Ltd.) and 30 parts of heavy calcium carbonate "Micro Powder 2R" (product name, manufactured by Bihoku Powder Chemical Co., Ltd.) were mixed until uniform (hereinafter obtained) The mixture is called base). On the other hand, each component shown in Table 1 was mixed and defoamed to obtain a catalyst composition. Next, the base and catalyst composition were mixed and defoamed at a ratio of 100: 10 (weight ratio) to obtain compositions 15 and 16 of the present invention.
Comparative Examples 10-12
Comparative compositions 10 to 12 were obtained and evaluated in the same manner as in Example 15 except that the type and amount of each component to be blended were changed as shown in Table 2. The results are shown in Table 2.

The hardness of this composition after 4 hours, 8 hours and 24 hours was examined. Further, the adhesion durability was evaluated by the following method.
<Method for evaluating adhesion durability of room temperature-curable organopolysiloxane composition>
An adhesion durability test specimen was prepared in accordance with the method specified in JIS K5758 architectural sealant. That is, a room temperature curable organopolysiloxane composition was filled between two float glass plates (float plate glass defined in JIS R3202) to prepare an adhesion durability test specimen (commonly known as an H-shaped test specimen). . This adhesion durability test specimen was allowed to stand for 7 days under conditions of a temperature of 23 ° C. and a humidity of 50% to cure the composition. The tensile adhesion strength of the obtained adhesion durability test specimen was measured, and the breaking state of the silicone rubber was observed together. Further, this adhesion durability test specimen was immersed in warm water at 80 ° C. for 14 days, then taken out, measured for tensile adhesive strength, and observed for the breaking state of the silicone rubber. These measurement results and observation results were expressed as follows.
M50: 50% tensile stress Tmax: Maximum tensile stress Emax: Elongation at maximum load CF: Cohesive failure (broken by silicone rubber layer)
TCF: Thin layer breakage (broken by leaving a thin layer of silicone rubber at the interface with the glass plate)
AF: Adhesion failure (peeling at the interface between glass plate and silicone rubber)
Examples 17-18
Collagen calcium carbonate `` Shiraka Hana '' surface-treated with rosin acid with a BET specific surface area of 16.0 m ² / g and an average particle size of 0.06 μm on 100 parts of polydimethylsiloxane with a viscosity of 10,000 mPas blocked at both ends by trimethoxysiloxy groups 75 parts of TDD (manufactured by Shiraishi Kogyo Co., Ltd., trade name) and 75 parts of heavy calcium carbonate “Micro Powder 2R” (trade name, manufactured by Bihoku Flour Chemical Co., Ltd.) were mixed until uniform. Next, 30 parts of polydimethylsiloxane having a viscosity of 100 mPas and having both ends of the molecular chain blocked with trimethylsiloxy groups were mixed until uniform. In addition, 5 parts of 2-octyldodecyltrimethoxysilane, 1 part of a reaction mixture of 3-aminopropyltrimethoxysilane and 3-glycidoxysilyltrimethoxysilane, 1,3,5-tris [3- (trimethoxysilyl) 1 part of propyl] cyclotriisocyanurate and 3 parts of diisopropoxybis (ethylacetylacetate) titanium were blended, and defoamed and mixed until uniform, whereby composition 17 was obtained. In the same manner, composition 18 was obtained using 2-dodecylhexadecyltrimethoxysilane instead of 2-octyldodecyltrimethoxysilane.
Comparative Examples 13-14
Comparative compositions 13 to 14 were obtained in the same manner as in Example 17 using the curing agent components shown in Table 3.
Example 19
Implemented except that polydimethylsiloxane with a viscosity of 10,000 mPas with both ends of the molecular chain blocked with methyldimethoxysiloxy groups was used instead of polydimethylsiloxane with a viscosity of 10,000 mPas with both ends of the molecular chain blocked with trimethoxysiloxy groups. A composition 19 was obtained in the same manner as in Example 17.

The extrusion force, tack free time, and hardness of these compositions were examined by the following methods. In addition, the storage stability was evaluated by the amount of change in the same items by heating acceleration (70 ° C., 5 days).
Extrusion force:
A commercially available 333 ml cartridge was used, a nozzle whose tip was adjusted to an inner diameter of 6.2 mm was mounted, and the force for pushing out the plunger at the bottom of the cartridge was measured by an autograph.
Tack free time:
After the composition was exposed to an atmosphere of 23 ° C. and 50% RH, the time taken to confirm that the composition was in a dry state by touching the surface with a finger was measured.
Hardness:
The composition was extruded into a sheet having a thickness of 2 mm, and the obtained sheet was left standing at 23 ° C. and 50% RH for 168 hours to be cured by moisture in the air, and the hardness of the cured product was measured according to JIS K6301.

  In addition, an adhesion durability test was conducted according to the method specified in JIS K5758 architectural sealant. The results are shown in Table 3.

Claims (4)

(A) 100 parts by weight of a polyorganosiloxane whose molecular chain end is blocked with a hydroxyl group or an alkoxysilyl group, and the viscosity at 23 ° C. is 50 to 100,000 mPas,
(B) 0.1-20 parts by weight of a long-chain alkyl group-containing silane compound represented by the following general formula,
R ¹ R ² _a Si (OR ³ ) _3-a
(Wherein R ¹ represents a branched alkyl group having 5 to 50 carbon atoms, R ² represents a monovalent hydrocarbon, and R ³ represents an alkyl group. A is an integer of 0 or 1. )
(C) 3 to 500 parts by weight of an inorganic filler, and
(D) A room temperature-curable organopolysiloxane composition comprising 0.001 to 10 parts by weight of a curing catalyst. (C) The room temperature-curable organopolysiloxane composition according to claim 1, wherein the inorganic filler is a surface-treated colloidal calcium carbonate having a BET specific surface area of 14.0 to 20.0 m ² / g and an average particle size of 0.05 to 0.20 μm. object.   The room temperature-curable organopolysiloxane composition according to claim 2, wherein the surface treatment agent for colloidal calcium carbonate is rosin acid or a metal salt of rosin acid.   Furthermore, 0.1-20 weight part of (A) component is mix | blended with (E) component 0.1-20 weight part of the mixture or reaction mixture of an aminoalkyl alkoxysilane and an epoxy silane of any one of Claims 1-3. Room temperature curable organopolysiloxane composition.