JPS6034987B2 - Room temperature curable polyorganosiloxane composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a rubber-like elastic material by crosslinking Q.-dihydroxypoly(diorganosiloxane) with an organosilicon compound having an average of two or more aminoxy groups in one molecule. The present invention relates to room temperature curable polyorganosiloxane compositions having particularly improved storage stability and anti-flow properties.

Furthermore, the present invention uses a compound mainly composed of Q.■-dihydroxypoly(diorganosiloxane) and a compound mainly composed of an organosilicon compound containing an organoaminoxy group, which are mixed at the time of use. A two-packaged room-temperature-curable polyorganosiloxane composition, in which essentially Q.-no dihydroxypoly(diorganosiloxane) and an organosilicon compound containing an organoaminoxy group are allowed to coexist and stored in a moisture-free state. In the case where the polyorganosiloxane composition is liquid or plastic, it is related to a one-pack room-temperature-curable polyorganosiloxane composition that hardens on contact with moisture to become a rubber-like elastic body. Recently, room-temperature-curing polyorganosiloxane elastomer (referred to as RTV silicone rubber) has been used as a sealant for construction.It has excellent weather resistance, durability, heat resistance, and cold resistance, has little change in physical properties due to temperature, and is It is widely used due to its excellent characteristics such as low deterioration due to ultraviolet rays.

Conventionally, acetic acid-depleted polyorganosiloxane elastomers have been mainly used for this purpose, but they do not provide sufficient adhesion to concrete or mortar even after being undercoated, and they are released. However, there are some drawbacks such as corrosion caused by acid, and a solution to these problems has been desired. Later, the above-mentioned difficulties were solved with polyorganosiloxane elastomers such as oxime-free and alcohol-free polyorganosiloxane elastomers, but when these elastomers are actually used as sealants, they have to have a large modulus and a low elongation at break. It was unsatisfactory as a sealant for high-rise buildings, as the sealant was limited to about 600%. In other words, in high-rise buildings, sealing materials with low modulus and high elongation at break are required because of the need to absorb vibrations caused by earthquakes. Siloxane elastomers cannot satisfy these requirements, and therefore there are restrictions on where they can be used. As a sealing material for a polyorganosiloxane elastomer with low modulus and high elongation, Q.-dihydroxypoly(diorganosiloxane) and an aminoxy group-containing organosilicon compound proposed in Japanese Patent Publication No. 43-24545. There is a dehydroxylamine type polyorganosiloxane elastomer made by combining with.

This has the advantage that a sealing material with low modulus and high elongation can be obtained by adjusting the ratio of the difunctional aminoxy group-containing silicon compound to the trifunctional aminoxy group-containing organosilicon compound. Currently, there are only two types of sealing materials based on this cross-linking mechanism, in which Q.■-dihydroxypoly(diorganosiloxane) and an aminoxy group-containing organosilicon compound are stored separately, and when used, they are mixed and cured at room temperature. has been put into practical use.

The biggest difficulty with this product is that it must be mixed uniformly and in a certain amount at construction sites under various adverse conditions. Therefore, the shapes of both components should be the same, and the mixing ratio should be 1:
It has long been strongly desired to bring the value close to 1. However, the aminoxy group-containing organosilicon compound itself is a very unstable compound, and it also requires
When a two-pack type composition with physical properties and curability is set, the mixing ratio is about 100:1 to 3, which is far from meeting the above requirements. Therefore, various efforts have been made to increase the amount of the aminoxy group-containing organosilicon compound by diluting it or mixing it with a suitable filler. However, because of this, stability was a concern, and when stored for a long period of time, the workability, physical properties, and curing properties changed, resulting in the product value being halved. In addition, when organic substances such as ethers are used as stabilizers, they are effective in improving stability, but the low boiling point of the added compounds increases the risk of ignition, and the cured composition may There were problems such as thinning of the meat. Proceeding further, 1 of this composition
Packaging type products have also been strongly desired.

In this case, there is no troublesome operation of mixing, and there are no measuring or mixing errors, which is advantageous in terms of time, physical properties, appearance, etc. Therefore, like the conventional deacetic acid type, deoxime type, and dealcohol type, Q.Yamaichi dihydroxypoly(diorganosiloxane)
It was hoped that a so-called single packaging model would be developed in which the material and crosslinking agent were stored in the same container and released into the air to be cured by the action of moisture. However, with conventional technology, when Q.-dihydroxypoly(diorganosiloxane) and an aminoxy group-containing organosilicon compound are mixed, a dehydroxylamine reaction and a siloxane failure reaction occur, even if moisture is removed. Even if you save it in a
Curing progresses within 3 hours, viscosity decreases in a sealed container, and conversely, even when released into the air and exposed to moisture, it does not harden to the desired hardness, resulting in a single package. I couldn't do it. However, recently, as a method to solve these problems, the organic hydroxylamine generated in the system is converted into a harmless one through a chemical reaction, or by adding an additive that has the effect of removing it by adsorption.
It has been proposed that the product be packaged. One method is to use aluminosilicate as an adsorbent (Japanese Unexamined Patent Publication No. 52
No. 132,949), but in this case, stability is improved but curing is slow. Furthermore, the method of adding a SiH bond-containing compound to react with organohydroxylamine to improve stability has the problem of foaming due to generation of hydrogen gas in the system. Furthermore, in sealing materials with low modulus that use such organoaminoxy group-containing organosilicon compounds as crosslinking agents, heavy, light, or porcine calcium carbonate powders are used as fillers.

When applying and curing such sealants on vertical surfaces, sloped surfaces, ceiling surfaces, and joints between these surfaces,
There is a so-called slump phenomenon in which the sealant flows out until it hardens, making it impossible to position the sealant in the correct position. To prevent this, thickeners such as amine-added castor oil, hydrogenated castor oil, pentonite, and surface-treated pentonite are added, but the system to which these are added is uniformly mixed. In addition, if a large shearing force is applied to the mixture, the flow prevention (slump prevention) effect is impaired. One of the inventors of the present invention conducted research to solve these drawbacks, and first removed the small amount of organohydroxylamine present in the system by adding a compound having one or more isocyanate groups in the molecule. It was discovered that the storage stability of the composition was significantly improved, and it became possible to produce a one-pack type sealing material using such a crosslinking system (Tokubuta Sho 53-36 Satoshi No. 3).
. As a result of further research by the present inventors, as a filler,
By using calcium carbonate that exhibits a cubic shape with an average particle size of 0.1 to 1.0 French, flowability during construction can be completely prevented without adding any thickeners, and it also improves storage stability. However, we have discovered that it exhibits excellent effects that cannot be achieved with conventional heavy, light, or pork calcium carbonate, and by using it in combination with the above-mentioned isocyanate group-containing compound, we have developed a single-pack sealing material. The present inventors have discovered that the compound exhibits excellent storage stability as a compound, and have accomplished the present invention. In addition, adhesive properties are required as a sealant,
The above composition using calcium carbonate exhibits better adhesion than using vehicle quality calcium carbonate or light quality calcium carbonate alone, and uses pork quality calcium carbonate having an average particle size of 0.1 French or less. It exhibits adhesion properties equivalent to those of the previous composition. That is, the present invention has the following features: (1) A general formula having a viscosity of 20 to 100,000 ratio p at 2-molar temperature.

(R chamber Si.) Q. Yamaichi dihydroxypoly( diorganosiloxane) 10 parts by weight, 0.1 to 3 parts by weight of an aminoxy group-containing organosilicon compound having an average of 2 or more organoaminoxy groups in the molecule, {C)
1 to 35 parts by weight of powdered calcium carbonate having an average particle diameter of 0.04 to 10 F, and at least 1% by weight of the powder having a cubic shape with an average particle diameter of 0.1 to 1.0 F, and a rib polyol compound 2.
A general formula with a viscosity of 20 to 100,000 p at 5oo.

(R chamber Sj.) Q.-dihydroxypoly(
diorganosiloxane) 10 parts by weight, [B) 0.1 to 3 parts by weight of an aminoxy group-containing organosilicon compound having an average of 2 or more organoaminoxy groups in the molecule, [C}
Average particle size of 0.04 to 10 F, and 1% by weight
1 to 35 parts by weight of powdered calcium carbonate having a cubic shape with an average particle size of 0.1 to 1.0, and a compound having one or more isocyanate groups in the molecule.
．． 001-2 parts by weight of room temperature curable polyorganosiloxane compositions.

Q.w-dihydroxyboly(diorganosiloxane), which is the harmful ingredient used in the present invention, has a general formula.

(R chamber Sj.) nH (in the formula, R1 and n are as described above)
The viscosity at 25℃ is 20 to 100,000.
It is of ratio p.

RI includes monovalent hydrocarbon groups such as methyl group, ethyl group, propyl group, butyl group, vinyl group, and phenyl group;
Monovalent substituted hydrocarbon groups such as a chloromethyl group, a cyanoethyl group, and a 3,3,3-trifluoropropyl group are exemplified, and they may be the same or different. In order to satisfy the properties as a sealant, especially low modulus, excellent weather resistance and properties, appropriate curing speed, and appropriate fluidity as a composition before curing,
It is preferable that 85% or more of RI be methyl groups, and in particular, those in which R is all methyl groups are advantageous in view of these characteristics and the ease of synthesis of Q.Yamaichi dihydroxypoly(diorganosiloxane). be. Furthermore, when flame retardancy, cold resistance, and heat resistance are required, it is recommended to use a phenyl group as a part of RI. The range of n is determined from the viewpoint of ease of handling, flowability of the composition, physical properties of the sealant after curing, etc., and the viscosity of Q. is selected to be within the range of The value of n varies depending on the type of RI and its molar ratio, but when all RIs are methyl groups, it corresponds to 20 to 3000. Among them,
The viscosity at 25°C is preferably in the range of 100 to 10,000 ratio p, and more preferably in the range of 500 to 5,000 ratio p. This is because if a material with a viscosity lower than this range is used, it will not be possible to obtain the low modulus and good elongation at break that are necessary for a sealant, and if a material with a high viscosity is used, workability will be poor. It is. {B} used in the present invention
The component aminoxy group-containing organosilicon compound is Q.
Dihydro.

By performing a dehydroxylamine reaction with the terminal silanol group of xypoly(diorganosiloxane), the shape of the polysiloxane is changed and the chain length is extended. A siloxane conductor may also be used. For the purpose of obtaining a sealing material with particularly good reactivity, low modulus, and high elongation, a combination of cyclic polysiloxanes having two and three aminoxy groups in one molecule is preferred. Also, an average of 2
An organosilicon compound having one aminoxy group in one molecule, especially a cyclic polysiloxane, may be used in combination within the range where more than one aminoxy group is present. Examples of organic groups to be bonded to the aminoxy group include methyl group, ethyl group,
Examples include two monovalent hydrocarbon groups such as propyl group, butyl group, and cyclohexyl group, or one divalent hydrocarbon group such as butylene group and bentene group, but depending on the availability of raw materials. An ethyl group is preferred from the viewpoint of ease of synthesis, reactivity, and ease of scattering of the organohydroxylamine to be released. Examples of such aminoxy stem-containing organosilicon compounds include the following. Hereinafter, for the sake of simplicity, the following abbreviations will be used for various organosilicon compounds. (Abbreviation) Me: methyl group, Et: ethyl group, Bu: butyl group, V
i: vinyl group, Ph: phenyl group Si (〇NE et al.) 4,
MeSi 〇NEt2)3, PhSi(〇NMe2)
3. PhSi (〇NE et al.) 3. Et2NOMe2SiS
iMe20NEt2Et2NOMe2SjOSiMe2
0NEt2Et2NOMe2SiOPh2SiOSjM
e20NEt2, MeSi [OMe2SiONEt2]
3. PhSi[OMe2SjONEt2]3 The amount of such aminoxy group-containing organosilicon compound added is 1
0.1 to 30 parts by weight, preferably 1 part by weight
-2 parts by weight.

If the amount of the aminoxy group-containing organosilicon compound added is less than 0.1 part by weight, the reaction rate with Q. Yamaichi dihydroxy poly(diorganosi. In the case of a mold, sufficient working time is not obtained, and if the amount added exceeds 3 parts by weight, storage stability and curability decrease. used in the present invention
Calcium carbonate, component C, gives the composition appropriate physical properties, especially workability as a building sealant, low modulus, and high elongation, and has an average particle size of 0.04.
~10 Buddhas, preferably 0.1 Buddhas or more in powder form, and
In order to maintain the storage stability of the composition and prevent slump, 10% by weight or more of the composition is cubic particles having an average particle diameter of 0.1 to 1.0 mm (hereinafter referred to as component (〇)).

The (C') component may be [the total amount of the C' component, or (C')
In addition to the ingredients, for example, carmine or light calcium carbonate may be used in combination, but if the component (C') is not present at least 1% by weight in the component (C), the composition that is the object of the present invention will not be produced. Storage stability and slump prevention effect are not exhibited. In other words, a composition using only heavy calcium carbonate obtained by pulverizing natural calcium carbonate has good storage stability, but is unfavorable in terms of physical properties and slump generation, and also has poor adhesive properties, so it is not suitable for sealing. Not suitable for wood. Light calcium carbonate, which has a pyramidal shape, is difficult to disperse in the system.
In addition, it has poor slump and storage stability, especially when packaged in one package. In addition, even if the average particle diameter is less than 0.1 French,
Even if the particle size exceeds the limit, slump may occur and storage stability may be poor.In particular, particles with an average particle diameter of less than 0.1 mm are likely to agglomerate without surface treatment, and this should be prevented. Since the surface is always treated with a large amount of anti-aggregation agent, when used in polyorganosiloxane compositions,
As a result, storage stability deteriorates and slump occurs. The average particle diameter of the component (〇) is 0.1 to 1.0 mm, preferably in the range of 0.12 to 0.6 mm,
If it is smaller or larger than this, the effect of improving storage stability and preventing slump will be inferior.

Although it can be used without surface treatment, from the viewpoint of dispersibility in the system, storage stability of the composition, and slump prevention effect, it is necessary to use a small amount, that is, 0.1 to 1.0% by weight. It is preferable to treat the surface with a surface treatment agent. Exceeding this range is undesirable because it may actually lead to slump. Examples of surface treatment agents include fatty acids such as stearic acid and oleic acid, resin acids such as rosin, cationic surfactants, and silicates, which may be used alone or as a mixture of two or more. However, from the viewpoint of the storage stability of the composition and the slump prevention effect, it is recommended to mix rosin or ogin with fatty acids. Such an average particle diameter of 0.1~
1. The manufacturing method for Buddha's cube-shaped powdered calcium carbonate dates back to the 5th century of the Samurai era.
It is disclosed in Japanese Patent No. 3-43694 and is also commercially available.

Commercially untreated cubic calcium carbonate products include Brilliant-1 and Brilliant 1500 (both manufactured by Shiroishi Kogyo Co., Ltd.; trade names), and fatty acid-treated products include Bigotto 15 (manufactured by Shiroishi Kogyo Co., Ltd.). (Product name), rosin treated product is Uniphant-1
5 (manufactured by Shiraishi Kogyo Co., Ltd.; trade name).
Unlike ordinary calcium carbonate fillers, such cubic calcium carbonate is composed of cubic particles with a stable and uniform surface, and has extremely few crystal defects. The amount of calcium carbonate added is 1 to 1 to 100 parts by weight of component Q-dihydroxypoly(diorganosixane).
35 parts by weight, preferably in the range of 20 to 250 parts by weight. If the amount is less than this range, the reinforcing effect will not be sufficient and slump will occur during curing. Also, if there are too many,
This is because the viscosity at the time of construction becomes high, resulting in poor workability, and the modulus becomes large, making it impossible to pass as a building sealant. Furthermore, the amount of component (○) is preferably in the range of 10 to 200 parts by weight. If the amount is less than this, the slump prevention effect will be weak, and if it exceeds 20 parts by weight, the mixture will become too thick. The storage stability and slump prevention effect of the component (○) of the composition is not sufficient by itself, but can be effectively exerted by using it in combination with a polyol as a dish component or an isocyanate group as a dish component. In particular, the storage stability when packaged in one package is enhanced by the combined use with component 'E'. The polyols of component [D} used in the present invention include ethylene glycol, propylene glycol, glycerin, diethylene glycol, triethylene glycol, and poly(oxyethylene) and poly(oxyph) having hydroxyl groups at both ends.
Examples thereof include oxyethylene-oxypropyrene copolymer, and glycerin is preferred from the viewpoint of effectiveness. The amount of polyol added depends on the harmful component Q.
The amount is 0.01 to 1 part by weight per 10 parts by weight of dihydroxypoly(diorganosiloxane). This is because if the amount is less than this range, there will be no effect, and if it is more than this range, the curability and physical properties will be affected. The isocyanate group-containing compound of the tE' component used in the present invention is a compound having the following four functions.

■ By preferentially reacting with moisture present in the system, it protects the composition from the effects of moisture.

■ Reacts with organohydroxylamine remaining or generated in the system to convert it into other harmless compounds, producing organohydride. Removes negative effects from xylamine. ■
It can function as an adhesion promoter and impart self-adhesive properties to such compositions.

(○) Due to the interaction with component (〇), it has the effect of preventing slump when the composition is cured.

In the case of the two-pack type according to the conventional technology, it is extremely difficult to completely remove the organohydroxylamine that remains in small amounts during manufacturing from the aminoxy group-containing organosilicon compound of component {B}, and this makes Tsukuda This reduced the storage stability of the ingredients and shortened the shelf life of the product itself. In this case, residual organohydroxylamine can be completely removed by adding an isocyanate group-containing compound, thereby dramatically improving shelf life. In addition, in the prior art, when adding silicone oil, other oily substances, fillers, and pigments to the aminoxy group-containing organosilicon compound of component 'B} to dilute, increase the amount, or color it, water is removed from it in advance. In order to remove it, it was necessary to dry it or knead it under heat and vacuum. In this case as well, the method of adding the isocyanate group-containing compound of the present invention not only eliminates the need for the above-mentioned troublesome operation due to the effect of (1) described above, but also allows the effect (2) to continue even after dilution, volume increase, and coloring. In this case as well, the shelf life is dramatically improved. Furthermore, in the case of a one-pack type, water can be removed from the raw material in advance by the action of ■, and the ingredients and [
Since the organohydroxylamine produced when mixed with component B' is also rendered harmless by the action of (2), excellent preservability can be obtained.

In addition, due to the effect of (2), self-sagging properties can be expected regardless of whether the two-pack type or the one-pack type is used. Conventionally, with this type of composition, sufficient adhesion was not achieved unless the base material was treated with an appropriate primer in advance. However, by adding this isocyanate group-containing compound, good adhesion can be obtained even without primer treatment. Moreover, as an effect (2), slump can be prevented. Examples of isocyanate group-containing compounds as CI components used in the present invention include monomers with isocyanate groups such as OCN-(CH2)6-NCO, multimers such as adducts of OCN-(CH2)6-NCO, and urethanes such as Polymers, etc.

Furthermore, Me3SINCo, Me2Si(NCO)2, Ph
Organosilicon compounds such as Si(NCO)3 are also useful.

The amount of such isocyanate group-containing compound added is 0.001 to 2 parts by weight, preferably 0.005 to 5 parts by weight, based on 10 parts by weight of Q.-dihydroxypoly(diorganosiloxane) of the wind component. selected from the range.

If the amount added is less than 0.001 part by weight, the composition will not have sufficient storage stability and adhesion, and if it exceeds 20 parts by weight, the reaction of formula [1} above will occur, causing the composition to be exposed to air during use. This is because the moisture causes foaming and the moisture delays curing. The composition of the present invention may further contain various substances known as additives for polyorganosiloxane compositions of this type.

Such additives include ground silica, fumed silica,
fillers such as precipitated silica, silica, titanium oxide, iron oxide, colored pigments such as force-pump rack, platinum compounds, flame retardants such as polymethylphenylsiloxane, and low to medium viscosity silicone oils. Examples thereof include extrudability modifiers such as, antifungal agents such as organic tin compounds, and the like. The composition of the present invention has a heavy particle size, a light particle size, and an average particle size of 0.
．． Compared to those using lumbar calcium carbonate of less than 1 French as a filler, it has excellent storage stability and there is no slump of the hardening agent.

This means that when containing isocyanate group-containing compounds,
The same can be said for both cases. In particular, a composition containing an isocyanate group-containing compound exhibits excellent storage stability in conjunction with the hydroxylamine exhausting effect of the compound, and this composition is stored in a moisture-blocking container, By extruding this into the air, it is cured by the action of moisture in the air, and can be used as a so-called one-pack type sealing material. Examples of moisture-blocking containers include cartridges, tubes, airtight bags, and containers made of plastic, paper (often containing an aluminum or polyethylene layer), and metal. The composition of the present invention is useful as a low modulus one-pack type and two-pack type sealant in architecture, particularly in high-rise buildings.

The present invention will be explained below with reference to Examples. In the examples, all parts represent parts by weight. In addition, the following abbreviations were used to describe physical properties in the examples. H: Hardness (JIS)
, Ts: tensile strength (kgf'), E: elongation (%), M
k: k% modulus (k9f'), CF: cohesive failure rate (%), TF: tack free time (h).

Furthermore, for the sake of simplicity, the following symbols are given to the aminoxy group-containing organosilicon compound, calcium carbonate, and isocyanate group-containing compound used in the examples.

Ami/oxy group-containing organosilicon compound B-1 B-2 B-3 B-4 E-2 B-5 B-6 Et2NOMe2SiOPh2SiOSiMe
20NEt2B-7 Calcium carbonate C-1 Cubic calcium carbonate with an average particle size of 0.15 mm (untreated) C-2 Cubic calcium carbonate with an average particle size of 0.15 mm (surface treated with 0.5 wt% stearic acid) C-3 Cubic calcium carbonate with an average particle size of 0.4
(Surface treated with 0.5% by weight each of rosin and oleic acid) C-4 Cubic calcium carbonate with an average particle size of 0.5F (
Untreated) C-5 Cubic calcium carbonate with an average particle size of 0.15 (surface treated with 0.25% by weight of each stearic acid and cationic surfactant) C-6 Average particle size 0.15 of cubic calcium carbonate (0.25% by weight each
surface treated with rosin and stearic acid) C-7
Pulverized calcium carbonate isocyanate group-containing compound E-1 Tolylene diisocyanate E-3 B-4 Me3SINCO E-5 E-6 0CN-(CH2)6-NCOE-7 with an average particle size of 0.5 French
The extrusion test in the 0CN-(CH2)4--NCO example was conducted as follows.

That is, the prepared product was placed in a plastic cartridge specified in JISA 5757, and the 3yC was 1.5.
After a period of time had elapsed, the sample was pressed using a special gun with the pressure of an lk9f/c fin, and the time required for the entire amount of the composition to be extruded was measured. The slump test in the examples is JISA
It was carried out according to the method specified in No. 5757.

That is, the stagnation part A of the smoked copper slump tester shown in FIG.
is filled with a composition, supported in a vertical direction to cure the composition, and the length through which the composition flows until it is cured is measured to determine the slump. Note that in JIS, the width of the base portion is 20 mm, but in this example, either or both of the 2 mm width and the 5 mm width was used. Example 1 The viscosity at 25 qo is 300 p.

Q. Yamaichi dihydroxypoly(dimethylsiloxane) 10
3 parts of C-1 and 35 parts of C-7 were added to 0 parts and uniformly kneaded to obtain a base compound. 10 pieces of this base compound, B-1 and B-2 in the amounts shown in Table 1.
, B-3, and glycerin and mix to form composition l
Compositions a to lc and comparative composition ld were prepared. Extraction test, slump test, and JISK 630 of these compositions
The physical properties tests specified in 1 were conducted. Also, C-1
Comparative Example Sample le, which was prepared in the same manner as Composition La except that 65 parts of C-7 was used instead of C-7, was measured using the same machine. The results are shown in Table 1. Table 1 Example 2 Q-dimethylpoly(dimethylsiloxane) with a viscosity of 100 p at 250°C, 4 parts of C, 15 parts of C
-2 and 2 parts of C-7 were added and kneaded uniformly to 22.
A curing agent masterbatch was obtained by mixing 5 parts of B-4 and 2.5 parts of B-5.

To this curing agent masterbatch, isocyanate group-containing compounds of the types and amounts shown in Table 2 were added to prepare curing agent samples 2 to 2. The previous curing agent masterbatch was used as Comparative Example Curing Agent Sample 2d, and 3 was prepared without using C-2.
A comparative curing agent sample was obtained in the same manner as in the original except that 5 parts of C-7 was used. These samples were packed into glass bottles, sealed tightly, and placed in a 50 oo bath to heat and deteriorate. After a predetermined time, the base compound of Example 1 was taken out, and 1 part of each was added to 10 parts of the base compound to prepare a composition and a comparative example composition. When the test was conducted, the results shown in Table 2 were obtained. Table 2 Example 3 To 100 parts of Q.-dihydroxypoly(dimethylsiloxane) having a viscosity of 8000 p at 25 qo, 3
A base compound was prepared by adding and kneading 6 parts of C-3 and 6 parts of C-7.

To 100 parts of this base compound, 2.7 parts of B-4
and 0.5 part of B-5 were kneaded to obtain a comparative composition *.
Further, E-6 was further added to the powder components as shown in Table 3 to give a composition effect of ~$. These compositions were packed in aluminum tubes with moisture sewn up and sealed, and after being stored for 3 months and 6 months at room temperature, they were each extruded into the air to form sheets with a thickness of 2 ribs. 2nd army ○, temperature 50
% RH for 7 days to fully cure and measure physical properties. In addition, slump was measured using a slump tester with a width of 2 mm. In addition, without using C-3, 9
Similar measurements were carried out on a comparative example composition $, which was prepared in the same manner as the composition phantom, using a base compound prepared using the sparse portion of C-7. These results are shown in Table 3. Table 3 Example 4 To 100 parts of the base compound prepared in Example 3 were added 2.25 parts of B-2, 0.4 parts of B-3, and 0.25 parts of B-3 in the same manner as in Example 3. A comparative example composition to which B-1 was added and a composition 4b to which 0.5 part of E-4 was further added were obtained.

The viscosity and tack-free time of these compositions were packed into aluminum tubes sealed in a moisture-free state and stored in a thermostat at 50 oo for 1 to 4 months. Similarly to example 3,
When we measured the physical properties of a sheet with a thickness of 2 and the slump of a sheet with a width of 2, we obtained the results shown in Table 4. Table 4 Example 5 8 mol % with a viscosity of 5000 p at 25 qo
Q-dihydroxypoly(diorganosiloxane) consisting of diphenylsiloxy units of I got the compound.

To 100 parts of this base compound, 2.75 parts of B-
6, add 0.25 parts B-3 and 1 part E-5,
The mixture was mixed at room temperature under sealed conditions to obtain a composition. This was extruded into the shape shown in Fig. 2 using aluminum and glass as an adhesive body, and left in air at room temperature for 3 weeks to prepare an H-shaped test specimen. The test specimen was subjected to a tensile test at a tensile rate of 50 sails/min under normal conditions and immediately after being immersed in hot water at 70° C. for 4 hours, cooled to room temperature, and taken out from the water. The results are shown in Table 5. Table 5. The slump of this composition at the width 20 side at the initial stage and after being left in a 50 qo constant temperature bath for one month was 0.

Example 6 10 mol% with a viscosity of 2800 p at 25°C
Q. Yamaichi dihydroxypoly(diorganosiloxane) 1 consisting of methyl (3,3,3-trifluoropropylene)siloxy units and 90 mol% dimethylsiloxy units.
0 anchor part'ko, 3 anchor part C-4, 30 part C-5, and 4
A base compound was obtained by uniformly drilling the crushed quartz in the anchorage.

B-7 with 2.5 parts of this base compound 10
and 1 part of E-6 were added and kneaded. After storing this in an aluminum tube with moisture sewn up at room temperature for 5 months, a sheet with a thickness of 2 was prepared in the same manner as in Example 3, and its slump and physical properties were measured. Width 20 willow) 1 willow, day 48, TS28E330. Example 7 30 parts of C in 100 parts of -dihydroxypoly(dimethylsiloxane) having a viscosity of 1000 p at 25°C
-1 and 5 parts of polydimethylsiloxane-treated fine silica powder were uniformly kneaded to obtain a base compound.

Separately, B-4 of the 9th part, B-5 of the 7th part, and E- of the 3rd part.
Pack the mixture obtained by mixing 6 into a glass bottle and make 50 qo.
The mixture was placed in a constant temperature bath and removed at a predetermined time, and 5 parts of the base compound was added to 10 parts of the base compound to prepare a roasted product. An extrusion test, a slump test on two sides, and measurement of physical properties were carried out in the same manner as in Example 1, and the results shown in Table 6 were obtained. Table 6 Example 8 Q.w-dihyde with a viscosity of 3000 p at 25 qo.

20 parts of C to 100 parts of xypoly(dimethylsiloxane)
-1 and C-7 at anchor 6 were added and kneaded. A curing agent composition was obtained by mixing 9 parts of B-2, 1 part of B-3, and 0.25 parts of E-7. Furthermore, the above-mentioned Q.-no-dihydride. Xypoly(dimethylsiloxane) 10 Ikari Mariko 3 Ikari Miyako C-1 and 5 Foundation C-7 were added and kneaded to obtain a base compound. After mixing the two in equal amounts, the mixture was defoamed, formed into a sheet with a thickness of 2 layers, and cured. This is J
When physical properties were measured by ISK 6301, day 15, TS13. It was E1300. Also, width 2
When a slump test was conducted using the 0 fence, the slump was 0. In addition, when the curing agent composition and the base compound were mixed and stored in an aluminum container sealed against moisture for 4 weeks, and then extruded into the air, both the physical properties and slump were the same as the initial values. It was the same. Example 9 25 parts of C in 100 parts of Q-dihydroxypoly(dimethylsiloxane) with a viscosity of 450 ratio p at 25 qo
A base compound was obtained by drilling C-7 from groups -6 and 4.

This base compound is 85% B-2, 5
Mixture 3 consisting of % B-3 and 10% dioxane
1.0 parts each of the polyol compounds shown in Table 7 were added. A composition was prepared by adding base powder and thickening. This composition was subjected to an extrusion test, a slump test, and measurements of physical properties, and the results were as shown in Table 7.
Table 7

[Brief explanation of the drawing]

FIG. 1 shows a slump tester, and FIG. 2 shows a test piece for an adhesive tensile test of a silicone sealant. The unit of dimensions shown in the drawing is wind. In Figure 2,
Tensile stress is applied perpendicular to the adhesive surface. 1...Adherent, 2...Silicone sealing village. Figure 1 Figure 2

Claims (1)

[Claims] 1 (A) Viscosity at 25°C is 20 to 1,000,000
cp with the general formula HO(R^1_2SiO)_nH (wherein R^1 is the same or different monovalent substituted or unsubstituted hydrocarbon group, n is a number that satisfies the above viscosity). 100 parts by weight of ω-dihydroxypoly(diorganosiloxane), (B) 0.1 to 30 parts by weight of an aminoxy group-containing organosilicon compound having an average of two or more organoaminoxy groups in the molecule, (C) average particle diameter 0.0
4 to 10μ, and 10% by weight or more has an average particle size of 0
．． Powdered calcium carbonate 1-1.0μ cube-shaped
~350 parts by weight, and (D) polyol compound 0.01
A room temperature curable polyorganosiloxane composition consisting essentially of ~10 parts by weight. 2. The composition according to claim 1, wherein 85% or more of R^1 in (A) is a methyl group. 3. The composition according to claim 1, wherein R^1 in (A) is a methyl group. 4 (A) has a viscosity of 100 to 10,000 at 25°C
2. The composition of claim 1, which has 0 cp. 5. The composition according to claim 1, wherein the organic group bonded to the aminoxy group in (B) is an ethyl group. 6. The composition according to claim 1, wherein (B) is two or more types of cyclic polysiloxanes having two and three aminoxy groups in the molecule. 7. On the surface of cubic calcium carbonate with an average particle diameter of 0.1 to 1.0μ, 0.1 to 1
．． The composition according to claim 1, which is coated with 0% by weight of a surface treatment agent. 8. The composition according to claim 7, wherein the surface treatment agent is at least one of a fatty acid, a resin acid, a cationic surfactant, and a silicate. 9. The composition of claim 1, wherein (C) is 20 to 250 parts by weight. 10 10% by weight or more of (C) has an average particle size of 0.1
2. A composition according to claim 1, having a cubic shape of 2 to 0.6 microns. 11. The composition according to claim 10, wherein 10 to 200 parts by weight of (C) is cubic with an average particle size of 0.12 to 0.6 μ. 12. The composition according to claim 1, wherein the polyol compound is glycerin. 13 (A) Viscosity at 25°C is 20 to 100,000
0 cp of the general formula HO(R^1_2SiO)_nH (wherein R^1 is the same or different monovalent substituted or unsubstituted hydrocarbon group, n is a number that satisfies the above viscosity). 100 parts by weight of ω-dihydroxypoly(diorganosiloxane), (B) 0.1 to 30 parts by weight of an aminoxy group-containing organosilicon compound having an average of 2 or more organoaminoxy groups in the molecule, (C) average particle size 0.0
4 to 10μ, and 10% by weight or more has an average particle size of 0
．． Powdered calcium carbonate 1 in cubic shape of 1 to 1.0μ
~350 parts by weight, and (E) 0.001 to 20 parts by weight of a compound having one or more isocyanate groups in the molecule.