JPH0841345A - Room-temperature-curing polyorganosiloxane composition - Google Patents

Abstract

PURPOSE:To obtain a room-temperature-curing polyorganosiloxane composition showing excellent adhesion to a wide variety of substrates including a silicone rubber by mixing an organosilicone compound having specified substituents i.e., an alkenyloxysilyl group and/or a guanidyl group. CONSTITUTION:This composition comprises 100 pts.wt., in total, terminal-reactive polyorganosiloxane represented by formula I and a silane represented by formula II or a partial hydrolyzate thereof (the rate of the compound of formula I is 85-100wt.%), 0.01-10 pts.wt. curing catalyst, 0.5-10 pts.wt. nitrogenous silicon compound in which the nitrogen atom is bonded to the silicon atom through one or more carbon atoms, and that nitrogen atom is directly bonded to that or another silicon atom and 0.05-50 pts.wt. silane or siloxane having at least either an alkenyloxysilyl group or a guanidyl group and represented by formula III or IV.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION The present invention relates to a polyorganosiloxane composition, which is stable particularly under sealed conditions without moisture, and is cured at room temperature upon contact with moisture in the air to become an elastic body at room temperature. It relates to a curable polyorganosiloxane composition.

[0002]

TECHNICAL BACKGROUND AND PROBLEMS OF THE INVENTION In a polyorganosiloxane composition that cures at room temperature to form a rubber-like elastic material, a curing reaction occurs in one package when in contact with moisture in the air. The type does not have the trouble of weighing the main body, the cross-linking agent, or the catalyst immediately before use or mixing them, and does not cause a mistake in the formulation.
Since it has excellent adhesiveness, it is widely used as an elastic adhesive or coating material in the electric and electronic industries and as a sealing material for construction. Such a composition is obtained by blending a silanol group-terminated polydiorganosiloxane having a molecular terminal blocked with a hydroxyl group with a cross-linking agent having an average of more than two hydrolyzable groups in the molecule. Depending on the type, acetic acid, long-chain carboxylic acid, organic amine, amide, organic hydroxylamine, oxime compound, alcohol, acetone, etc. are released upon curing. Of these, those that release acetic acid have excellent adhesiveness and curability, but due to their pungent odor, environmental hygiene considerations are required, and when the adherend is a metal, Since it rusts, there are problems such as the need for rust prevention measures. Further, although the long-chain carboxylic acid-releasing type does not have a problem of irritating odor, it was difficult to prevent metal rusting, particularly rusting after water immersion. Similarly, the deamine type has a problem in the odor and toxicity of the generated amine, and the dehydroxylamine type, deoxime type and deamidated type have a problem that metal, particularly copper and its alloy, are easily rusted. . Further, although the deacetone type cures quickly and is not corrosive, it has a problem in that it is difficult to synthesize a crosslinking agent and yellowing during storage of the uncured product is significant. On the other hand, dealcohol-type products are said that not only can alkoxysilane, which is a cross-linking agent, be available at a low price, but because the substance to be released is an alcohol such as methanol or ethanol, it easily volatilizes and does not have odor or corrosive problems. There are advantages. However, on the other hand, there is a problem that the curing is slow and the storage stability is poor because the alcohol generated by hydrolysis of the cross-linking agent by the trace amount of water present in the system during storage cleaves the base polymer and overcomes it. Was requested. Particularly in the electric and electronic industries, a room temperature curable polyorganosiloxane composition is often cured in a state of being in contact with a copper metal to form a rubber-like elastic body for the purpose of an adhesive or a coating material. Therefore, currently deoxime type, deacetone type,
Although dealcohol-type products have been used, it has been desired to improve the above-mentioned difficulties that each has. A one-pack type room temperature curable polyorganosiloxane composition comprising a polyorganosiloxane having an alkoxy group bonded to a terminal silicon atom, an alkoxysilane, a curing catalyst, and an alcohol scavenger has recently been found, and it has a stable storage stability. Good properties and fast curability (see JP-A-59-500219 and JP-A-58-501040). Further, as the alcohol scavenger, it has been found that when a silicon-nitrogen bond-containing compound that reacts with alcohol to form a non-volatile nitrogen-containing compound is used, it does not show corrosiveness to copper-based metals. Has been done. Such a room-temperature-curable polyorganosiloxane composition which is fast-curing and does not cause rust on copper-based metals is useful as an adhesive or coating material in the electrical and electronic industries, but it is a rubber-like elastic material obtained by curing. , The silicon-nitrogen bond-containing compound used as the alcohol scavenger is hydrolyzed, and the hydrolysis product penetrates into the surface and becomes a resin, thereby generating cracks on the surface and lowering the physical properties and durability. May bring. On the other hand, a compound containing a polyoxyalkylene chain in the molecule was found to be effective in preventing such resinification (Japanese Patent Application No. 58-125649).
No., JP-A-60-18544). However, the composition thus obtained does not show sufficient adhesion to certain plastics. That is, in addition to being poor in adhesiveness to polycarbonate, satisfactory adhesiveness to acrylic resin may not be obtained depending on use conditions. Various studies have been made to solve this problem, and it has been proposed to use an aminoalkyl group-containing polyorganosiloxane instead of the compound having a polyoxyalkylene chain (Japanese Patent Laid-Open No. 62-62863). However, this composition does not show sufficient adhesion to silicone rubber (which is cured by peroxide vulcanization and hydrosilylation reaction). For this reason, this composition has many advantages that it is not corrosive to copper-based metals, it cures in a relatively short time at room temperature, and there is no resinification on the surface. It was not suitable for use as an element.

[0003]

OBJECTS OF THE INVENTION It is an object of the present invention to provide a room temperature curable polyorganosiloxane composition which exhibits excellent adhesion to a wide range of adherends containing silicone rubber without impairing the above advantages. It is a thing.

[0004]

The present inventor has conducted earnest studies to achieve the above object, and as a result, alkenyloxysilyl groups and / or
Alternatively, by adding an organosilicon compound containing a specific substituent of a guanidyl group, a room-temperature-curable polyorganosiloxane composition having improved adhesiveness to silicone rubber can be obtained without lowering the adhesiveness to engineering plastics. The inventors have found that they can be obtained and have completed the present invention. That is, the present invention is the following (A) ~
The component of (D), that is, (A) (1) general formula R ¹ _a (R ² O) _3-a SiO [R ₂ SiO] _n Si (OR ² ) _3-a R ¹ _a (where R and R ¹ is a monovalent substituted or unsubstituted hydrocarbon group which is the same or different from each other, and R ² is 1 selected from the group consisting of an alkyl group having 1 to 4 carbon atoms and an alkoxyalkyl group having 1 to 6 carbon atoms in total. Valency group, a is 0
Or the number of 1, n is the viscosity of (A) at 25 ℃ is 100-50
End-reactive polyorganosiloxane represented by the formula (1), and (2) the general formula R ³ _b Si (OR ⁴ ) _4-b (wherein R ³ is a monovalent substituted or unsubstituted). Hydrocarbon group, R
⁴ is an alkyl group having 1 to ⁴ carbon atoms and a total of 1 to 6 carbon atoms
A monovalent group selected from the group consisting of alkoxyalkyl groups, and b is a number of 0 or 1, and the total amount of the silane or its partial hydrolyzate is 100 parts by weight (however,
(A) (1) (2) (A) (1) is 85 to 100% by weight); (B) Curing catalyst 0.01 to 10 parts by weight; (C) Nitrogen atom is one or more carbon atoms. 0.5 to 10 parts by weight of a nitrogen-containing silicon compound bound to a silicon atom through the nitrogen atom and the nitrogen atom directly bound to the silicon atom or another silicon atom; and (D) in the molecule, the following general formula: Silane or siloxane having at least one of alkenyloxysilyl group and / or guanidyl group represented by (I) and (II) 0.05 to 50 parts by weight

[0005]

Embedded image

(Wherein R ⁹ is the same or different, substituted or unsubstituted monovalent hydrocarbon group, R ¹⁰ and R ¹¹ are hydrogen atoms or the same or different, substituted or unsubstituted monovalent hydrocarbon group, m is a number from 1 to 3, R ¹² , R ¹³ , R ¹⁴ and
R ¹⁵ contains a hydrogen atom or the same or different substituted or unsubstituted monovalent hydrocarbon group), and relates to a room-temperature-curable polyorganosiloxane composition.

The structure of the present invention will be described in detail below. (A) (1) used in the present invention is a base polymer of the composition of the present invention, and has the general formula R ¹ _a (R ² O) _3-a SiO [R ₂ SiO] _n Si (OR ² ) _{3- It is represented by a} R ¹ _a (however, R, R ¹ , R ² , a, and n are as described above).
R may be the same as or different from each other, a methyl group,
Alkyl group such as ethyl group, propyl group, butyl group, hexyl group and decyl group; alkenyl group such as vinyl group and allyl group; aryl group such as phenyl group; β-phenylethyl group, β-phenylpropyl group Examples of the aralkyl group such as and those in which a part of hydrogen atoms of these hydrocarbon groups are substituted with a halogen atom, a nitrile group or the like, but a methyl group, a vinyl group, a phenyl group or the like is used because of easy synthesis. Preferably, the other organic group is
It is selected and used only when imparting special properties such as oil resistance and paintability to the rubber-like elastic body after curing. Among them, the methyl group is not only the easiest to obtain a raw material intermediate, but also has the lowest viscosity corresponding to the degree of polymerization of siloxane,
It is preferable that 85% or more of all organic groups are methyl groups, because it makes the balance between the extruding workability of the composition before curing and the physical properties of the rubber-like elastic body after curing advantageous, and substantially all organic groups. Is more preferably a methyl group. However, when the rubbery elastic body after curing requires cold resistance, it is preferable to use a phenyl group as a part of the organic group. Next, examples of R ¹ include the same organic groups as R,
A methyl group or a vinyl group is preferred because of ease of synthesis and a high crosslinking reaction rate. Also, in the above general formula
Examples of R ² include a methyl group, an ethyl group, a propyl group, an alkyl group such as a butyl group, an methoxyethyl group, and an alkoxyalkyl group such as an ethoxyethyl group.
A methyl group is most preferred because it is easy to synthesize and has a high crosslinking reaction rate. Further, in the present invention, the end-reactive polydiorganosiloxane is added at 25 ° C. in order to impart an appropriate extrudability to the composition before curing and to impart excellent mechanical properties to the rubber-like elastic body after curing. It is desirable that the viscosity is in the range of 100 to 500,000 cP. If the viscosity of the end-reactive polydiorganosiloxane is less than 100 cP, the elongation of the rubber-like elastic body after curing will be insufficient, while
If it exceeds 500,000 cP, it is difficult to obtain a uniform composition, and the extrusion workability also deteriorates. A particularly preferred viscosity range is in the range of 500 to 200,000 cP in terms of reconciling the properties of the composition before and after curing.

The silane of (A) (2) or its partial hydrolysis-condensation product used in the present invention reacts with the alkoxy group of (A) (1) in the presence of water and a curing catalyst to cure the composition. It is intended to act as a crosslinking agent for the general formula R ³ _b Si
It is represented by (OR ⁴ ) _4-b (where R ³ , R ⁴ , and b are as described above). Here, as R ³ in the above general formula, the same organic group R directly bonded to the silicon atom of the component (A) (1) can be exemplified, but in view of easy availability and curing speed, It is preferably a methyl group or a vinyl group. As R ⁴ , the same as R ^{2 of the} component (1) can be exemplified. Examples of such compounds include tetramethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, and phenyltriethoxy. Examples thereof include silane, tetrakis (ethoxyethoxy) silane, methyltris (methoxyethoxy) silane, vinyltris (methoxyethoxy) silane, and siloxane which is a partial hydrolysis-condensation product of these silanes. Among these, tetramethoxysilane, methyltrimethoxysilane, vinyltrimethoxysilane, and methyltris (methoxyethoxy) silane are particularly preferable because they are easy to synthesize, do not impair the storage stability of the composition, and stop the curing rate thereof. It is preferable to use vinyl tris (methoxyethoxy) silane or the like.

(A) is a base polymer (A) (1) which may itself be crosslinkable, or a mixture of (A) (1) and a crosslinking agent (A) (2). . The ratio is (A) (A) (1)
Is preferably 85 to 100% by weight and (A) (2) is 0 to 15% by weight. If the content of (A) (2) exceeds 15% by weight, not only (A) (2) separates from the composition during storage, but also significant shrinkage occurs during curing, and the physical properties of the obtained rubber-like elastic body deteriorate. Because I will do it. (A) (1) When the number of alkoxy groups on the terminal silicon atom of the polydiorganosiloxane used as (A) (1) is more than 2 on average per molecule of (A) (1), the silane of (A) (2) or Even without the partial hydrolyzate, the reaction proceeds in the presence of water and the curing catalyst. However, considering the balance between curability and mechanical properties after curing, (A) of (A)
It is preferable to use 0.4 to 5% by weight of (2).

(B) used in the present invention is (A) (1) alone,
Or (A) (1) and (A) (2) is a curing catalyst for reacting in the presence of water to obtain a rubber-like elastic body, iron octoate, cobalt octoate, manganese octoate,
Carboxylic acid metal salts such as zinc octoate, tin naphthenate, tin caprylate, tin oleate; dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin dioleate,
Examples of organotin compounds such as diphenyltin diacetate, dibutyltin oxide, dibutyltin methoxide, dibutylbis (triethoxysiloxy) tin, and dioctyltin dilaurate are mentioned. Preferably there is. The compounding amount of (B) is 0.01 to 10 parts by weight, preferably 0.1 to 1 part by weight, per 100 parts by weight of (A). Limiting the blending amount to such a range is that 0.01 parts by weight at the terminal does not sufficiently act as a curing catalyst, and it not only takes a long time to cure, but especially in the deep part of the rubber layer far from the contact surface with air. This is because the curing becomes insufficient, and conversely, when it exceeds 10 parts by weight, the storage stability becomes poor.

The nitrogen atom of (C) used in the present invention is bonded to a silicon atom through one or more carbon atoms, and the nitrogen atom is directly bonded to the silicon atom or another silicon atom. The nitrogen-containing silicon compound is
This is for improving the storage stability of the composition by trapping alcohol generated during the production of the mixed composition of (A) and (B) or during closed storage. As (C), N-trimethylsilyl-γ-aminopropyltrimethoxysilane, N-trimethylsilyl-γ-aminopropyltriethoxysilane, N- (N′-trimethylsilyl-β-aminoethyl) aminopropyltrimethoxysilane, 1 , 1
-Dimethoxy-2-methyl-1-sila-2-azacyclopentane, 1,1-dimethoxy-2-trimethylsilyl-
Examples thereof include 1-sila-2-azacyclopentane and poly (1,1-dimethoxy-5-trimethylsilyl-1-sila-5-azapentane). These may be used alone or as a mixture. Among these, due to the ease of synthesis and the alcohol scavenging effect, N-
Trimethylsilyl-γ-aminopropyltriethoxysilane, 1,1-dimethoxy-2-trimethylsilyl-1-
Sila-2-azacyclopentane and its ring-opening polymer, poly (1,1-dimethoxy-5-trimethylsilyl-)
1-sila-5-azapentane) is preferred. like this
The blending amount of (C) is suitably 0.5 to 10 parts by weight, more preferably 1 to 5 parts by weight, based on 100 parts by weight of (A). If the blending amount is less than 0.5 parts by weight, the storage stability of the composition will be deteriorated. On the other hand, if the blending amount exceeds 10 parts by weight, it is meaningless and uneconomical, and the rubbery product obtained by curing is obtained. The physical properties and heat resistance of the elastic body are deteriorated, and yellowing due to heating becomes remarkable.

The (D) alkenyloxysilyl group- and / or guanidyl group-containing silane or siloxane used in the present invention is a characteristic component in the present invention, and includes (A) and (B)
It is effective in improving the adhesion of the composition consisting of (C) to silicone rubber. As the alkenyloxysilyl group-containing material, methyltri (isopropenoxy) silane, vinyltri (isopropenoxy) silane, phenyltri (isopropenoxy) silane, propyltri (isopropenoxy) silane, tetra (isopropenoxy) silane, 3,3,3-trifluoropropyl ( Isopropenoxy) silane, 3-chloropropyltri (isopropenoxy) silane, 3-chloropropyltri (isopropenoxy) silane, methyltri (1-phenylethynyloxy)
Silane, methyltri (1-isobutenyloxy) silane,
Methyltri (1-methyl-1-propenoxy) silane,
Vinyltri (cyclopentoxy) silane, methyltri (cyclohexanoxy) silane and their partial hydrolysates,

[0013]

[Chemical 3]

Examples of alkenyloxysilyl group-containing siloxanes such as: and guanidyl group-containing substances include

[0015]

[Chemical 4]

## STR1 ## Examples are given below, but among these, the formula is used because of their easy synthesis.

[0017]

[Chemical 5]

Those represented by are preferred.
In addition, compounds having both groups in one molecule are naturally effective, and examples thereof include 1,1,3,3-tetramethylguanidylpropyltri (isopropenoxy) silane. The blending amount of component (D) is 0 with respect to 100 parts by weight of (A).
05 to 50 parts by weight. If the blending amount is less than 0.05 parts by weight, the desired effect cannot be obtained.On the other hand, blending more than 50 parts by weight is not only uneconomical, but also the physical properties and heat resistance of the rubber-like elastic body obtained by curing are not improved. There is a problem that the yellowing due to deterioration and heating is remarkable, and also yellowing during storage.

Although not particularly essential in the present invention, it is preferable to add a substituted or unsubstituted aminoalkyl group-containing polyorganosiloxane as the component (E),
It is effective to prevent the surface of the rubber-like elastic body obtained by curing the composition comprising (A) to (D) from becoming a resin and to improve the physical properties and durability. (E) is represented by the general formula [R ⁵ ₂ NR ⁶ SiR ⁷ _c O _{(3-c) / 2} ] _p [R ⁸ _d SiO _{(4-d) / 2} ] _q (where R ⁵ is a hydrogen atom or a substituted or Monovalent groups identical to or different from each other selected from the group consisting of unsubstituted hydrocarbon groups, R ⁶ is a divalent hydrocarbon group, and R ⁷ and R ⁸ are substituted or unsubstituted groups identical to or different from each other. Monovalent hydrocarbon group, c is a number of 0, 1 or 2, d is a number of 0 or 1 to 3, p and q have a viscosity (E) of 5 at 25 ° C. of 5
Each number is 1 or more, which is ~ 10,000 cP, and p / (p + q) is
It is a liquid aminoalkyl group-containing polyorganosiloxane which may have a small amount of a hydroxyl group or an alkoxy group bonded to a silicon atom.
As R ⁵ , in addition to the same hydrogen atom and R as the component (A) (1), β-aminoethyl group, γ-aminopropyl group,
Examples thereof include a δ-aminobutyl group, a methylaminoethyl group, and a 2-hydroxy-3- (3-trimethoxysilylpropyloxy) propyl group. Examples of R ⁶ include methylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, pentamethylene group, and the like.
A propylene group is preferable because it is chemically stable, is not easily hydrolyzed, the raw material intermediate is easily available, and it is easy to handle. As such a substituted or unsubstituted aminoalkyl group R ⁵ ₂ NR ⁶ bonded to a silicon atom, γ-
Aminopropyl group, N- (β-aminoethyl) -γ-aminopropyl group, N-phenyl-γ-aminopropyl group, and the like may be used for the composition surface after curing while maintaining easiness of synthesis and adhesiveness. It is preferable from the effect of preventing resinification. R ⁷ is a substituted or unsubstituted aminoalkyl group-containing siloxane unit, R ⁸
Is an organic group bonded to the silicon atom of other siloxane units, and examples thereof include those similar to R of component (A) (1), but to provide a polysiloxane of relatively low viscosity that is easy to synthesize. From the above, a methyl group is preferable, and in consideration of the compatibility with the component (A) (1), the component (A) (1) has 1 as R 1 other than a methyl group.
Similar organic groups may be present as part of R ⁷ and / or R ⁸ when containing large amounts of valent substituted or unsubstituted hydrocarbon groups. Viscosity of (D) is 5 ~ 10,000c at 25 ℃
P, preferably 10 to 2,000 cP. Those of less than 5 cP are volatile and practically have poor reliability for exerting effects in the composition. If it exceeds 10,000 cP, not only is it difficult to synthesize with good control, but it is not sufficiently dispersed in the component (A) (1), and the effect of preventing resinification of the surface of the rubber-like elastic body after curing is low. In (E), the silicon functionality of the siloxane unit containing a substituted or unsubstituted aminoalkyl group is 1,2,3
Either of them may be used. In other words, c can be either 2,1,0. The silicon functionality of the siloxane units not containing the above groups may be 1,2,3,4, that is, d may be 0 or 1 to 3, and the siloxane units are appropriately mixed. However, in order to synthesize (E) in the above viscosity range with good control, it is preferable that d is 2, or a mixture of 2 and 3. In addition, depending on the synthesis method, some hydroxyl groups, methoxy groups, or ethoxy groups bonded to silicon atoms may remain at the ends of the molecule. As long as the viscosity of (E) is within the above range, the siloxane skeleton may be any of chain, branched, cyclic and network. (E)
At least one siloxane unit containing a substituted or unsubstituted aminoalkyl group among the siloxane units constituting is required in the molecule, and
It must be 33% or less (that is, P / (P + Q) should be 0.33 or less). If it exceeds 33%, the compatibility with (A) (1) becomes low, and it tends to be separated, and the effect of preventing resinification of the surface of the rubber-like elastic body after curing is lowered. Also,
If the proportion of such siloxane units is extremely large, on the contrary, the resinification of the surface is promoted. The preferred amount of the siloxane unit is in the range of 0.05 to 20% from the effect of preventing resinification. The amount of component (E) added is 0.05 parts based on 100 parts by weight of (A).
-50 parts by weight, preferably 0.1-10 parts by weight. If it is less than 0.05 parts by weight, the effect of preventing surface resinification does not appear, or if it is too much, it is meaningless and uneconomical, and the cured product becomes soft and oil bleeding easily occurs.

In the present invention, in order to impart appropriate fluidity to the composition before curing and impart high mechanical strength required as a sealing material to the rubber-like elastic body after curing, the above-mentioned components are used. In addition to the above, it is preferable to add a fine powdery inorganic filler. Examples of such reinforcing inorganic fillers include fumed silica, pyrogenic silica, precipitated silica,
Fume titanium and organochlorosilanes of these surfaces, polyorganosiloxanes, and those hydrophobized with hexamethyldisilazane, etc., and other fillers, calcium carbonate, organic acid surface-treated calcium carbonate, Diatomaceous earth, ground silica, aluminosilicate, magnesia, alumina, etc. When it is required that the building sealing material has a particularly low modulus, it is preferable to use a non-reinforcing filler among these. If the addition amount of the above-mentioned reinforcing inorganic filler is too small, the effect of improving the mechanical properties hardly appears. On the contrary, if it is too large, the modulus becomes large and the elongation at break becomes small. Therefore, it is desirable that the addition amount of these fillers is appropriately selected from the range of 1 to 500 parts by weight, more preferably 5 to 150 parts by weight, per 100 parts by weight of (A). Furthermore, the composition of the present invention includes a pigment, a thixotropy imparting agent, a viscosity modifier for improving extrusion workability, a UV inhibitor, an antifungal agent, a heat resistance improver, an adhesion improver, and flame retardant. It is also possible to add various additives such as agents.

The composition of the present invention can be obtained by mixing all the above components and, if necessary, various additives in a state where moisture is blocked. The obtained composition can be used as a so-called one-pack type room temperature curable polyorganosiloxane composition, which is stored in a closed container as it is and is cured only by exposing it to moisture in the air during use. Further, in the composition of the present invention, (A),
Use as a so-called two-pack type room temperature curable polyorganosiloxane composition in which components (C) and (D), (E) and component (B) are stored separately in separate containers and mixed at the time of use. You can also

[0022]

The room-temperature-curable polyorganosiloxane composition obtained by the present invention is fast-curing, has no corrosiveness to copper-based metals, and prevents the silicone rubber surface obtained by curing from becoming resinous. Moreover, it exhibits good adhesiveness to silicone rubber and other adherends. Such a composition has extremely excellent characteristics as an elastic adhesive or a coating agent in various industries, particularly in the electric and electronic industries.

[0023]

EXAMPLES The present invention will be further described below with reference to examples. The invention is not limited by these examples. In the examples, all parts are parts by weight, and all physical properties such as viscosity are values at 25 ° C. In the examples, the following E-1 and E-2 were used as the substituted or unsubstituted aminoalkyl group-containing polyorganosiloxane of the component (E). _{E-1 [H 2 N (} CH 2) 3 SiO 3/2] [(CH 3) 2 SiO] 33 molecular terminal: ethoxy Viscosity: 45 cP

[0024]

[Chemical 6]

Viscosity: 420 cP Examples 1 and 2 100 parts of α-ω-bis (methyldimethoxysilyl) polydimethylsiloxane having a viscosity of 20,000 cP and a specific surface area of 200 m ²
14 parts of fumed silica / g was added and mixed uniformly to obtain a base compound X-1. 4 parts of methyltrimethoxysilane, 5 parts of γ-aminopropyltriethoxysilane,
1 part of dibutyltin dilaurate and 7 parts of N-trimethylsilyl-γ-aminopropyltriethoxysilane were mixed to obtain a crosslinking agent mixture Y-1. 100 parts of base compound X-1, 4 parts of crosslinker mixture Y-1, 1 part of E-1 and 3 parts of methyltri (isopropenoxy) silane are mixed until moisture is uniform and degassed. , Sample 1 was obtained. In addition, 100 parts of the base compound X-1, 4 parts of the crosslinker mixture Y-1, 1 part of E-1 and 4 parts of 1,1,3,3-tetramethylguanidylpropyltrimethoxysilane were used in Sample 1 Sample 2 was obtained by mixing and defoaming in the same manner as above. These were extruded into a 2 mm sheet and cured by moisture in the air. After about 5 minutes, it became dry to the touch, but after curing, no resinification of the surface of the cured product was observed and no cracks were generated. The same 2 mm sheet extruded was left at room temperature for 168 hours and its physical properties were measured according to JIS K 6301.
Was measured by The results are shown in Table 1.

Comparative Example 1 The same method as in Example 1 was used except that 3 parts of methyltri (isopropenoxy) silane was not added and the base compound X-1 and the crosslinker mixture Y-1 and E-1 used in Example 1 were used. Sample 3 was prepared by mixing with, and cured in the same manner as in Example 1 to obtain a rubber-like elastic body. This product has a touch dry time of 6
It was a minute. Also, its physical properties were measured according to JIS K 6301. The results are shown in Table 1.

Examples 3-4 Methyltrimethoxysilane 4 parts, 1,3,5- (γ-trimethoxysilylpropyl) isocyanurate 4.5 parts, dibutyltin dilaurate 2 parts, 1,1-dimethoxy-2-trimethylsilyl-1 -Sila-2-azacyclopentane 5
The parts were mixed to obtain a crosslinking agent mixture Y-2. 100 parts of the base compound X-1 used in Example 1, 4 parts of the crosslinker mixture Y-2, 1 part of E-2, vinyltri (isopropenoxy)
Sample 4 was prepared by mixing 3 parts of silane in the same manner as in Example 1. Similarly, Sample 5 was prepared by using 4 parts of 1,1,3,3-tetramethylguanidylpropyltri (isopropenoxy) silane instead of vinyltri (isopropenoxy) silane. The physical properties of these samples were measured as in Example 1. The results are shown in Table 1. These samples 1 to 5 were cured in the same manner as in the example, and the adhesiveness to silicone rubber was qualitatively evaluated by a hand peel test. The results are shown in Table 1. Further, using Samples 1 to 5, a similar manual peel test was performed on polycarbonate, acrylic resin, ABS, epoxy resin, aluminum and copper to compare the adhesiveness to various adherends. The results are shown in Table 1.

[0028]

[Table 1]

* 1 TSE221 * 2 SH861u * 3 TSE3250 * 4 SE1281 Example 5 100 parts of α, β-bis (trimethoxysilyl) polydimethylsiloxane having a viscosity of 10,000 cp and fumed silica having a specific surface area of 200 m ² / g 14 Parts were added and uniformly mixed to obtain a base compound X-2. Also, tetramethoxysilane 4 parts, N
-(Β-aminoethylaminopropyl) trimethoxysilane 2 parts, γ-aminopropyltriethoxysilane-γ
-Glycidoxypropyl trimethoxysilane, etc. 1 mole reaction product, dibutyltin 1.5 parts, 1,1-dimethoxy-2-
5 parts of trimethylsilyl-1-sila-2-azacyclopentane were mixed to obtain a crosslinking agent mixture Y-3. 100 parts of base compound X-2, 4.5 parts of crosslinking agent mixture Y-3, 1 part of aminoalkyl group-containing organopolysiloxane E-1, 1,
A composition was prepared by blending 8 parts of 3-diisopropenoxyhexamethylcyclotetrasiroquine in the same manner as in Example 1. When this was cured in the same manner as in Example 1, it became dry to the touch after 5 minutes. After curing, no resinification of the surface of the cured product was observed and no cracks were generated. In addition, the physical properties are hardness 30, tensile strength 16 kgf / cm ² , elongation
It was 320%. In addition, when a sample for measuring the adhesiveness was prepared by using the same silicone rubber as the adherend as in Example 1 (shown in Table 1) of this composition, and a manual peel test was carried out after curing. It was 100%.

Example 6 100 parts of polydiorganosiloxane having a viscosity of 20,000 cP, which was composed of 11 mol% of diphenylsiloxane units and the rest of dimethylsiloxane units and had both ends blocked with methyldimethoxysilyl groups, had a specific surface area of 200 m ² Add 15 parts of fumed silica / g and mix evenly to form base compound X-
Got 3 To 100 parts of this base compound X-3, 5.5 parts of the crosslinking agent mixture Y-2 used in Example 3 and 1 part of the aminoalkyl group-containing polyorganosiloxane E-2, 1,3-bis [(N, N, N ', N'-tetramethyl) guanidylpropyl]
A composition was prepared by blending 6 parts of tetramethyldisiloxane in the same manner as in Example 1. When this was cured in the same manner as in Example 1, it became dry to the touch after 8 minutes. After curing, no resinification of the surface of the cured product was observed and no cracks were generated. The physical properties were a hardness of 34, a tensile strength of 14 kgf / cm ² , and an elongation of 280%. When the adhesiveness to silicone rubber was evaluated in the same manner as in Example 3, the cohesive failure rate was 100% in all cases.

Example 7 100 parts of the base compound X-1 used in Example 1 were mixed with 4 parts of the crosslinking agent mixture Y-2 and 2 parts of methyltri (isopropenoxy) silane in the same manner as in Example 1. , A composition was prepared. When this was cured in the same manner as in Example 1, it became dry to the touch after about 6 minutes. Also,
The physical properties were a hardness of 27, a tensile strength of 14 kgf / cm ² and an elongation of 480%. When the adhesiveness to silicone rubber was evaluated in the same manner as in Example 3, the cohesive failure rate was 100% in all cases.

Example 8 100 parts of the base compound X-2 used in Example 5, 4 parts of the crosslinker mixture Y-2 and 3 parts of 1,1,3,3-tetramethylguanidylpropyltrimethoxysilane are used. Was blended in the same manner as in Example 1 to prepare a composition. This is Example 1
When it was cured by the same method as above, it became dry to the touch after about 5 minutes. The physical properties are hardness 29, tensile strength 17kgf /
It had a cm ² and an elongation of 440%. When the adhesion to silicone rubber was evaluated in the same manner as in Example 3, the cohesive failure rate was 100% for all.

Claims (26)

[Claims] 1. The following components (A) to (D), namely (A) (1) the general formula R ¹ _a (R ² O) _3-a SiO [R ₂ SiO] _n Si (OR ² ) _{3 -a} R ¹ _a (wherein R and R ¹ are the same or different monovalent substituted or unsubstituted hydrocarbon groups, R ² is an alkyl group having 1 to 4 carbon atoms and a total of 1 to 6 carbon atoms, respectively) Monovalent group selected from the group consisting of alkoxyalkyl groups, a is 0
Or the number of 1, n is the viscosity of (A) at 25 ℃ is 100-50
End-reactive polyorganosiloxane represented by the formula (1), and (2) the general formula R ³ _b Si (OR ⁴ ) _4-b (wherein R ³ is a monovalent substituted or unsubstituted). Hydrocarbon group, R
⁴ is an alkyl group having 1 to ⁴ carbon atoms and a total of 1 to 6 carbon atoms
A monovalent group selected from the group consisting of alkoxyalkyl groups, and b is a number of 0 or 1, and the total amount of the silane or its partial hydrolyzate is 100 parts by weight (however,
(A) (1) (2) (A) (1) is 85 to 100% by weight); (B) Curing catalyst 0.01 to 10 parts by weight; (C) Nitrogen atom is one or more carbon atoms. 0.5 to 10 parts by weight of a nitrogen-containing silicon compound bound to a silicon atom through the nitrogen atom and the nitrogen atom directly bound to the silicon atom or another silicon atom; and (D) in the molecule, the following general formula: Silane or siloxane having at least one of alkenyloxysilyl group and / or guanidyl group represented by (I) and (II) 0.05 to 50 parts by weight (However, R ⁹ is the same or different, substituted or unsubstituted 1
A valent hydrocarbon group, R ¹⁰ and R ¹¹ are hydrogen atoms or the same or different substituted or unsubstituted monovalent hydrocarbon groups,
m is a number from 1 to 3, and R ¹² , R ¹³ , R ¹⁴ and R ^{15 each} represent a hydrogen atom or the same or different substituted or unsubstituted monovalent hydrocarbon group) at room temperature. Curable polyorganosiloxane composition. 2. The composition according to claim 1, wherein the terminal group of (A) (1) is a methyldimethoxysilyl group. 3. The composition according to claim 2, wherein (A) (1) is polydimethylsiloxane blocked with a methyldimethoxysilyl group. 4. The viscosity of (A) (1) at 25 ° C. is 500 to 200,
The composition according to any one of claims 1 to 3, which is 000 cP. 5. The method according to claim 1, wherein R ^{4 in} (A) (2) is a methyl group.
4. The composition according to any one of 4 above. 6. The composition according to claim 5, wherein (A) (2) is tetramethoxysilane. 7. The composition according to claim 5, wherein (A) (2) is methyltrimethoxysilane. 8. A blending amount of (A) (2) is 0.4 to 5% by weight of (A).
The composition according to any one of claims 1 to 7, which is 9. The method according to claim 1, wherein (B) is an organotin compound.
9. The composition according to any one of item 8. 10. The composition according to claim 1, wherein the compounding amount of (B) is 0.1 to 1 part by weight. 11. The method according to claim 1, wherein (C) is N-trimethylsilyl-γ-aminopropyltriethoxysilane.
The composition according to any one of 1. 12. The composition according to claim 1, wherein (C) is 1,1-dimethoxy-2-trimethylsilyl-1-sila-2-azacyclopentane. 13. The composition according to claim 1, wherein (C) is poly (1,1-dimethoxy-5-trimethylsilyl-1-sila-5-azapentane). 14. The composition according to claim 1, wherein the compounding amount of (C) is 1 to 5 parts by weight. 15. The composition according to claim 1, wherein (D) is methyltri (isopropenoxy) silane. 16. The composition according to claim 1, wherein (D) is vinyltri (isopropenoxy) silane. 17. The method according to claim 1, wherein (D) is 1,1,3,3-tetramethylguanidylpropyltrimethoxysilane.
The composition according to any one of 1. 18. The composition according to claim 1, further comprising 0.05 to 50 parts by weight of a substituted or unsubstituted aminoalkyl group-containing polyorganosiloxane represented by the following general formula as the component (E).
7. The composition according to any one of 7. [R ⁵ ₂ NR ⁶ SiR ⁷ _c O _{(3-c) / 2} ] _p [R ⁸ _d SiO _{(4-d) / 2} ] _q (where R ⁵ is a hydrogen atom and a substituted or unsubstituted hydrocarbon group R ⁶ is a divalent hydrocarbon group, R ⁷ and R ⁸ are substituted or unsubstituted monovalent hydrocarbon groups selected from the group consisting of , C is the number 0, 1 or 2, d is the number 0 or 1 to 3, p and q are the viscosities of (E) at 25 ° C of 5
Each number is 1 or more, which is ~ 10,000 cP, and p / (p + q) is
(0.33 or less) 19. The composition according to claim 18, wherein R ⁵ ₂ NR ^{6 in} (E) is a γ-aminopropyl group. 20. A composition of claim 18 R ⁵ ₂ NR ⁶ is N-(beta-aminoethyl)-.gamma.-aminopropyl groups (E). 21. The method according to claim 18, wherein R ^{7 of} (E) is a methyl group.
21. The composition according to any one of 20 to 20. 22. The method according to claim 18, wherein R ^{8 of} (E) is a methyl group.
22. The composition according to any one of claims 21 to 21. 23. The composition according to claim 18, wherein the p / (p + q) of (E) is 0.005 to 0.2. 24. The viscosity of (E) at 25 ° C. is 10 to 2,000 c.
The composition according to any one of claims 18 to 23, which is P 2. 25. The composition according to any one of claims 18 to 24, wherein d in (E) is 2, or a mixture of 2 and 3. 26. The composition according to any one of claims 18 to 25, wherein the compounding amount of (E) is 0.1 to 10 parts by weight.