JP2003221506A - Room temperature-curable organopolysiloxane composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a room temperature curable organopolysiloxane composition, not deteriorating a working environment by a smell, etc., on curing it, exhibiting good adhesion to various substrates such as glass, plastics, metals, etc., and after the curing, capable of becoming a silicone rubber excellent in adhesion durability, maintaining the adhesion force even under a severe environment such as immersion in warm water, etc., and almost not reducing rubbery physical properties. <P>SOLUTION: This composition is characterized by consisting of (A) a single or mixed material consisting of (A-1) diorganopolysiloxane of which both molecular chain terminals are blocked by a silanol or an alkoxy group, and (A-2) a diorganopolysiloxane of which one molecular chain terminal is blocked by the silanol group or the alkoxy group and another molecular chain terminal is blocked by an alkyl group or an alkenyl group, (B) a disilaalkane compound, (C) a reaction mixture of an aminoalkylalkoxysilane with an epoxyalkylalkoxysilane and (D) a curing catalyst. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a room-temperature-curable organopolysiloxane composition, and more specifically, it has excellent adhesiveness to various base materials which are in contact with each other during curing, and has excellent adhesive durability after curing. The present invention relates to a room temperature curable organopolysiloxane composition capable of forming a silicone rubber having excellent properties.

[0002]

2. Description of the Related Art Conventionally, diorganopolysiloxane having a silanol group at the terminal of the molecular chain,
Room temperature curable organopolysiloxane compositions comprising alkoxysilanes and aminoalkylalkoxysilanes and curing catalysts are known. However, the silicone rubber obtained by curing this composition has a drawback that it is inferior in water resistance, and in particular, has a drawback that the adhesive strength and the rubber physical properties are deteriorated under a harsh environment such as hot water immersion. In order to solve this drawback, a room temperature curable organopolysiloxane composition has been proposed in which a disilaalkane compound such as 1,2-bis (trimethoxysilyl) ethane is added to the room temperature curable organopolysiloxane composition (JP (See JP-A-64-60656). However, since the disilaalkane compound specifically used or exemplified has a small molecular weight, a high volatility, and a peculiar odor, it is volatilized during preparation of the composition, particularly during defoaming of the mixture. There is a problem that properties such as adhesiveness are deteriorated, and further, a work environment is deteriorated during preparation and curing of the composition.

The present inventors have arrived at the present invention as a result of extensive studies to solve these drawbacks and problems. That is, the purpose of the present inventor, without the above problems,
During curing, it does not deteriorate the working environment due to odor, etc., and shows good adhesion to various substrates such as glass, plastic, metal, etc. After curing, it has excellent adhesion durability and is harsh such as immersion in hot water. An object of the present invention is to provide a room-temperature-curable organopolysiloxane composition capable of forming a silicone rubber which retains its adhesive force even under various environments and whose rubber properties are hardly deteriorated.

[0004]

The present invention provides "(A) (A
-1) General formula (1):

[Chemical 8] {In the formula, R ¹ is a hydrogen atom, an alkyl group or an alkoxyalkyl group, R ² is an alkyl group or an alkoxyalkyl group, and R ³ is a monovalent hydrocarbon group, a halogenated hydrocarbon group or a cyanoalkyl group. A is 0, 1 or 2 when R ¹ is an alkyl group or an alkoxyalkyl group, and a is 2 when R ¹ is a hydrogen atom. Y is an oxygen atom, a divalent hydrocarbon group, or general formula (2):

[Chemical 9] (In the formula, R ³ is the same as above, Z is a divalent hydrocarbon group.), And n has a viscosity at 25 ° C. of 20 to 1,000,000 mPa · s. Represents such a number. } Diorganopolysiloxane (20 to 100 parts by weight) and (A-2) general formula (3):

[Chemical 10] (In the formula, R ¹ , R ² , R ³ , Y and a are the same as defined above, and R
⁴ is an alkyl group or an alkenyl group, m is 25 ° C.
Represents the number such that the viscosity at 20 to 1,000,000 mPa · s. ) Diorganopolysiloxane (0 to 80 parts by weight) and a diorganopolysiloxane (100 parts by weight), (B) general formula (4):

[Chemical 11] (In the formula, R ⁵ and R ⁹ are alkyl groups or alkoxyalkyl groups, R ⁶ and R ⁸ are monovalent hydrocarbon groups, R ⁷ is a substituted or unsubstituted alkylene group, and The number of atoms is 4 to 10, and b and c are 0.
Or 1. ) Disilaalkane compound
(0.5 to 15 parts by weight), and (C) (C-1) general formula (5):

[Chemical 12] (In the formula, X is a hydrogen atom or an aminoalkyl group,
R ¹⁰ is a substituted or unsubstituted divalent hydrocarbon group, R ⁵
And R ⁶ are as described above, and e is 0 or 1. ) And an aminoalkylalkoxysilane (C-2) represented by the general formula (6):

[Chemical 13] (In the formula, Q is a glycidoxy group or an epoxycyclohexyl group.
Sil group, R^Five, R⁶, R^Ten And e are as described above
It ) And an epoxyalkylalkoxysilane represented by
Reaction mixture (0.1-10 parts by weight) and (D) curing
It is characterized by comprising a catalyst (0.001 to 20 parts by weight)
A room temperature curable organopolysiloxane composition, and
And (E) the general formula (7):

[Chemical 14]

To explain this, the component (A) is the main ingredient of the composition of the present invention, and the component (A-1) is a diorgano in which both ends of the molecular chain are blocked with silanol groups or alkoxy groups. Polysiloxane (20-100 parts by weight)
And (A-2) a diorganopolysiloxane (0 to 80 parts by weight) in which one end of the molecular chain is capped with a silanol group or an alkoxy group and the other end of the molecular chain is capped with an alkyl group or an alkenyl group. Is a single substance or a mixture. If the component (A-2) is too much in this component, the strength of the silicone rubber after curing tends to decrease.
The mixing ratio is (A-1) :( A-2) = (1 by weight.
It is preferably in the range of 00:00) to (20:80). Further, if the viscosity is too low, the strength of the silicone rubber after curing will be low, and if it is too high, the workability during production and use will be reduced, so the viscosity at 25 ° C.
It is necessary to be in the range of 1,000,000 mPa · s, and preferably in the range of 100 to 100,000 mPa · s.

The component (A-1) is a diorganopolysiloxane having silanol groups, alkoxy groups or alkoxyalkoxy groups at both ends of the molecular chain. Such a diorganopolysiloxane is represented by the following general formula (1):
R ¹ is a hydrogen atom or an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group or an octyl group; an alkoxyalkyl group such as a methoxyethyl group, an ethoxyethyl group, a methoxypropyl group or a methoxybutyl group, R ² Are alkyl groups such as methyl group, ethyl group, propyl group, butyl group and octyl group; and alkoxyalkyl groups such as methoxyethyl group, ethoxyethyl group, methoxypropyl group and methoxybutyl group. R ³ 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 or a cyclohexyl group; an alkenyl group such as a vinyl group or an allyl group; a phenyl group, a tolyl group or a naphthyl group. Groups such as aryl groups; benzyl groups, phenylethyl groups, phenylpropyl groups, and other aralkyl groups; trifluoropropyl groups, chloropropyl groups, and other halogenated hydrocarbon groups; β-cyanoethyl groups, γ-cyanopropyl groups, γ -A cyanoalkyl group such as a cyanopropyl group. Of these, a methyl group is preferable.
Y and Z are divalent hydrocarbon groups, preferably alkylene groups such as ethylene group, propylene group and butylene group. The component (A-1) can be synthesized by a known method (for example, see JP-B-3-4566 and JP-A-63-270762).

The component (A-2) is a diorganopolysiloxane having a silanol group, an alkoxy group or an alkoxyalkoxy group only at one end of the molecular chain. The component (A-2) serves to lower the modulus of the silicone rubber which is a cured product of the composition of the present invention. Such component (A-2) is represented by R ¹ , R ² , and R in the general formula (3).
³ , a, n, and Z are the same as those described for the component (A-1). R ⁴ is a methyl group, an ethyl group, a propyl group,
An alkyl group such as a butyl group and an octyl group; an alkenyl group such as a vinyl group and an allyl group. The viscosity of the component (A-2) at 25 ° C. is 20 to 1,000,0.
00 mPa · s, but 100 to 100,000 mP
a · s is preferable. Such a diorganopolysiloxane can be synthesized by a well-known method (Japanese Patent Laid-Open No. Hei 4)
-13767, JP-A-63-270762).

The component (B) functions as a cross-linking agent for the component (A), and when used in combination with the component (C) described later, it improves the adhesiveness of the composition of the present invention to various substrates,
In particular, it functions to impart water resistance to the cured silicone rubber. In the general formula (4) representing the component (B), R ⁶ and R ⁸ are alkyl groups such as methyl group, ethyl group and propyl group; alkenyl groups such as vinyl group and allyl group; aryl groups such as phenyl group. An exemplified monovalent hydrocarbon group,
Lower alkyl groups are preferred. R ⁵ and R ⁹ are methyl groups,
An alkyl group such as an ethyl group and a propyl group; an alkoxyalkyl group such as a methoxyethyl group, which has 4 or less carbon atoms are preferable. R ⁷ is a substituted or unsubstituted alkylene group having 4 to 10 carbon atoms, preferably 5 to 7 carbon atoms. The unsubstituted alkylene group is a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, the hydrogen atom is a methyl group, an ethyl group, a propyl group, a butyl group, a cyclopentyl group, a cyclohexyl group, Vinyl group, allyl group, 3,3,3-
It may be substituted with a trifluoropropyl group or a 3-chloropropyl group. The component (B) can be synthesized by a well-known method of hydrolyzing gen with trialkoxysilane or organodialkoxysilane.

Specific examples of the component (B) include 1,4-bis (trimethoxysilyl) butane, 1,4-bis (triethoxysilyl) butane, 1-methyldimethoxysilyl-4-trimethoxysilylbutane, 1-methyldiethoxysilyl-4-triethoxysilylbutane, 1,4-bis (methyldimethoxysilyl) butane, 1,4-bis (methyldiethoxysilyl) butane, 1,5-bis (trimethoxysilyl) pentane 1,5-bis (triethoxysilyl) pentane, 1,4-bis (trimethoxysilyl) pentane, 1,4-bis (triethoxysilyl)
Pentane, 1-methyldimethoxysilyl-5-trimethoxysilylpentane, 1-methyldiethoxysilyl-5
-Triethoxysilylpentane, 1,5-bis (methyldimethoxysilyl) pentane, 1,5-bis (methyldiethoxysilyl) pentane, 1,6-bis (trimethoxysilyl) hexane, 1,6-bis (tri Ethoxysilyl) hexane, 1,4-bis (trimethoxysilyl) hexane, 1,5-bis (trimethoxysilyl) hexane, 2,5-bis (trimethoxysilyl) hexane, 1
-Methyldimethoxysilyl-6-trimethoxysilylhexane, 1-phenyldiethoxysilyl-6-triethoxysilylhexane, 1,6-bis (methyldimethoxysilyl) hexane, 1,7-bis (trimethoxysilyl) heptane, 2,5-bis (trimethoxysilyl) heptane, 2,6-bis (trimethoxysilyl) heptane, 1,8-bis (trimethoxysilyl) octane,
2,5-bis (trimethoxysilyl) octane, 2,7
-Bis (trimethoxysilyl) octane, 1,9-bis (trimethoxysilyl) nonane, 2,7-bis (trimethoxysilyl) nonane, 1,10-bis (trimethoxysilyl) decane, 3,8-bis (Trimethoxysilyl)
Decane can be mentioned. These may be used alone or in combination of two or more.

The blending amount of the component (B) is 100 parts of the component (A).
It is 0.5 to 15 parts by weight with respect to parts by weight, but in the general formula (1) showing the component (A), when R ¹ is a hydrogen atom, the number of moles of the alkoxy group in the component (B). It is preferable that the amount exceeds the number of moles of silanol groups in the component (A). In the general formula (1) showing the component (A), R
^{When 1} is an alkyl group or an alkoxyalkyl group, the blending amount of the component (B) is preferably 2 to 15 parts by weight with respect to 100 parts by weight of the component (A).

The component (C) imparts adhesiveness to the composition of the present invention.
It acts as an adhesive and has an adhesive strength after immersion in water or warm water.
It works to prevent deterioration. Of the (C) components,
In the general formula (5) showing the component (C-1), aminoalkyl
Examples of the group include γ-aminopropyl group, R^TenIs
Alkylene groups are preferred R⁷ An example similar to
R^FiveAnd R⁶Examples of the same are the same as those described above.
R in the general formula (6) showing the component (C-2)^Five, R⁶, R^Ten
And e are as described above. Where (C-1)
As a specific example of the component, α-aminomethyltriethoxy
Orchid, γ-aminopropyltriethoxysilane, γ-a
Minopropylmethyldimethoxysilane, N- (β-amido
Noethyl) aminomethyltributoxysilane, N- (β
-Aminoethyl) aminopropyltrimethoxysilane,
N- (β-aminoethyl) aminopropylmethyl dimeth
Xysilane, γ-anilinopropyltriethoxysilane
Is mentioned. Specific examples of the component (C-2) include γ-
Glycidoxypropyltrimethoxysilane, γ-glycy
Doxypropylmethyldimethoxysilane, 3,4-epo
Xycyclohexylethyltrimethoxysilane, 3,4
-Epoxy cyclohexyl ethyl methyl dimethoxy sila
Are listed.

The component (C) can be easily obtained by charging a predetermined amount of the component (C-1) and a predetermined amount of the component (C-2) into a reaction vessel and mixing and reacting at room temperature or under heating. In this reaction, (C-1) component and (C
The molar ratio of the component (-2) is preferably 1: 1 to 1: 5, more preferably 1: 1 to 1: 4. Reaction temperature is 20 ~
50 degreeC is preferable and 15-40 degreeC is more preferable. If the molar ratio is out of the above range, the adhesive strength under hot water immersion tends to decrease, and if the reaction temperature is 50 ° C. or higher, the reaction mixture tends to gel and good rubber physical properties cannot be obtained. is there.

The blending amount of the component (C) is 100 parts of the component (A).
It is 0.1 to 10 parts by weight, preferably 0.5 to 5 parts by weight, based on parts by weight. If the amount of the component (C) is less than 0.1 parts by weight, the adhesiveness is insufficient, and if it exceeds 10 parts by weight, the curing speed becomes slow and the silicone rubber after curing becomes too hard. This is because

(D) As a curing catalyst, tin, titanium,
Examples thereof include organic acid salts of metals such as zirconium, iron, antimony, bismuth, and manganese, organic titanate esters, and organic titanium chelate compounds. Specific examples of such a curing catalyst include dibutyltin dilaurate, dibutyltin dioctoate, organic tin compounds such as stannas octoate, tetrabutyl titanate, tetraisopropyl titanate, diisopropoxybis (acetylacetone) titanium, diisopropoxybis. An organic titanium compound such as (ethyl acetoacetate) titanium is exemplified.
The addition amount is 0.0 with respect to 100 parts by weight of the component (A).
The amount is 01 to 20 parts by weight, preferably 0.01 to 5 parts by weight.

In addition to the components (A) to (D), the composition of the present invention further comprises (E) a general formula (7):

[Chemical 15] (In the formula, R ⁵ and R ⁶ are as described above, and f is 0 or 1.) Alkoxysilane (0.0
01 to 20 parts by weight) can be added. Specific examples of such alkoxysilanes include tetramethoxysilane, tetraethoxysilane, methyl cellosolve orthosilicate, n-propyl orthosilicate, and other tetraalkoxysilanes; methyltrimethoxysilane,
Examples thereof include trialkoxysilanes such as methyltriethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, and methyltrimethoxyethoxysilane, and partially hydrolyzed condensates thereof.

The composition of the present invention comprises the above-mentioned component (A)
In addition to the component (D) or the components (A) to (E),
The addition of various additives known to be added to the room temperature-curable organopolysiloxane composition may be added unless the object of the present invention is impaired. Examples of such additives include dry method silica, wet method silica, quartz fine powder, calcium carbonate powder, titanium dioxide powder, diatomaceous earth powder, aluminum hydroxide powder, particulate alumina,
Examples include magnesia powder, zinc oxide powder, and fine powdery inorganic fillers obtained by surface-treating these with silanes, silazanes, low-polymerization degree polysiloxanes, and the like. The amount of such an inorganic filler added is 1 to 200 parts by weight, preferably 5 to 100 parts by weight, relative to 100 parts by weight of the component (A).
Parts by weight. As other additives, dialkoxysilanes such as diphenyldimethoxysilane and dimethyldimethoxysilane, which are components for lowering the modulus of the cured silicone rubber, dimethylpolysiloxane capped with trimethylsiloxy groups at both ends; platinum Compounds, flame retardants such as zinc carbonate powder, plasticizers, thixotropic agents,
There are fungicides, pigments, organic solvents, etc.

The composition of the present invention can be easily produced by uniformly mixing the above-mentioned components (A) to (D), or components (A) to (E) under the exclusion of moisture. . At that time, components (A) to (C) are mixed in advance and then mixed with other components, or components (B) to (D) are mixed in advance and then mixed with component (A), ( B) ingredient ~
The component (E) may be mixed in advance and then the component (A) may be mixed. And two packaging types consisting of a mixture of (A) component and (B) component to (D) component, (A) component, a mixture of (B) component and (C) component, and three packaging consisting of (D) component. May be type.

The composition of the present invention as described above comprises glass,
China, mortar, concrete, wood, aluminum,
Copper, stainless steel, iron, galvanized iron, tinplate, brass,
It adheres to zinc, epoxy resin, phenol resin, polycarbonate resin, polyester resin, ABS resin, nylon resin, polyvinyl chloride resin, etc., but if stronger adhesion is required, a suitable primer for the surface of these base materials. May be applied, and the composition of the present invention may be adhered to the primer application surface. In the case of the 2-pack type and the 3-pack type, the adhesiveness does not decrease even if the mixture is defoamed. When mixed or cured, it does not deteriorate the working environment due to odor, etc., and shows good adhesion to various substrates such as glass, plastic, and metal. After curing, it has excellent adhesion durability and warm water. Silicone rubber that retains its adhesive strength even in a harsh environment such as immersion and has almost no deterioration in rubber physical properties can be used.
It is suitable as a sealing material for building members, particularly as a sealing agent for bonding glass. It is also useful as a sealing material, coating material, and adhesive for electric / electronic parts.

[0019]

EXAMPLES The present invention will be described below with reference to examples. In the examples, all parts are parts by weight and the viscosity is 25.
It is a value in ° C. The adhesion durability of the room temperature curable organopolysiloxane composition was evaluated according to the following method. <Evaluation Method of Adhesion Durability of Room Temperature Curable Organopolysiloxane Composition> An adhesion durability test body was prepared according to the method specified in JIS K5758 Building Sealing Material. That is, the room temperature-curable organopolysiloxane composition is filled between two float glass plates (float plate glass defined in JIS R3202), and FIG.
An adhesion durability test body (commonly known as an H-shaped test body) shown in was prepared. This adhesion durability test piece was tested at a temperature of 23 ° C and a humidity of 50%.
The composition was allowed to cure for 7 days under the conditions of. The tensile adhesion strength of the obtained adhesion durability test body was measured, and the breaking state of the silicone rubber was also observed. Further, this adhesion durability test body was immersed in warm water of 80 ° C. for 7 days, then taken out, the tensile adhesion strength was measured, and the fracture state of the silicone rubber was also observed. These measurement results and observation results are expressed as follows. M50: 50% tensile stress, Tmax: Maximum tensile stress Emax: Elongation at maximum load CF: Cohesive failure (broken by silicone rubber layer) AF: Adhesive failure (peeled at interface between glass plate and silicone rubber)

[0020]

[Reference Example 1] 220 g of γ-aminopropyltriethoxysilane (I) and 500 g of γ-glycidoxypropyltrimethoxysilane (II) (the molar ratio of II to I is 2.2) were uniformly mixed, The mixture was allowed to stand at room temperature for 7 days in a sealed state to prepare a reaction mixture of γ-aminopropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane. The reaction mixture had a viscosity of 170 mPa · s. (Hereinafter, referred to as the adhesion imparting agent A).

[0021]

Reference Example 2 N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane (III) 222 g and γ-glycidoxypropyltrimethoxysilane (II) 708 g
(II) to (III) in a molar ratio of 3.0) is uniformly mixed to obtain a reaction mixture of N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane and γ-glycidoxypropyltrimethoxysilane. Was prepared. The viscosity of this reaction mixture was 210 mPa · s (hereinafter referred to as adhesion promoter B).

[0022]

[Reference Example 3] 220 g of γ-aminopropyltriethoxysilane (I) and 278 g of γ-glycidoxypropyltriethoxysilane (IV) (IV molar ratio to I: 1.0) were uniformly mixed. , Leave it in a sealed room temperature for 14 days, and
A reaction mixture with glycidoxypropyltriethoxysilane was prepared. The reaction mixture has a viscosity of 36 mPa · s.
(Hereinafter referred to as adhesion promoter C).

[0023]

Example 1 Dimethylpolysiloxane 1 having a viscosity of 12,000 mPa · s and both ends of a molecular chain blocked with silanol groups 1
Calcium carbonate powder treated with 00 parts of fatty acid (manufactured by Shiraishi Industry Co., Ltd., trade name Shirotan CCR, average particle size 0.0
8 μm) and 100 parts were mixed until uniform (hereinafter,
The resulting mixture is referred to as Base 1). On the other hand, n-propyl orthosilicate, 1,6-bis (trimethoxysilyl) hexane, the adhesion-imparting agent A obtained in Reference Example 1 and dibutyltin dilaurate were mixed in the proportions shown in Table 1 to prepare a catalyst composition. I got a thing. Next, the base 1 and the catalyst composition were mixed at a ratio of 100: 5 (weight ratio) and defoamed under reduced pressure to obtain a room temperature curable organopolysiloxane composition. Then, for this composition,
The adhesion durability was measured. The results of these measurements are shown in Table 2. For comparison, a room temperature curable organopolysiloxane composition was prepared in the same manner as above except that the catalyst composition as shown in Table 1 above was used, and its properties were measured in the same manner as above. . These results are shown in Table 2.
Also described in.

[0024]

[Table 1]

[0025]

[Table 2]

[0026]

Example 2 70 parts of 1,6-bis (trimethoxysilyl) hexane, 30 parts of adhesion promoter A and 1 part of dibutyltin dilaurate were uniformly mixed to obtain a catalyst composition. Then, the base 1 obtained in Example 1 and this catalyst composition were mixed at a ratio of 100: 5 (weight ratio), and defoamed under reduced pressure to obtain a room temperature curable organopolysiloxane composition. The characteristics of this composition were measured in the same manner as in Example 1. The results are shown in Table 3.

[0027]

[Table 3]

[0028]

[Example 3] 70 parts of dimethylpolysiloxane having both ends of a molecular chain having a viscosity of 13,000 mPa · s blocked with silanol groups, one end of the molecular chain blocked with a silanol group, and the other end of the molecular chain being methyl Viscosity blocked by base 13,
30 parts of 000 mPa · s dimethylpolysiloxane, fatty acid-treated calcium carbonate powder (Shiraishi Industry Co., Ltd.,
Product name Shiro Gloss CCR average particle diameter 0.08 μm) 10
0 parts were mixed until uniform and defoamed under reduced pressure to obtain base 2. On the other hand, n-propyl orthosilicate 40
Part, 1,6-bis (trimethoxysilyl) hexane 15
Parts, 15 parts of the adhesion-imparting agent A obtained in Reference Example 1 and 1 part of dibutyltin dilaurate were uniformly mixed to obtain a catalyst composition. Next, the base 2 and this catalyst composition were mixed at a ratio of 100: 5 (weight ratio), and defoamed under reduced pressure to produce a room temperature curable organopolysiloxane composition. The properties of this composition were measured as in Example 1. The results are shown in Table 4.

[0029]

[Table 4]

[0030]

Example 4 Dimethylpolysiloxane 4 having a viscosity of 13,000 mPa · s in which both ends of the molecular chain are blocked with silanol groups
0 part, viscosity at which one end of the molecular chain was blocked with a silanol group and the other end of the molecular chain was blocked with a methyl group 13,0
60 parts of dimethylpolysiloxane of 00 mPa · s, fatty acid-treated calcium carbonate powder (manufactured by Shiraishi Industry Co., Ltd.,
Product name White gloss flower CCR, average particle size 0.08 μm) 10
0 part was mixed until uniform and defoamed to obtain base 3. On the other hand, 40 parts of n-propyl orthosilicate, 1,
15 parts of 6-bis (trimethoxysilyl) hexane, 15 parts of the adhesion promoter A obtained in Reference Example 1 and 1 part of dibutyltin dilaurate were uniformly mixed to obtain a catalyst composition. Then base 3 and 1 of this catalyst composition
The mixture was mixed at a ratio of 00: 5 (weight ratio) and defoamed under reduced pressure to produce a room temperature curable organopolysiloxane composition. The properties of this composition were measured as in Example 1. The results are shown in Table 5.

[0031]

[Table 5]

[0032]

[Example 5] Dimethylpolysiloxane 4 having a viscosity of 13,000 mPa · s in which both ends of the molecular chain were blocked with silanol groups 4
0 part, viscosity at which one end of the molecular chain was blocked with a silanol group and the other end of the molecular chain was blocked with a methyl group 13,0
20 parts of dimethylpolysiloxane of 00 mPa · s, 40 parts of dimethylpolysiloxane blocked with silanol groups at both ends having a viscosity of 4,000 mPa · s, and calcium carbonate powder treated with fatty acid (manufactured by Shiraishi Kogyo Co., Ltd., product name Shirotanka CC
100 parts of R and an average particle diameter of 0.08 μm) were mixed to obtain a base 4. On the other hand, 40 parts of 1,6-bis (trimethoxysilyl) hexane, 50 parts of the adhesion promoter C obtained in Reference Example 3 and 0.5 part of dibutyltin dilaurate were uniformly mixed to obtain a catalyst composition. Then base 4 and this catalyst composition 100: 4.
The mixture was mixed at a ratio of 5 (weight ratio) and defoamed under reduced pressure to produce a room temperature curable organopolysiloxane composition. The properties of this composition were measured as in Example 1. The results are shown in Table 6.

[0033]

[Table 6]

[0034]

Example 6 Dimethylpolysiloxane 1 having a viscosity of 50,000 mPa · s and both ends of a molecular chain blocked with silanol groups 1
00 parts, fatty acid-treated calcium carbonate powder (manufactured by Shiraishi Kogyo Co., Ltd., trade name Shiro Gloss CCR, average particle size 0.
08 μm) 60 parts, dry process silica surface-treated with hexamethyldisilazane (specific surface area 200 m ² / g) 10
Parts and 2 parts of dimethylpolysiloxane capped with silanol groups at both ends having a viscosity of 40 mMpa · s are mixed until uniform,
I got base 5. On the other hand, 60 parts of n-propyl orthosilicate, 10 parts of 1,6-bis (trimethoxysilyl) hexane, 30 parts of the adhesion promoter B obtained in Reference Example 2 and 1 part of dibutyltin dilaurate were uniformly mixed to prepare a catalyst composition. Then, the base 5 and this catalyst composition were mixed at a ratio of 100: 5 (weight ratio) and defoamed under reduced pressure to produce a room temperature curable organopolysiloxane composition. The properties of this composition were measured as in Example 1. The results are shown in Table 7.

[0035]

[Table 7]

[0036]

Example 7 100 parts of diorganopolysiloxane having both ends of the molecular chain with a viscosity of 12,000 mPa · S blocked with methyldimethoxylyl groups and calcium carbonate powder treated with fatty acid (trade name: Shiraishi CCR, manufactured by Shiraishi Industry Co., Ltd.) ,
100 parts of average particle diameter 0.08 μm) were mixed until uniform. Methyltrimethoxysilane 2 in this composition
Part, 1,6-bis (trimethoxysilyl) hexane 2
Parts, 1 part of the adhesion-imparting agent A obtained in Reference Example 1 and 1 part of diisopropoxybis (ethyl acetoacetate) titanium were added and mixed under a moisture barrier until uniform. Next, the adhesive durability of this composition was measured according to JIS A 5758. In addition, in this example, the prepared adhesion durability test body was subjected to a test under conditions of a temperature of 23 ° C. and a humidity of 50%.
The room temperature curable silicone rubber composition was left to stand for 4 days to be cured. The tensile adhesion strength of the obtained adhesion durability test body was measured, and the breaking state of the silicone rubber was also observed. In addition, this adhesive durability test piece was placed in warm water at 80 ° C for 14
After soaking for a day, it was taken out, and the tensile adhesion strength of this adhesion durability test body was measured, and the fracture state of the silicone rubber was also observed. The results are shown in Table 8.

[0037]

[Table 8]

[0038]

The room temperature curable organopolysiloxane composition of the present invention comprises the components (A) to (D) or (A) to:
Since it is composed of the component (E), and particularly contains the disilaalkane compound of the component (B), the adhesiveness does not deteriorate even when defoaming during the composition preparation, and the work environment is affected by odor during the composition preparation and curing. It shows good adhesiveness to various substrates such as glass, plastic, metal, etc. without deteriorating, and retains its adhesive force after curing even in harsh environments such as immersion in warm water, and has physical properties of rubber. Also has the characteristic that it can be a silicone rubber that is hardly reduced.

[Brief description of drawings]

FIG. 1 is a schematic diagram of Examples 1 to 4 and Comparative Example 1.
FIG. 3 is a schematic diagram of an adhesion durability test body used for evaluation of adhesion durability of a room temperature curable silicone rubber composition in Comparative Example 2. FIG.

[Explanation of symbols]

1. Adhesion durability test body 2. Float glass plate silicone rubber

Continued front page    (72) Inventor Miyoji Miyama             2-2 Chikusaigan, Ichihara-shi, Chiba Toray Dow             Corning Silicone Manufacturing Division             Chiba factory F-term (reference) 4J002 CP021 CP032 DE239 EX036                       EX069 EX077 EX078 FB239                       GJ02 GL00

Claims (7)

[Claims] 1. (A) (A-1) general formula (1): [Chemical 1] {In the formula, R¹Is a hydrogen atom, an alkyl group or an alcohol
A xyalkyl group, R²Is an alkyl group or alco
A xyalkyl group, R³Is a monovalent hydrocarbon group, halogen
Group selected from a fluorinated hydrocarbon group and a cyanoalkyl group
And R¹Is an alkyl group or an alkoxyalkyl group
A is 0, 1 or 2, and R is¹Is hydrogen
When it is an atom, a is 2. Y is an oxygen atom, divalent
Hydrocarbon group or general formula (2): [Chemical 2] (In the formula, R³Is the same as above, Z is a divalent hydrocarbon group
Is. ), Where n is the viscosity at 25 ° C.
The degree is 20 to 1,000,000 mPa · s
Represents a number. } Diorganopolysiloxane
(20 to 100 parts by weight) and (A-2) general formula (3): [Chemical 3] (In the formula, R¹, R², R³, Y, a are the same as above, and R
^FourIs an alkyl group or an alkenyl group, and m is 25 ° C.
Viscosity of 20 to 1,000,000 mPa · s
Represents a number like ) Diorganopolyshiroki
Diorganopolyshiro consisting of sun (0 to 80 parts by weight)
Xane (100 parts by weight), (B) general formula (4): [Chemical 4] (In the formula, R^FiveAnd R⁹Is an alkyl group or alkoxy group
Rukiru group, R⁶And R⁸Is a monovalent hydrocarbon group
R⁷Is a substituted or unsubstituted alkylene group,
The number of carbon atoms of the alkylene group is 4 to 10, and b and c are 0.
Or 1. ) Disilaalkane compound
(0.5 to 15 parts by weight), and (C) (C-1) general
Formula (5): [Chemical 5] (In the formula, X is a hydrogen atom or an aminoalkyl group,
R^TenIs a substituted or unsubstituted divalent hydrocarbon group, R^Five
And R⁶Is as described above and e is 0 or 1.
It ) And an aminoalkylalkoxysilane
(C-2) General formula (6): [Chemical 6] (In the formula, Q is a glycidoxy group or an epoxycyclohexyl group.
A silyl group, R^Five, R⁶ , R^TenAnd e are as described above
Is. ) Epoxy alkyl alkoxy sila
Reaction mixture with benzene (0.1-10 parts by weight) and (D)
Specially consisting of a curing catalyst (0.001 to 20 parts by weight)
A room temperature curable organopolysiloxane composition. 2. The composition according to claim 1, further comprising (E) the general formula (7): (In the formula, R ⁵ and R ⁶ are as described above, and f is 0 or 1.) Alkoxysilane (0.5
Room temperature-curable organopolysiloxane composition. 3. The room temperature curable organopolysiloxane composition according to claim 1, wherein the component (B) is 1,6-bis (trimethoxysilyl) hexane. 4. The room temperature curable organopolysiloxane composition according to claim 1, wherein the component (D) is an organic tin compound. 5. The room temperature curable organopolysiloxane composition according to claim 1, wherein the component (D) is an organic titanium compound. 6. A sealing material for construction use according to claim 1.
The room temperature curable organopolysiloxane composition according to any one of 1. 7. The room temperature curable organopolysiloxane composition according to claim 1, which is a sealing material for bonding glass.