KR102001681B1 - Room temperature curable organopolysiloxane composition - Google Patents

Abstract

(A) a diorganopolysiloxane having a viscosity of 20 to 1,000,000 mPa.s at 25 DEG C, both ends of which are blocked with a hydroxysilyl group,
(B) a surface-treated calcium carbonate having a BET specific surface area of 25 to 40 m ² / g and having a surface of calcium carbonate particles treated with a fatty acid, wherein the amount of the surface-treated carbonated product obtained by toluene extraction is 0.2% calcium,
(C) an organosilicon compound having at least one alkoxysilyl group in one molecule (excluding a silane coupling agent),
(D) Curing catalyst
Curable organopolysiloxane composition.
According to the room temperature curable organopolysiloxane composition of the present invention, it is possible to provide a curable organopolysiloxane composition which has a high curing rate and is excellent in adhesion to an adherend having an active surface such as float glass, A silicone rubber that maintains the modulus is obtained.

Description

[0001] ROOM TEMPERATURE CURABLE ORGANOPOLYSILOXANE COMPOSITION [0002]

TECHNICAL FIELD The present invention relates to a room temperature curable organopolysiloxane composition which is cured at room temperature to become a silicone rubber. More specifically, the present invention relates to a room temperature curable organopolysiloxane composition which is excellent in workability because of high thixotropy of a composition before curing, Which is excellent in adhesiveness to glass, metal, plastic and the like after curing and which is excellent in water resistance to maintain adhesiveness and rubber properties even in a severe environment such as prolonged immersion in water, To a curable organopolysiloxane composition.

Conventionally, room temperature curable organopolysiloxane compositions comprising a diorganopolysiloxane, alkoxysilane, aminoalkyl group-containing alkoxysilane and a curing catalyst having a silanol group or an alkoxysilyl group at the molecular chain end are known. However, although the composition is quickly adhered to an adherend after curing, there has been a problem in that, particularly when immersed in water for a long time, the surface of float glass, template glass or the like is peeled off from an adherend having an active surface. Therefore, it has not been possible to use it as a structural sealant for a structural adhesive method typified by the SSG method and a SAG method, which require long-term adhesion reliability and load-bearing property, or as a secondary sealing material for a multilayer glass sealing attachment portion.

There is a method of mechanically or chemically treating an adherend to obtain a long-term adhesion reliability by adhering a room temperature curable organopolysiloxane composition to an adherend having an active surface such as float glass, There is a problem that a costly material or an object to be treated is present, or a desired design property can not be obtained by the treatment.

It has been conventionally known that the addition of an epoxyalkylalkoxysilane to an organopolysiloxane composition improves adhesion durability upon immersion in hot water. In order to improve adhesion and adhesion reliability, a reaction product or mixture of an aminoalkylalkoxysilane and an epoxyalkylalkoxysilane (See, for example, Patent Document 1: Japanese Patent Publication (Kokai) No. 52-8854; and Patent Document 2: Japanese Patent Publication (Kokoku) No. 63-23226).

However, the silicone rubber obtained by curing these room temperature-curable organopolysiloxane compositions has a drawback in that the water-resistant adhesiveness is inferior and the adhesive strength is greatly lowered especially in a harsh environment such as hot water immersion or the like in float glass. In addition, the hardness of the rubber, which is a criterion of the curing rate, was not sufficient.

Further, a room temperature curable organopolysiloxane composition in which a tetrafunctional alkoxysilane, a trifunctional alkoxysilane, and an amino group-containing silane are added to a diorganopolysiloxane in order to improve immersion adhesion to an adherend has been proposed For example, Patent Document 3: Japanese Patent No. 2914838).

However, also in the organopolysiloxane composition described in Japanese Patent No. 2914838 (Patent Document 3), adhesion to an adherend having a surface active surface such as float glass after hot water immersion was not sufficient.

(Dimethyoxysilyl) ethane or 1,6-bis (trimethoxysilyl) hexane or the like is used for the organopolysiloxane composition in order to suppress the adhesion strength after immersion in hot water, (Japanese Patent Application Laid-Open No. 64-60656, Patent Document 5: Japanese Patent Application Laid-Open No. 2003-221506) discloses a composition comprising a carbazolyl compound as an adhesion-imparting agent (for example, See the publication).

However, the disilazalkane compound specifically used or exemplified in Japanese Patent Publication (Tokukai) No. 64-60656 (Patent Document 4) has a small molecular weight, high volatility, and emits a specific odor. Therefore, And the working environment is deteriorated at the time of curing. Disclosed in Japanese Patent Application Laid-Open No. 2003-221506 (Patent Document 5) are disilaraalkane compounds having 4 to 10 carbon atoms in the alkylene group, Japanese Patent Laid-Open Publication No. 2009-275098 (Patent Document 6) (Alkoxysilylalkyl) disiloxane, which is proposed in Japanese Patent Application Laid-Open No. 2002-348995, is insufficient to prevent the modulus reduction of the cured product after immersion in hot water.

It is possible to maintain a higher modulus in applications such as a double-layered glass sealing material and a sealing material for structural bonding requiring a high modulus, and also has high thixotropy (thixotropic property) at the time of construction, Temperature curable organopolysiloxane composition that exhibits hardness in a short period of time.

Japanese Patent Publication No. 52-8854 Japanese Patent Publication No. 63-23226 Japanese Patent No. 2914838 Japanese Patent Publication No. 64-60656 Japanese Patent Application Laid-Open No. 2003-221506 Japanese Patent Application Laid-Open No. 2009-275098

An object of the present invention is to provide a thermosetting resin composition which has high thixotropic property, has a high curing rate, is excellent in adhesion to an adherend having a surface active on float glass and the like, Temperature curable organopolysiloxane composition which provides a cured product that does not allow curing of the cured product.

Means for Solving the Problems The present inventors have intensively studied to achieve the above objects, and as a result, they have arrived at the present invention, and the present invention provides the following room temperature curable organopolysiloxane composition.

[1] A resin composition comprising (A) 100 parts by mass of a diorganopolysiloxane having a viscosity of 20 to 1,000,000 mPa 25 at 25 캜 in which both ends of a molecular chain are blocked with a hydroxysilyl group,

(B) a surface-treated calcium carbonate having a BET specific surface area of 25 to 40 m ² / g and 3.0 to 10.0 parts by mass of a fatty acid treated on the surface of calcium carbonate as 100 parts by mass of calcium carbonate, 15 to 150 parts by mass of surface-treated calcium carbonate having an extraction surface treating agent amount of 0.2 mass%

(C) 0.5 to 20 parts by mass of an organosilicon compound having at least one alkoxysilyl group in one molecule (excluding silane coupling agent)

(D) Curing catalyst 0.001 to 10 parts by mass

Curable organopolysiloxane composition. ≪ Desc / Clms Page number 20 >

[2] The room temperature curable organopolysiloxane composition according to [1], wherein the surface-treated calcium carbonate has a BET specific surface area of 27 to 40 m ² / g.
[3] The room temperature curable organopolysiloxane composition according to [1], wherein the component (B) is a surface-treated calcium carbonate treated with a fatty acid of 4.8 to 10.0 parts by mass based on 100 parts by mass of calcium carbonate.

[4] The polishing pad according to [1], wherein the total content of palmitic acid and oleic acid in the surface treating agent present on the surface of the calcium carbonate of the component (B) is 70% by mass or more and the content of stearic acid is 20% The room temperature curable organopolysiloxane composition according to any one of [1] to [3].

(5) A composition comprising at least a composition (i) comprising a component (A) and a component (B) and a composition (ii) comprising at least a component (C) and a component (D) Curable organopolysiloxane composition according to any one of [1] to [4], characterized in that it is a two-liquid mixed type.

[6] The room temperature curable organopolysiloxane according to any one of [1] to [5], further comprising 1 to 200 parts by mass of calcium carbonate other than the component (B) in 100 parts by mass of the component (A) Composition.

[7] The room temperature curable organopolysiloxane composition according to any one of [1] to [6], which is a secondary sealant for a double-layer glass or a sealant for glass glazing.

According to the room temperature curable organopolysiloxane composition of the present invention, it is possible to provide a curable organopolysiloxane composition which has a high curing rate and is excellent in adhesion to an adherend having an active surface such as float glass, A silicone rubber that maintains the modulus is obtained.

The room temperature curable organopolysiloxane composition of the present invention comprises

(A) 100 parts by mass of a diorganopolysiloxane having a viscosity of 20 to 1,000,000 mPa 25 at 25 캜 in which both ends of the molecular chain are blocked with a hydroxysilyl group,

(B) a surface-treated calcium carbonate having a BET specific surface area of 25 to 40 m ² / g and having a surface of calcium carbonate particles treated with a fatty acid, wherein the amount of the surface-treated carbonated product obtained by toluene extraction is 0.2% 15 to 150 parts by mass of calcium,

(C) 0.5 to 20 parts by mass of an organosilicon compound having at least one alkoxysilyl group in one molecule (excluding silane coupling agent)

(D) Curing catalyst 0.001 to 10 parts by mass

And a control unit.

The diorganopolysiloxane of the component (A) is the main component of the composition, and it is a diorganopolysiloxane in which both ends of the molecular chain are blocked with a hydroxysilyl group. If the viscosity is too low, the rubber elasticity after curing becomes insufficient. If the viscosity is too high, the workability deteriorates. Therefore, the viscosity at 25 ° C needs to be in the range of 20 to 1,000,000 mPa · s and is preferably 100 to 100,000 mPa · s s. < / RTI > The molecular structure of the organopolysiloxane is substantially linear, but a part of the molecular chain may be branched so long as the cured product does not impair rubber elasticity. This viscosity is a value measured by a rotational viscometer.

The preferred component (A) is a diorganopolysiloxane represented by the following general formula (1).

(1)

(One)

Wherein R ¹ is a group of 1 to 10 carbon atoms selected from a monovalent hydrocarbon group, a halogenated hydrocarbon group and a cyanoalkyl group, and is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group or an octyl group; A cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; Alkenyl groups such as a vinyl group and an allyl group; Aryl groups such as phenyl, tolyl and naphthyl; Aralkyl groups such as benzyl group, phenylethyl group and phenylpropyl group; A halogenated monovalent hydrocarbon group such as a trifluoropropyl group and a chloropropyl group; cyanoalkyl groups such as? -cyanoethyl group,? -cyano propyl group, and the like. Among them, a methyl group is preferable.

n is the number at which the viscosity measured at 25 캜 with a rotational viscometer is 20 to 1,000,000 mPa.. The component (A) can be prepared by a known method.

The surface-treated calcium carbonate of the component (B) is a component that characterizes the present invention and has a BET specific surface area of 25 to 40 m ² / g, and the surface of the calcium carbonate particles is a surface- However, in particular, when the following conditions are satisfied, more sufficient thixotropy is manifested and durability under hot water immersion is realized.

(1) 3.0 to 10.0 parts by mass of fatty acid relative to 100 parts by mass of calcium carbonate is surface treated calcium carbonate treated on the surface of calcium carbonate.

(2) the total content of palmitic acid and oleic acid in the surface treatment agent is 70% by mass or more, and the content of stearic acid is 20% by mass or less.

(3) The amount of the extracted surface treatment agent obtained by extraction with toluene is 0.2 mass% or less.

The surface-treated calcium carbonate needs to have a BET specific surface area of 25 to 40 m ² / g, preferably 27 to 40 m ² / g, as described above. If it exceeds 40 m ² / g, the mechanical strength of the resulting silicone rubber becomes insufficient, and if it is less than 25 m ² / g, the modulus retention at the time of immersing in hot water becomes insufficient.

The optimum amount of the surface treatment agent varies depending on the BET specific surface area of the calcium carbonate as a raw material before treatment. However, in the range of the BET specific surface area, 3.0 to 10.0 parts by mass of fatty acid is treated with respect to 100 parts by mass of calcium carbonate .

The surface-treated calcium carbonate in the present invention is preferably calcium carbonate whose surface has been treated with a fatty acid containing at least palmitic acid, oleic acid, and stearic acid. The surface treatment with a fatty acid may be surface-treated in the form of an acid, or may be surface-treated in the form of a metal salt such as a sodium salt or a potassium salt, or in the form of an ester. The number of carbon atoms in the fatty acid is preferably 5 to 30, more preferably 10 to 20. More preferably, the content of palmitic acid and oleic acid in the total amount of the surface treating agent is 70% by mass or more, more preferably 75 to 85% by mass, the content of stearic acid is 20% by mass or less, Is not more than 15% by mass.

In the present invention, the amount of the extracted surface treatment agent obtained by extracting the surface-treated calcium carbonate with toluene is 0.2 mass% or less.

In the present invention, as a method of surface-treating the surface of calcium carbonate with a fatty acid, a surface treatment agent of a form selected from a fatty acid, a sodium salt of a fatty acid, a potassium salt of a fatty acid and an ester of a fatty acid is added to a slurry of calcium carbonate particles, And the like. It is considered that the surface treatment agent added to the slurry of the calcium carbonate particles reacts with the calcium present on the surface of the calcium carbonate to form the calcium salt of the fatty acid. Since the calcium salt of the fatty acid is difficult to dissolve in toluene, the surface-treated calcium carbonate is extracted with toluene as described above, whereby the fatty acid in the form of an acid adhering to the surface of the surface-treated calcium carbonate, and the sodium salt, As an index showing the content ratio of the surface treatment agent adhered in the form of ester, the amount of the surface treatment agent to be extracted is defined in the present invention. The amount of the extracted surface treatment agent can be obtained from the following formula.

(Mass of the surface-treated calcium carbonate before extraction) - (mass of the surface-treated calcium carbonate after extraction)} / (mass of the surface-treated calcium carbonate before extraction)] x 100

From the amount of the extracted surface treatment agent, the content ratio of the fatty acid and its salt attached to the surface of the surface-treated calcium carbonate in the form of an acid and in the form of a sodium salt or a potassium salt can be obtained.

In the present invention, the amount of the extracted surface treatment agent is 0.2 mass% or less, more preferably 0.1 mass% or less.

In this case, when the extracted surface treatment agent exceeds 0.2% by mass, the adhesiveness may be lowered or the modulus at the time of hot water immersion may be lowered.

As the method of making the extract surface treating agent to 0.2 mass% or less, the amount of the surface treatment agent can be selected according to the theoretical required amount of the surface treatment agent calculated from the BET method specific surface area of calcium carbonate before surface treatment, You can also choose between.

In the present invention, the composition of the surface treating agent in the surface treated calcium carbonate can be determined by measuring the components of the surface treating agent obtained after decomposition of the surface treated calcium carbonate with an acid or a base, for example, by gas chromatography.

The blending amount of the component (B) is preferably 15 to 150 parts by mass, particularly preferably 30 to 120 parts by mass, per 100 parts by mass of the component (A). When the amount is less than 15 parts by mass, the effect of the present invention can not be obtained. When the amount exceeds 150 parts by mass, the viscosity of the composition becomes excessively high, and the intended workability is not obtained.

The organosilicon compound having at least one alkoxysilyl group in at least one molecule of the component (C) is a component for curing the composition of the present invention. The organosilicon compound having at least one alkoxysilyl group The alkoxysilyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 3 carbon atoms, and the alkoxysilyl group includes at least one dialkoxysilyl group and trialkoxysilyl group in one molecule . The silicon atom may be bonded to a group other than the hydrolyzable group, and the molecular structure thereof may be either a silane or siloxane structure. Particularly, in the case of a siloxane structure, it may be any of linear, branched or cyclic. The component (C) does not contain a silane coupling agent described later.

Specific examples of the component (C) of the present invention include ethyl silicate, propyl silicate, methyltrimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, methyltris (methoxy (Methoxy) silane, and vinyltris (methoxyethoxy) silane, and alkoxyalkoxysilanes and partial hydrolyzed condensates thereof. In addition, 1,3-bis [(triethoxysilyl) ethyl] -1,1,3,3-tetramethyldisiloxane, 1,3-bis [ , 3-tetramethyldisiloxane, 1,3-bis [(methyldimethoxysilyl) ethyl] -1,1,3,3-tetramethyldisiloxane, 1 - [(trimethoxysilyl) 1 - [(methyldimethoxysilyl) ethyl] -3 - [(trimethoxysilyl) ethyl] -1,1,3,3-tetramethyldisiloxane, Bis (trimethoxysilyl) hexane, 1,8-bis (trimethoxysilyl) octane and 1,4-bis (trimethoxysilyl) And bis-silylalkane compounds such as bis (trimethoxysilyl) butane, 1,10-bis (trimethoxysilyl) decane, and 1,6-bis (dimethoxysilyl) hexane.

These may be used alone or in combination of two or more.

The amount of the component (C) is 0.5 to 20 parts by mass, preferably 1 to 10 parts by mass, per 100 parts by mass of the component (A).

Examples of the catalyst for accelerating the curing of component (D) include organic carboxylates, alkoxides of metals such as tin, titanium, zirconium, iron, antimony, bismuth and manganese; Organic titanic acid esters and organic titanium chelate compounds. Specific examples thereof include dibutyltin dilaurate, dibutyltin dioctoate, dioctyltin dilaurate, dibutyltin maleate ester, dimethyltin dineodecano Tin compounds such as dibutyltin dimethoxide, dioctyltin dineodecanoate, stannous octoate and the like; There may be mentioned titanium compounds such as tetrabutyl titanate, diisopropoxybis (acetylacetonate) titanium and diisopropoxybis (ethylacetoacetate), dibutylamine, laurylamine, tetramethylguanidine, tetramethylguanidylpropyl And amine compounds such as trimethoxysilane and salts thereof. They may be used alone or in combination of two or more. It is preferable to add an organotin compound in view of the excellent curing properties such as fast curability and deep curing property of the composition of the present invention. Among them, dialkyl tin dialkoxide and dialkyl tin dicarboxylate are preferable, Dimethyl tin dicarboxylate, dioctyl tin dicarboxylate, and the like. The addition amount thereof is 0.001 to 10 parts by mass, preferably 0.005 to 5 parts by mass, per 100 parts by mass of the component (A).

It is preferable in the composition of the present invention to blend not only the above components (A) to (D) but also a silane coupling agent in that the curing rate of the composition of the present invention and the adhesion to various adherends are further improved. As the silane coupling agent, those having a known epoxy group and an amino group other than the component (C) described above in the technical field are preferably used. As the hydrolyzable group, those having an alkoxysilyl group or alkenoxysilyl group are preferable, and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane,? -Glycidoxypropyltrimethoxysilane,? - Aminopropyltrimethoxysilane, 3- (N-aminomethylbenzylamino) propyltrimethoxysilane, N, N-dimethylaminopropyltrimethoxysilane, N- , N, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine, N, N-bis [3- (trimethoxysilyl) propyl] amine, gamma -mercaptopropyltrimethoxysilane, -Glycidoxypropyltriisopropenoxysilane,? -Glycidoxypropylmethyldiisopropenoxysilane, 1,3,5-tris (trimethoxysilylpropyl) isocyanurate, (meth) acrylsilane And a reactant of an aminosilane and a halogenated alkyl group-containing silane, such as a reaction product of an aminosilane and an epoxy silane, And the like. It is particularly preferable to use a silane coupling agent containing at least one amino group in the molecule.

The blending amount of the silane coupling agent is 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, per 100 parts by mass of the component (A). If it is less than 0.1 part by mass, sufficient adhesion can not be obtained. If it exceeds 20 parts by mass, not only the price is deteriorated, but also the adhesion of hot water is deteriorated.

In the composition of the present invention, surface-treated calcium carbonate and / or untreated calcium carbonate that does not correspond to component (B) may be blended as long as the effect of the present invention is not impaired. For example, the addition of the surface-treated calcium carbonate that does not correspond to the component (B) has the effect of imparting good mechanical properties to the cured product of the composition of the present invention. In addition, irrespective of the treatment and the treatment, the addition of heavy calcium carbonate has an effect of enhancing the adhesiveness. The BET specific surface area of the surface-treated calcium carbonate and untreated calcium carbonate not corresponding to the component (B) is preferably 25 m ² / g or less, and particularly preferably 0.1 to 20 m ² / g.

The amount of the surface-treated calcium carbonate and the untreated calcium carbonate not corresponding to the component (B) is 1 to 200 parts by mass, preferably 5 to 150 parts by mass based on 100 parts by mass of the component (A). This is because if the blending amount of the surface-treated calcium carbonate and untreated calcium carbonate not corresponding to the component (B) is excessively small, the effect of the addition is insufficient, while if it is excessively large, the viscosity of the composition of the present invention becomes high, It is because.

[Other ingredients]

In addition, as long as the effect of the present invention is not impaired, generally known additives other than the above-mentioned components may be used. Examples of the additives include dry process silica, wet process silica, quartz fine powder, titanium dioxide powder, diatomaceous earth powder, aluminum hydroxide powder, magnesium hydroxide powder, particulate alumina, magnesia powder, zinc oxide powder, zinc carbonate powder, barium sulfate powder, Inorganic fillers other than fine calcium carbonate in the form of finely divided particles surface-treated with silane residues, low-polymerization polysiloxanes and the like. The amount of the inorganic filler to be added is 1 to 400 parts by mass, preferably 5 to 200 parts by mass based on 100 parts by mass of the component (A).

Examples of other additives include platinum compounds as flame retardants such as dimethylpolysiloxane and isoparaffin blocked with trimethylsiloxy groups at both ends, zinc oxide powder, polyether as a thixotropic agent, pigments, dyes, fluorescent whitening agents, A heat resistance improving agent such as iron oxide and cerium oxide, a cold resistance improving agent, an antirust agent, a disinfectant, and an antibacterial agent. Solvents such as toluene, xylene, solvent gasoline, cyclohexane, methylcyclohexane and low boiling isoparaffin may also be added.

The room temperature curable organopolysiloxane composition of the present invention can be prepared by mixing the components described above. In this case, the composition (i) comprising at least components (A) and (B) And a composition (ii) comprising the component (D), and it is preferable to mix and apply these compositions (i) and (ii) in use. In this case, the silane coupling agent is preferably incorporated in the composition (ii). Further, an inorganic filler other than calcium carbonate or calcium carbonate other than the component (B) is preferably blended in the composition (i). The other components may be appropriately compounded into the composition (i) or the composition (ii).

The room temperature-curable organopolysiloxane composition of the present invention can be cured at room temperature (room temperature) where neither heating nor cooling is required, and is usually from 0 to 50 ° C, preferably from 5 to 40 ° C. The curing time is usually about 1 hour to 2 weeks, preferably about 3 hours to 1 week.

The room temperature curable organopolysiloxane composition of the present invention is excellent in fast curability. Here, fast curing is a hardness of a cured product by a Type A durometer prescribed in JIS K6253, and is preferably 25 or more after 3 hours of application when left under an environment of 23 캜 and 50% RH.

The room-temperature-curable organopolysiloxane composition of the present invention as described above has a high curing rate and is excellent in adhesion to an adherend having a surface active on float glass or the like and also has a long-term adhesive reliability even under harsh environments such as hot water immersion . Therefore, the composition of the present invention is preferably used as a secondary sealant of a waterproof sealant, a structural sealant of a structural glazing, or a multilayer glass seal attachment portion in applications where such characteristics are required, for example, in civil engineering applications.

[Example]

EXAMPLES Hereinafter, examples and comparative examples of the present invention will be described, but the present invention is not limited by the following examples. The viscosity in the examples is a value measured by a B-type rotational viscometer at 23 캜, and all parts mean parts by mass. The curability and the resistance to hot water adhesion of the composition of the present invention were evaluated according to the following methods. The surface treated calcium carbonate used in the following was the BET specific surface area, surface treatment agent component, amount of surface treatment agent, and amount of extracted surface treatment agent shown in Table 1.

[Example 1]

100 parts by mass of the surface-treated calcium carbonate represented by A in Table 1 and 100 parts by mass of untreated heavy calcium carbonate (trade name " Super S " Maruo Calcium Co.) 40 parts by mass of polydimethylsiloxane having both ends hydroxyl groups blocked with a viscosity of 5,000 mPa.s And the mixture was uniformly mixed using a three-roll mill to prepare a base composition.

On the other hand, to 5 parts by mass of both terminal trimethylsiloxy-terminated polydimethylsiloxane having a viscosity of 5,000 mPa.s, 1 part by mass of carbon black, 3 parts by mass of bis (trimethoxysilylethyl) -1,1,3,3-tetramethyldisiloxane 0.35 parts by mass of N-β- (aminoethyl) γ-aminopropyltrimethoxysilane, 0.65 parts by mass of 1,3,5-tris (trimethoxysilylpropyl) isocyanurate, 0.35 parts by mass of dimethyl tin dineodecano Eight were mixed, and this was used as a catalyst composition. Further, the base composition and the catalyst composition were mixed at a mass ratio of 100: 10 to prepare a room temperature curable organopolysiloxane composition.

[Example 2]

Except that 1,6-bis (trimethoxysilyl) hexane was used in place of 1,6-bis (trimethoxysilylethyl) -1,1,3,3-tetramethyldisiloxane. To obtain a polysiloxane composition.

[Comparative Example 1]

A room temperature curable organopolysiloxane composition was obtained in the same manner as in Example 1 except that the surface-treated calcium carbonate shown by B in Table 1 was used instead of the surface-treated calcium carbonate shown by A in Table 1.

[Comparative Example 2]

A room temperature curable organopolysiloxane composition was obtained in the same manner as in Example 1 except that the surface-treated calcium carbonate shown by C in Table 1 was used in place of the surface-treated calcium carbonate shown by A in Table 1.

[Comparative Example 3]

A room temperature curable organopolysiloxane composition was obtained in the same manner as in Example 1 except that the surface-treated calcium carbonate shown by D in Table 1 was used instead of the surface-treated calcium carbonate shown by A in Table 1.

[Comparative Example 4]

A room-temperature-curable organopolysiloxane composition was obtained in the same manner as in Example 1 except that the surface-treated calcium carbonate shown by E in Table 1 was used instead of the surface-treated calcium carbonate shown by A in Table 1.

[Comparative Example 5]

A room temperature curable organopolysiloxane composition was obtained in the same manner as in Example 1 except that the surface-treated calcium carbonate shown by F in Table 1 was used instead of the surface-treated calcium carbonate shown by A in Table 1.

[Comparative Example 6]

The same procedure as in Example 1 was repeated except that 90 parts by mass of the surface calcium carbonate shown by F in Table 1 and 10 parts by mass of the surface-treated calcium carbonate represented by A were used instead of 100 parts by mass of the surface-treated calcium carbonate shown by A in Table 1 To obtain a room temperature curable organopolysiloxane composition.

[Comparative Example 7]

A room temperature curable organopolysiloxane composition was obtained in the same manner as in Example 1, except that the surface-treated calcium carbonate shown by G in Table 1 was used instead of the surface-treated calcium carbonate shown by A in Table 1.

[Viscosity test]

After curing the obtained room temperature curable organopolysiloxane composition at 23 占 폚 for 24 hours or more, the viscosity at 1 rpm and 10 rpm was measured using an No. 7 rotor of a B-type rotational viscometer under an environment of 23 占 폚, When the viscosity is 2,000 Pa.s or more and the measured value at 1 rpm divided by the viscosity measured at 10 rpm (thixotropic index) is 5 or more, sufficient thixotropy is obtained and it is judged that the workability is good Respectively.

[Curability test]

The room temperature curable organopolysiloxane composition thus obtained was poured in a thickness of about 6 mm and left under the conditions of a temperature of 23 캜 and a humidity of 50% RH after the pouring. After 3 hours and 7 days from the completion of the preparation of the composition, The curability was evaluated by measuring hardness using a Type A durometer as specified. In the present invention, when the hardness after 3 hours is 25 or more, it is judged that the fast curability is good.

[Hot water adhesion test]

Using the obtained room temperature-curable organopolysiloxane composition and a float glass as an adherend, an H-shaped block was produced in accordance with JIS A1439. The H-shaped block was allowed to stand for 7 days in an atmosphere of 23 ° C and 50% RH, and then left in a drier adjusted to 50 ° C for 7 days. The H-shaped block was subjected to a tensile adhesion test, and the modulus and maximum tensile stress at 10% elongation were measured, and the rupture state of the silicone rubber was visually observed and evaluated. This was used as initial data. Next, as the accelerated deterioration test for evaluating the adhesion water resistance for a long period of time, the remaining H-shaped blocks were immersed in hot water at 80 캜 for 28 days and taken out. The modulus and maximum tensile stress at 10% elongation were measured, The fracture state was visually observed and evaluated. This was taken as data after immersion in hot water. The rupture state of the silicone rubber was evaluated as a cohesive failure rate by visually observing the ratio of the area where the rupture of the silicone rubber was observed at the fracture surface. That is, in the case where the entire fractured surface is the cohesive fracture of the silicone rubber, the cohesive failure rate is 100% and the adhesion is judged to be good. In the case where the whole fractured section is interface delamination, the cohesive failure rate is 0% and it is judged that the adhesiveness is poor. Further, when the modulus after immersion in hot water was 0.2 N / mm ² or more, it was judged that the effect of suppressing the decrease of modulus was sufficiently obtained. When it is less than 0.2 N / mm < ^{2 &} gt ;, it was judged that the effect of suppressing the decrease of modulus was insufficient.

The results of the curability test and the hot water adhesion test of the room temperature curable organopolysiloxane compositions obtained in Examples 1 and 2 and Comparative Examples 1 to 7 are shown in Table 2.

As can be seen from Table 2, the room temperature curable organopolysiloxane compositions obtained in Examples 1 and 2 are excellent in curability and adhesiveness, and the adhesiveness is hardly lowered even after being set in a harsh environment such as hot water immersion for a predetermined time And a modulus of 0.20 N / mm ² or more at 10% elongation, it is useful as a sealing material for glass or aluminum such as a waterproof sealant for structural civil engineering applications, a structural adhesive sealant, and a secondary sealant for a double- can do.

[Example 3]

100 parts by mass of the surface-treated calcium carbonate shown by A in Table 1 was added to 100 parts by mass of both end hydroxyl group-blocked polydimethylsiloxane having a viscosity of 5,000 mPa 占 퐏 and uniformly mixed using a three-roll mill to prepare a base composition.

On the other hand, 3 parts by mass of 1,6-bis (trimethoxysilyl) hexane, 0.3 parts by mass of? -Aminopropyltrimethoxysilane and 0.01 part by mass of dimethyltin dinneodecanoate were mixed and used as a catalyst composition. Further, the base composition and the catalyst composition were mixed at a mass ratio of 100: 3.3 to prepare a room temperature curable organopolysiloxane composition.

Claims (7)

(A) 100 parts by mass of a diorganopolysiloxane having a viscosity of 20 to 1,000,000 mPa 25 at 25 캜 in which both ends of the molecular chain are blocked with a hydroxysilyl group,
(B) a surface-treated calcium carbonate having a BET specific surface area of 25 to 40 m ² / g and 3.0 to 10.0 parts by mass of a fatty acid treated on the surface of calcium carbonate as 100 parts by mass of calcium carbonate, 15 to 150 parts by mass of surface-treated calcium carbonate having an extraction surface treating agent amount of 0.2 mass%
(C) 0.5 to 20 parts by mass of an organosilicon compound having at least one alkoxysilyl group in one molecule (excluding silane coupling agent)
(D) Curing catalyst 0.001 to 10 parts by mass
Curable organopolysiloxane composition. ≪ Desc / Clms Page number 20 > The room temperature curable organopolysiloxane composition according to claim 1, wherein the BET specific surface area of the surface-treated calcium carbonate is 27 to 40 m ² / g. 4. The room temperature curable organopolysiloxane composition according to claim 1 or 2, wherein the component (B) is a surface-treated calcium carbonate in which 4.8 to 10.0 parts by mass of the fatty acid is treated on the surface of calcium carbonate with respect to 100 parts by mass of the calcium carbonate. The surface treatment agent according to claim 1 or 2, wherein the total content of palmitic acid and oleic acid in the surface treatment agent present on the surface of the calcium carbonate of the component (B) is 70% by mass or more and the content ratio of stearic acid is 20% % Or less of the organopolysiloxane composition. The composition according to any one of claims 1 to 3, which comprises at least a composition (i) comprising at least components (A) and (B) and a composition (ii) comprising at least components (C) and Packed, and mixed in a two-pack form to mix them before use. ≪ RTI ID = 0.0 > 20. < / RTI > The room temperature curable organopolysiloxane composition according to claim 1 or 2, further comprising calcium carbonate other than the component (B) in an amount of 1 to 200 parts by mass based on 100 parts by mass of the component (A). The room temperature curable organopolysiloxane composition according to claim 1 or 2, which is used for a secondary sealing adhesive material for double-layer glass or a structural sealant for glass glazing.