JPH11302395A - Production of organopolysiloxane composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for efficiently producing an organopolysiloxane composition useful as a sealing material or the like for the periphery of a glass and the joint seal of a construction material by a simple process of obtaining a base compound consisting essentially of an organopolysiloxane and an inorganic filler, and subjecting the obtained base compound to an irradiation treatment of a high frequency wave. SOLUTION: Components of an organopolysiloxane e.g. a compound of the formula [R is a monovalent hydrocarbon; (a) is an integer for regulating the viscosity of the organosiloxane at 25 deg.C so as to be 100-100,000,000 cSt] or the like} and/or an inorganic filler (preferably calcium carbonate, silica and titanium oxide having photocatalytic activities), or a base compound obtained by compounding the components is subjected to a treatment of irradiating a high-frequency wave by a high-frequency output device when obtaining the base compound consisting essentially of the organopolysiloxane and the inorganic filler to provide the objective composition, preferably a silicone rubber composition and a moisture-hardenable silicone rubber composition in the method for producing the organosiloxane composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an organopolysiloxane composition comprising an organopolysiloxane and an inorganic filler as essential components, and more particularly to a sealing material for a glass surrounding sealing material and a sealing material for building materials. The present invention relates to a method for producing an organopolysiloxane composition that can efficiently produce a high-quality organopolysiloxane composition suitable as a simple process.

[0002]

2. Description of the Related Art
The organopolysiloxane composition is produced by blending an organopolysiloxane with an inorganic filler and, if necessary, a dispersant and the like, and using a mechanical mixing device. In this case,
In a batch-type production method, it is manufactured using a roll kneader, a Shinagawa-type mixer, a gate mixer, or the like. In a continuous production method, it is extruded and kneaded with a single-screw or twin-screw type or the like.

[0003] However, the production method using such a conventional production apparatus is a method for producing an organopolysiloxane composition in which an inorganic filler having water of crystallization such as calcium carbonate is blended, particularly a product whose water content is strictly controlled. However, there has been no effective method to solve this problem, relying only on packaging containers and the like.

On the other hand, the organopolysiloxane composition comprises:
There are non-curable types such as silicone grease and cured types such as silicone rubber. The curing type is an addition curing type in which an alkenyl group-containing compound bonded to the siloxane terminal and a compound having a Si-H group are cured by an addition reaction in the presence of a platinum compound, and a base having a hydroxyl group or a hydrolyzable group at the terminal. It is broadly classified into a condensation-curing type that cures a polymer and a silane or siloxane having a hydrolyzable group, a peroxide-curing type that cures a siloxane compound having an alkenyl group with a peroxide, and a UV-curing type. You. Among these, the curing type is particularly important in moisture management.

When such an organopolysiloxane composition is produced, the base compound is extruded and kneaded with a roll kneader, a Shinagawa mixer, a planetary mixer, a universal mixer, a gate mixer, a twin screw type or the like as described above. To manufacture. When producing this base compound, heat treatment at, for example, 80 to 280 ° C. under reduced pressure or normal pressure is performed several times in order to prevent variation in physical properties due to a difference in water content or the like of the powder mixed in the composition. It is performed over a period of time to several tens of hours to remove moisture and the like. However, in this method, it takes a very long time to perform the treatment, and it is difficult to obtain a composition having stable quality by controlling the moisture according to the seasonal variation.

That is, for example, in a moisture-curable organopolysiloxane composition containing calcium carbonate, the powder is flow-dried with a heating hopper having a jacket before the powder is introduced into the mixer, or the jacket is dried. After the powder is charged into the mixing kettle, heat treatment is performed for about 1 to 2 hours at a temperature of about 100 to 150 ° C. by steam or heating with a heating medium, and then the α, ω-dihydroxyorgano of the oil as the main agent is heated. It is manufactured by mixing polysiloxane and trimethoxyorganopolysiloxane at the end.

In addition, in the production of an addition-reactive organopolysiloxane composition, various treating agents are preliminarily mixed and treated in order to block silanol groups on the powder surface due to a decrease in storage stability of the composition. That is being done.

However, these manufacturing methods have a problem that a large amount of heat treatment time must be spent to remove by-products and unreacted processing agent components of the processing agent.

Furthermore, in the above-mentioned production method, usually, a kneader or a mixer for at least 6 to 30 hours is required to produce an appropriate homogeneous material which can become a silicone rubber having satisfactory physical rubber properties after curing. Had to make use of. For example, in the production method described in Japanese Patent Publication No. 3-47664, after the organopolysiloxane, silica, silazane and water are once mixed, the mixture is heated up to 200 ° C.
In addition, a step of heating for 2 hours or more under the conditions described above to remove by-produced ammonia to 50 ppm or less is further added. In general, silica powder, silazane and water are mixed in advance to produce a homogenous modified powder, and then mixed with an organopolysiloxane by a mixer, and further subjected to a heat treatment. .

[0010] In a continuous production method which has been actively studied in recent years and is being put to practical use, a continuous kneading extruder having a single-screw or twin-screw is generally used. For example, in Japanese Patent Publication No. 1-56736, in order to stabilize rubber properties, 150 to 35
At a temperature of 0 ° C., a pressure of 0.2 kg / cm ² G or more is applied,
After drying and surface treatment of silica powder containing a large amount of silanol groups, the mixture is introduced into a continuous kneading extruder represented by a twin-screw extruder to produce an organopolysiloxane composition. In the above pretreatment, for several minutes of the kneading time, 22 minutes
The treatment was performed for 1 hour at 0 ° C.

In Japanese Patent Application Laid-Open No. 61-40327, a heat treatment at 100 to 300 ° C. is performed at the time of compounding an organopolysiloxane as a main ingredient and an inorganic filler in order to stabilize physical properties. According to this method, the compound can be kneaded continuously in a short time, but since the heat treatment is directly performed by a continuous kneader having a short residence time, the substantial heating time is extremely short, so that heat treatment is not possible. This was sufficient, and the thixotropic peak characteristics were still in a sufficiently remaining state.

In this respect, in the method described in Japanese Patent Application Laid-Open No. 5-131516, a bypass pipe that can be continuously extruded is provided in the middle of one continuous kneader to extend and manage the heat treatment time and the moisture adjustment time. ing. Further, JP-A-6-3130
In the method described in Japanese Patent Publication No. 46, two continuous kneading extruders are connected in series to increase heat treatment time and obtain desired physical properties.

Regarding the reinforcement of a series of residence times, Japanese Patent Application Laid-Open No. 9-277252 is insufficient in the production method using a continuous kneader by connecting a heatable cylinder and a heatable pump to a continuous kneader. The required heating residence time is ensured.

However, any of the above-mentioned methods requires a great deal of effort to remove silazane, nitrogen compounds and water necessary for treating powder, for example, silica powder.
Since additional steps and equipment such as high-temperature treatment, long-time kneading, and vacuum removal treatment for the treatment are indispensable, the production process is complicated, and is not industrially advantageous.

As a method of shortening the mixing time during kneading, pretreatment of the powder required for the production of silicone is actively performed. For example, Japanese Patent Application Laid-Open No. Hei 5-262983 discloses a method of frequently using a continuous kneading method. To obtain a free flowing powder,
An appropriate amount of a polyorganopolysiloxane as a main ingredient is added to the powder heated to 100 to 200 ° C. before or immediately before the introduction,
It is processed in a high-speed shearing machine for about 30 minutes or more to produce a flowable powder. However, this method also has to add an extra step of pretreatment, which is troublesome.

As described above, in the method for producing an organopolysiloxane composition, heat treatment and pretreatment for stabilizing physical properties are indispensable in any of the conventional batch method and continuous method. At present, it requires a lot of effort and energy, and is becoming a complicated process.
The solution of these problems has been an issue.

The present invention has been made in view of the above circumstances, and provides a method for producing an organopolysiloxane composition capable of efficiently and efficiently obtaining an organopolysiloxane composition having a stable quality in a simple process in a short time. The purpose is to do.

[0018]

Means for Solving the Problems and Embodiments of the Invention The present inventors have made intensive studies in order to achieve the above object, and as a result, when producing a base compound using an organopolysiloxane and an inorganic filler, By performing a process of irradiating the organopolysiloxane and / or the inorganic filler component or the obtained base compound with a high frequency by a high frequency output device, performing a troublesome and extra processing step such as a heat treatment and a pretreatment. It has been found that an organopolysiloxane composition having stable quality can be obtained efficiently and in a short time in a simple process.

In the present invention, the organopolysiloxane and / or the inorganic filler component or the obtained base compound is irradiated with a high frequency using a high frequency output device (microwave) to be incorporated into the composition. Degassing by skipping the crystallization water attached to the powder to be prepared,
It is possible to reduce the water content of the powder affected by seasonal factors such as humidity, and also to remove excess water, nitrogen compounds, ionic compounds, and the like contained in the crystal water and the composition even after the base compounding. It can be easily and efficiently removed in a short time. Furthermore, an oil whose terminal is efficiently blocked can be obtained from a base oil whose terminal is blocked by a hydroxyl group and a hydrolyzable silane or siloxane.

The production method of the present invention is applicable not only to the production of three types of organopolysiloxane compositions of addition-curable type, condensation-curable type and peroxide-curable type, but also to the use of water of crystallization in other fields. Very useful for those sensitive to moisture. It is particularly useful for silicone rubber compositions, especially moisture-curable silicone rubber compositions.

The addition-type and peroxide-curable silicone compositions obtained by the method of the present invention have no plastic reversion, no poor curing or discoloration due to residual nitrogen compounds, and a condensation-curable silicone rubber. In the composition, it is also possible to reduce the variation in physical properties due to the return and storage properties and the process, and also to reduce the amount of hydrolyzable curing agent by taking measures against moisture,
Improvements in rubber properties, stabilization of quality, cost reduction, and the like can be achieved.

Conventionally, JP-A-52-37966, JP-A-1-243020, and JP-A-2-170
No. 81, Japanese Patent Publication No. 7-63619, etc., have proposed microwaves. However, the use of a high-frequency output device for the production of an organopolysiloxane composition allows the above-described effects to be obtained. This is a new finding of the present inventors.

Accordingly, the present invention relates to a process for producing a base compound comprising an organopolysiloxane and an inorganic filler as essential components, when the organopolysiloxane and / or the inorganic filler component or the obtained base compound is used. Provided is a method for producing an organopolysiloxane composition, which comprises performing a process of irradiating a high frequency with a high frequency output device.

Now, the present invention will be described in further detail. The method for producing an organopolysiloxane composition of the present invention is as follows: an organopolysiloxane composition for producing a base compound using an organopolysiloxane and an inorganic filler. It is applied to various curable organopolysiloxane compositions such as addition-curable, peroxide-curable and condensation-curable types, and non-curable organopolysiloxane compositions such as silicone grease.

Here, in the organopolysiloxane composition, as the organopolysiloxane which is a main component of the base compound, one corresponding to the target organopolysiloxane composition is used. As the vulcanized silicone, any organopolysiloxane having two or more alkenyl groups may be used, but the one represented by the following formula (1) is particularly preferable.

[0026]

Embedded image (In the above formula, R represents an unsubstituted or substituted monovalent hydrocarbon group which may be the same or different, and a represents a viscosity of the organopolysiloxane at 25 ° C. of 100 to 100,0.
It is an integer in the range of 00,000 cs. )

The substituent R in the above formula (1) is an unsubstituted or substituted monovalent hydrocarbon group, preferably having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, a propyl group and a butyl group. And unsubstituted monovalent hydrocarbon groups such as an alkyl group such as an alkyl group, an alkenyl group such as a vinyl group, and an aryl group such as a phenyl group, and a part or all of the hydrogen atoms bonded to carbon atoms of these groups are halogen atoms. A chloromethyl group substituted with
Examples include a substituted monovalent hydrocarbon group such as a cyanoethyl group and a 3,3,3-trifluoropropyl group. Among these, having an appropriate curing speed, properties after curing,
Methyl groups are most preferred because of their low physical properties, especially modulus, but when cold resistance is required depending on the application,
It is preferable to introduce a phenyl group or a 3,3,3-trifluoropropyl group. Further, it is necessary to have two or more alkenyl groups, and it is particularly preferable that the terminal is blocked with an alkenyl group.

The viscosity of the organopolysiloxane of the above formula (1) at 25 ° C. is from 200 to 1,000,000 cs, especially from 10, in the case of a liquid composition from the viewpoint of physical properties and workability.
000 to 500,000 cs is preferable, and 100,000 to 100,000,000 c for a millable type.
s, especially 1,000,000 to 10,000,000 c
s is preferred.

The condensation-curable silicone base oil may be any organopolysiloxane having a hydroxyl group at the terminal or two or more hydrolyzable groups in one molecule, and in particular, the following formula (2) or Those represented by (3) are preferably used.

[0030]

Embedded image (Where R is a substituted or unsubstituted monovalent hydrocarbon group, X
Is a hydroxyl group or a hydrolyzable group, m is an integer of 1, 2 or 3, n is an integer of 2 to 8, and a is a viscosity of the organopolysiloxane at 25 ° C of 100 to 1,000,000 c.
It is an integer in the range of s. )

In the above formulas (2) and (3), the substituent R
Is a substituted or unsubstituted monovalent hydrocarbon group, preferably one having 1 to 10 carbon atoms, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group, an alkenyl group such as a vinyl group, and a phenyl group Unsubstituted 1 such as an aryl group such as
Substitution of a valent hydrocarbon group or a chloromethyl group, a cyanoethyl group, a 3,3,3-trifluoropropyl group in which part or all of the hydrogen atoms bonded to the carbon atoms of these groups are substituted with a halogen atom or the like; And the like. Among these, having an appropriate curing rate, properties after curing, physical properties, especially since the modulus is low, it is most preferable that the methyl group, but when cold resistance is required depending on the application, It is preferable to introduce a phenyl group or a 3,3,3-trifluoropropyl group.

X is a hydroxyl group or a hydrolyzable group, for example, an alkoxy group such as a methoxy group, an ethoxy group and a propoxy group, an alkenoxy group such as a vinyloxy group and a propenoxy group, an acyloxy group such as an acetoxy group, and a methylethylketoxime group. A ketooxyimino group, an aminoxy group,
Examples include an amino group and an amide group. When X is a hydroxyl group, m = 1 is preferable, and when X is a hydrolyzable group, m = 2.
Or 3 is preferred.

The viscosity at 25 ° C. of the organopolysiloxanes of the above formulas (2) and (3) is 200 to 1,000,
000 cs, especially 10,000- from the viewpoint of physical properties and workability
A range of 500,000 cs is preferred.

The organopolysiloxanes of the above formulas (1), (2) and (3) may be linear or have a branched structure. In addition, RSiO _3/2 (where R
Is the same as described above, and the oxygen atom forms a siloxane bond with another silicon atom), and may have 1 to 5, particularly 1 to 3, especially 1 or 2 Is preferred. The branched structure represented by RSiO _3/2 is 5
When the number of base oils exceeds 1, the base oil may not be stably obtained due to pulping (hardening locally), and when it is less than 1, the effect may not be obtained.

The method for introducing the above-mentioned RSiO _3/2 unit is not particularly limited. For example, the compound of the above formula (1) or (2) or (3) and the source of the T unit are represented by the following formula ( 4) or the required amount of the compound of the formula (5), water and potassium hydroxide are added in a required amount, and polymerization is carried out at about 130 ° C. for 6 to 8 hours in a vessel capable of performing a pressure reaction of about 2 atm. To obtain an oil by neutralization with triethylamine, cyclotrisiloxane and a necessary amount of water, T
As a unit source, a compound of the following formula (4) or (5) is polymerized at about 130 ° C. for 6 to 8 hours in a vessel capable of performing a pressure reaction of about 2 atm using rubidium hydroxide as a catalyst, and neutralized with triethylamine. And the like.

[0036]

Embedded image (In the formula, R ² has the same meaning as R.)

Next, examples of the inorganic filler as a filler include fumed silica, calcined silica, precipitated silica, silica obtained by treating these with silane, silazane, siloxane, etc., and a treating agent (silane, carboxylic acid, 50 ° C. or more Calcium carbonate such as colloidal calcium carbonate, calcined clay, talc, titanium oxide, zinc oxide, alumina, boron nitride, carbon, quartz powder and the like. Can be

The method of the present invention is more effective in crushing the surface of an inorganic filler containing -OH groups on the surface with untreated calcium carbonate or raw filler than in the case where an inorganic filler having a low water content is blended. When water is allowed to coexist, the effect is particularly exhibited by using a high-frequency output device. Therefore, as the filler, a raw silica filler, calcium carbonate not treated or treated with a treating agent, particularly colloidal calcium carbonate having a large specific surface area, and titanium oxide having photocatalytic ability are preferably used.

The base compound may contain a dispersant and the like, if necessary, in addition to the above-mentioned organopolysiloxane and inorganic filler.

In the present invention, when a base compound is produced using the above-mentioned organopolysiloxane and inorganic filler, a high-frequency wave is applied to the organopolysiloxane and / or inorganic filler component or the obtained base compound. The output device performs a process of irradiating high frequency.

Here, first, as the production apparatus used for producing the organopolysiloxane composition in the present invention,
Any device can be used as long as it can be mixed in a state where moisture is shut off, and any of the above-described conventionally used devices can be used. In addition, it is preferable that the manufacturing apparatus be an apparatus capable of removing harmful substances, moisture, and the like generated under reduced pressure when high-frequency irradiation is performed by a high-frequency output device as described later. As such a production device, a device having a twin screw extruder and capable of defoaming under reduced pressure is preferable, and the material is preferably a nonmetal such as ceramics.

As the high-frequency output device (microwave) used in the method for producing the organopolysiloxane composition of the present invention, various types can be used, but it is generally recognized as a microwave having a high frequency of about 900 to 9,000 MHz. A device capable of outputting the frequency of the specified frequency is preferable.

In the present invention, the compound that can be removed from the composition can be changed depending on the frequency.
The device is preferably of variable output. Also,
The high-frequency output device can be installed in the manufacturing device as needed.

In the present invention, the treatment of irradiating the organopolysiloxane and / or the inorganic filler component or the obtained base compound with a high frequency using a high-frequency output device is not particularly limited in the type of the component to be treated and the irradiation timing. Not
The irradiation time can be appropriately determined depending on the irradiation purpose, but the irradiation time is usually in the range of 3 to 60 minutes, particularly in the range of 5 to 30 minutes.

Here, the timing of irradiating the high frequency is
Irradiation may be performed in any step because it differs depending on the type of filler and application. If you want to proceed the surface treatment at the same time, necessary organopolysiloxane and inorganic filler, dispersant,
After the base compound is manufactured by adding water or the like, the high-frequency output device may be irradiated.

In the case of using a filler (particularly calcium carbonate or the like) in which water is present as water of crystallization in the powder, it is difficult to remove water after the base compound is prepared. After irradiating with a high frequency, it is preferable to prepare a base compound.

For example, when blending an inorganic filler containing water such as to retain water of crystallization, the inorganic filler is irradiated beforehand with a high-frequency wave using a high-frequency output device, and an organopolysiloxane or the like is blended therewith to form a base compound. First, an inorganic filler is mixed with a high-frequency output device (2,450
While irradiating (megahertz) for several minutes, water of crystallization is taken out of the inorganic filler. At the same time, water was removed by degassing, and after the moisture was shut off, an organopolysiloxane irradiated with a high-frequency output device for several minutes was obtained in the same manner, and then mixed and kneaded to obtain a base compound. Can be obtained. At that time, a thixocontrol agent may be added as necessary.

When the inorganic filler is irradiated with high frequency by the high-frequency output device, the shape and the irradiation position of the inorganic filler can be appropriately adjusted. In addition, the irradiation effect in the microwave depends on the thickness of the inorganic filler, and it is basically preferable to irradiate in a state where the inorganic filler is thin.

When the organopolysiloxane is reacted with the terminal of the organopolysiloxane to produce it in one pot, the base oil whose terminal is blocked with a hydroxyl group is mixed with a hydrolyzable silane or siloxane and irradiated with high frequency by a high frequency output device. The terminal may be sealed by irradiating the inorganic filler with a high frequency by a high frequency output device in a pre-process or a post-process to remove water, and then use the base compound as a base compound. At this time, a non-sag agent may be added to control thixo.

In the present invention, a cross-linking agent, a catalyst, various property improving agents and the like are added to the base compound obtained as described above, if necessary, to obtain the desired organopolysiloxane composition. Can be.

Here, the addition-curable silicone composition comprises:
The target composition can be obtained by using an organohydrogensiloxane having two or more Si—H bonds as a cross-linking agent and adding a platinum compound and a control agent.
In this case, the organohydrogensiloxane has its S
It is preferable to add i-H groups in an amount of 0.5 to 2.0 with respect to the vinyl groups of the organopolysiloxane of the base polymer.

The peroxide-cured silicone composition is prepared by adding an organic peroxide or the like as a crosslinking agent to a siloxane composition containing an alkenyl group in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of an organopolysiloxane as a base polymer. It can be added and cured.

The condensation-curable silicone composition is also used as a crosslinking agent in the following general formula (6): R ¹ _c SiX _4-c (6) (where X is a hydrolyzable group, R ¹ is unsubstituted or halogen) It is a substituted monovalent hydrocarbon group. C is an integer of 0 to 2.) or a partial hydrolyzate thereof.

In the above formula (6), examples of the hydrolyzable group of X are the same as those exemplified in formulas (2) and (3). The organic group R ¹ other than the hydrolyzable group bonded to the silicon atom preferably has 1 to 8 carbon atoms, for example, a methyl group, an ethyl group, a propyl group,
Alkyl group such as butyl group, alkenyl group such as vinyl group,
A monovalent hydrocarbon group such as an aryl group such as a phenyl group, a chloromethyl group in which part or all of the hydrogen atoms bonded to these carbon atoms have been substituted with halogen atoms, 3,3,3-
And a trifluoropropyl group. Among these, a methyl group, a phenyl group, and a vinyl group are particularly preferable. By using these groups, a cured product having a high curing rate can be obtained.

Examples of the organosilane of the formula (6) include vinyltrimethoxysilane, vinyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, and tetramethoxysilane. , Tetraethoxysilane, vinyltri (isopropenoxy) silane,
Phenyltri (isopropenoxy) silane, propyltri (isopropenoxy) silane, tetra (isopropenoxy) silane, 3,3,3-trifluoropropyltri (isopropenoxy) silane, methyltri (2-butenoxy) silane and the like. Hydrolysates can also be used.

The compounding amount of the condensation type curing agent is preferably 0.5 to 20 parts by weight, more preferably 1 to 8 parts by weight based on 100 parts by weight of the organopolysiloxane of the formulas (2) and (3). is there. If the amount of the curing agent is less than 0.5 part by weight, a cured product having excellent elasticity and mechanical strength may not be obtained, and if it exceeds 20 parts by weight, the cured product may become brittle. In the method of the present invention, the amount of the curing agent can be reduced as compared with the case where the compounding is performed by a usual method.

Further, optional components can be added to the organopolysiloxane composition as needed, as long as the effects of the present invention are not impaired. Examples of the optional component include a condensation catalyst, a fungicide, a colorant, a bulking agent, an adhesion aid (silane coupling agent), a flame retardant, a heat resistance improver, an antibacterial agent, and a fragrance. By adding any optional component, a higher performance organopolysiloxane composition can be obtained.

[0058]

According to the process for producing the organopolysiloxane composition of the present invention, the method of the present invention can be applied to a case where an inorganic filler having water of crystallization or an inorganic filler used for promoting surface treatment by coexisting with water is blended. Also, with the addition type, heat vulcanization type composition, there is little return over time, and a composition excellent in curability that does not discolor because of a small nitrogen content is obtained.
In the condensation type composition, it is possible to reduce the amount of the curing agent because water can be sufficiently removed, and it is also possible to produce an oil or the like that effectively blocks the terminal, and to obtain a particularly excellent condensation type composition. It is suitable. Therefore, according to the method of the present invention, a high quality organopolysiloxane composition can be industrially advantageously produced.

[0059]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, Comparative Examples and Reference Examples, but the present invention is not limited to the following Examples. In addition, in the following examples, a part shows a weight part.

A base compound was prepared as shown below, and a silicone rubber composition was obtained by the following method.

Example 1 Colloidal calcium carbonate having an average particle size of 0.03 μm and surface-treated with rosin acid at 1.5% was subjected to high frequency (2,450 MHz) by a high frequency output device.
Was irradiated for 3 minutes while removing the steam with a vacuum pump. α,
100 parts of ω-dihydroxydimethylpolysiloxane (viscosity of 20,000 cs at 25 ° C.), 0.02 parts of polypropylene glycol, and 60 parts of calcium carbonate treated by a high-frequency output device are mixed and stirred for 10 minutes with a Shinagawa mixer under the cutoff of moisture. Thus, a base compound (base compound 1) was obtained.

Example 2 60 parts of colloidal calcium carbonate obtained in the same manner as in Example 1 and 100 parts of dimethylpolysiloxane terminated at 25 ° C. (viscosity of 20,000 cs) with a methoxy group were mixed with Shinagawa formula The mixture was mixed and stirred with a mixer for 10 minutes while blocking moisture, to obtain a base compound (base compound 2).

Example 3 α, ω-dihydroxydimethylpolysiloxane (viscosity at 25 ° C. 50,000 cs) 10
0 parts and 0.02 parts of colloidal calcium carbonate and polyethylene glycol having an average particle size of 0.06 μm and surface-treated with 2.5% of stearic acid were mixed and stirred by a Shinagawa mixer for 10 minutes. The mixture was irradiated with high frequency (2,450 MHz) for 5 minutes with a high frequency output device while further mixing and stirring, and a base compound (base compound 3) was obtained while removing steam with a vacuum pump.

Example 4 α, ω-dihydroxydimethylpolysiloxane (viscosity at 25 ° C. 20,000 cs) 10
0 parts and 10 parts of surface-treated dry silica R-972 (manufactured by Nippon Aerosil Co., Ltd.), polyethylene glycol 0.1 part.
02 parts were mixed and stirred with a Shinagawa mixer for 10 minutes. The mixture was irradiated with high frequency (2,450 MHz) by a high frequency output device for 8 minutes while further mixing and stirring, and a base compound (base compound 4) was obtained while removing steam with a vacuum pump.

Example 5 α, ω-dihydroxydimethylpolysiloxane (viscosity of 20,000 cs at 25 ° C.) 10
0 parts, 15 parts of dry silica AEROSIL 300 (manufactured by Nippon Aerosil Co., Ltd.), and trimethylsilyldimethylamine 2
The mixture was mixed and stirred with a Shinagawa mixer for 15 minutes. The mixture was irradiated with high frequency (2,450 MHz) for 10 minutes with a high frequency output device while further mixing and stirring, and a base compound (base compound 5) was obtained while removing the reaction fraction with a vacuum pump.

Example 6 α, ω-dihydroxydimethylpolysiloxane (viscosity of 20,000 cs at 25 ° C.) 10
0 parts and 10 parts of tetramethoxysilane were mixed and stirred for 3 minutes, and then high-frequency (2,450 MHz) was irradiated for 15 minutes with a high-frequency output device while further mixing and stirring, and the reaction fraction was removed by a vacuum pump. Example 1
Colloidal calcium carbonate 60 obtained in the same manner as
And 0.02 part of polypropylene glycol in a state where moisture was shut off, and mixed and stirred with a Shinagawa mixer for 10 minutes to obtain a base compound (base compound 6).

Example 7 Oil 1 having vinyl dimethylpolysiloxane terminated (viscosity of 10,000 cs at 25 ° C.)
00 parts, 40 parts of silica powder (Erosil 300, manufactured by Nippon Aerosil Co., Ltd.) having a specific surface area of 300 m ² / g, 8 parts of trimethylsilyldiethylamine and 2 parts of water were added to a kneader mixer, and homogenous mixing was performed for 30 minutes. Thereafter, while further mixing and stirring, a high frequency (2,450
(Megahertz) for 15 minutes, the reaction fraction was removed by a vacuum pump, and the base compound (base compound 7)
I got

Example 8 Oil 1 having a terminal vinyldimethylpolysiloxane (viscosity at 25 ° C. of 10,000 cs)
00 parts, 40 parts of silica powder having a specific surface area of 300 m ² / g (Erosil 300, manufactured by Nippon Aerosil Co., Ltd.) and 8 parts of trimethylsilyldimethylamine were added to a kneader mixer, and homogenous mixing was performed for 30 minutes. Thereafter, high frequency (2,450 MHz) was irradiated for 30 minutes with a high frequency output device while further mixing and stirring, and the reaction fraction was removed with a vacuum pump.
A base compound (base compound 8) was obtained.

Example 9 Oil 1 having a terminal vinyldimethylpolysiloxane (viscosity of 10,000 cs at 25 ° C.)
00 parts, 40 parts of dry silica powder (Erosil 200, manufactured by Nippon Aerosil Co., Ltd.) having a specific surface area of 200 m ² / g, 8 parts of hexamethyldisilazane and 2 parts of water were continuously fed to a continuous kneading extruder having a twin screw. And mix homogeneously with 1
Minutes. Further, a plurality of continuous kneading extruders are connected in a row after the kneading machine, and a silicone base homogenized by the continuous kneading machine is passed through the extruder, and a high frequency output device (2,450 MHz) is used. To obtain a base compound (base compound 9). At this time, a vacuum chamber was installed in each of the continuous kneaders.

Example 10 30 parts of titanium oxide (Taipec ST-11, manufactured by Ishihara Sangyo Co., Ltd.) having photocatalytic activity were irradiated with high frequency (2,450 MHz) for 15 minutes by a high frequency output device, and then moisture was removed. In a cut-off state, 100 parts of α, ω-dihydroxydimethylpolysiloxane (viscosity at 25 ° C. of 20,000 cs) was distilled off under vacuum with a Shinagawa mixer for 15 minutes under moisture cut-off to obtain a base compound (base compound). 10) was obtained.

Comparative Example 1 Forty parts of colloidal calcium carbonate having an average particle size of 0.03 μm and surface-treated with 1.5% rosin acid were mixed with α, ω-dihydroxydimethylpolysiloxane (viscosity at 25 ° C. 20,000 cs) 100 And 0.02 part of polypropylene glycol were mixed and stirred for 15 minutes with a Shinagawa mixer under a moisture cutoff, and the base compound (base compound 1) was removed while removing a distillate with a vacuum pump.
1) was obtained.

Comparative Example 2 Colloidal Calcium Carbonate 6
0 parts and 100 parts of dimethylpolysiloxane (viscosity of 20,000 cs at 25 ° C.) whose ends are blocked with a methoxy group are mixed and stirred for 15 minutes with a Shinagawa mixer under a moisture-shielded condition, to give a base compound (base compound 12). Obtained.

Comparative Example 3 α, ω-dihydroxydimethylpolysiloxane (viscosity at 25 ° C. 50,000 cs) 10
0 parts, 60 parts of colloidal calcium carbonate having an average particle size of 0.06 μm and a surface treatment of 2.5% with stearic acid, and 0.02 part of polyethylene glycol were mixed in a Shinagawa mixer with 1 part.
The mixture was stirred for 5 minutes, and a base compound (base compound 13) was obtained while removing a fraction with a vacuum pump.

Comparative Example 4 α, ω-dihydroxydimethylpolysiloxane (viscosity of 20,000 cs at 25 ° C.) 10
0 parts and 10 parts of surface-treated dry silica R-972 (manufactured by Nippon Aerosil Co., Ltd.), polyethylene glycol 0.1 part.
Mix and stir 02 parts with Shinagawa mixer for 15 minutes,
While removing the reaction fraction with a vacuum pump, a base compound (base compound 14) was obtained.

Comparative Example 5 α, ω-dihydroxydimethylpolysiloxane (viscosity of 20,000 cs at 25 ° C.) 10
0 parts, 15 parts of dry silica AEROSIL 300 (manufactured by Nippon Aerosil Co., Ltd.), and trimethylsilyldimethylamine 2
The mixture was mixed and stirred with a Shinagawa mixer for 15 minutes, and the base compound was mixed and stirred for 15 minutes, and a base compound (base compound 15) was obtained while removing the reaction fraction with a vacuum pump.

Comparative Example 6 α, ω-dihydroxydimethylpolysiloxane (viscosity of 20,000 cs at 25 ° C.) 10
0 parts and 10 parts of tetramethoxysilane were charged into a planetary mixer, mixed and stirred at 25 ° C. for 15 minutes in a state where moisture was shut off, and further, 60 parts of colloidal calcium carbonate was added.
0.02 parts of polypropylene glycol are mixed in a state where moisture is shut off, and mixed and stirred with a Shinagawa mixer for 15 minutes.
Vacuum mixed. The fraction was taken to obtain a base compound (base compound 16).

Comparative Example 7 Forty parts of colloidal calcium carbonate having an average particle size of 0.01 μm and surface-treated with 1.5% rosin acid (dicarboxydehydroabietic acid) were charged into a planetary mixer, and heated at 130 ° C. to 80 parts. Heat treatment was performed for minutes. Then, α, ω-dihydroxydimethylpolysiloxane (viscosity of 20,000 c at 25 ° C.)
60 parts of the oil (s) was added, mixed for 30 minutes, and further mixed under reduced pressure for 20 minutes. The heating and vacuum processing time spent for stabilizing the physical properties other than the homogenization of the base material and the filler was 100 minutes in total. Thus, a base compound (base compound 17) was obtained.

Comparative Example 8 Oil 1 having a vinyldimethylpolysiloxane terminal (viscosity of 10,000 cs at 25 ° C.)
00 parts, 40 parts of dry silica powder (Erosil 300, manufactured by Nippon Aerosil Co., Ltd.) having a specific surface area of 300 m ² / g, 8 parts of trimethylsilyldiethylamine and 2 parts of water were added to a kneader mixer, and homogenous mixing was performed for 2 hours. afterwards,
Further, a heating and vacuum treatment was performed at 160 ° C. for 4 hours to produce a silicone base. The heating and vacuum processing time spent for stabilizing the physical properties other than the homogenization of the base material and the filler was 240 minutes or more in total including the time for raising the temperature. Thus, a base compound (base compound 18) was obtained.

[Comparative Example 9] Oil 1 having a terminal vinyl dimethylpolysiloxane (viscosity of 10,000 cs at 25 ° C)
00 parts, 40 parts of dry silica powder (Erosil 300, manufactured by Nippon Aerosil Co., Ltd.) having a specific surface area of 300 m ² / g, 8 parts of trimethylsilyldimethylamine and 2 parts of water were added to a kneader mixer, and homogenous mixing was performed for 2 hours. . The heating and vacuum treatment time spent for stabilizing the physical properties other than the homogenization with the base material was 0 minutes in total. Thus, a base compound (base compound 19) was obtained.

Comparative Example 10 100 parts of oil having vinyl dimethylpolysiloxane terminal (viscosity of 10,000 cs at 25 ° C.) and dry silica powder having a specific surface area of 200 m ² / g (Aerosil 200, manufactured by Nippon Aerosil Co., Ltd.) 40 Department,
8 parts of silazane and 2 parts of water were continuously added to a continuous kneading extruder having a twin screw, and homogenous mixing was performed for 1 minute. Further, a plurality of continuous kneading extruders were connected in a row in succession to the kneading machine, and the inside was passed through a silicone base homogenized by the continuous kneading machine and maintained at the following residence time and temperature. At this time, a vacuum chamber was installed in each of the continuous kneaders. The temperature and residence time in the continuous kneader are 2
50 ° C., 15 minutes. Thus, a base compound (base compound 20) was obtained.

Comparative Example 11 Dry Silica Powder (Erosil 200, manufactured by Nippon Aerosil Co., Ltd.) 40 having 100 parts of oil as vinyl dimethylpolysiloxane terminated (viscosity of 10,000 cs at 25 ° C.) and a specific surface area of 200 m ² / g Department,
8 parts of silazane and 2 parts of water were continuously added and homogenously mixed for 1 minute. The temperature in the continuous kneader was set to 250 ° C. at a 50% portion from the outlet of the continuous kneader. Heating time spent for stabilization of physical properties other than homogenization of base material and filler is 3
It was 0 seconds. Thus, a base compound (base compound 21) was obtained.

Comparative Example 12 α, ω-dihydroxydimethylpolysiloxane (having a viscosity at 25 ° C.) of 30 parts of titanium oxide having photocatalytic ability (Taipec ST-11, manufactured by Ishihara Sangyo Co., Ltd.) was cut off from moisture. 20,000 cs) 10
The 0 part was distilled off in vacuo with a Shinagawa mixer under a cutoff of moisture for 15 minutes to obtain a base compound (base compound 22).

Next, a curing agent and the like were added to the above-mentioned base compound and blended by the following method to obtain a silicone rubber composition, and further a cured product thereof was obtained. The obtained composition and cured product were evaluated by the following methods. The results are shown in Tables 1 to 3. Preparation of silicone rubber composition and cured product: The type of curing agent used in this case was a condensation type (Examples 1, 3, 4, 5, 10, Comparative Examples 1, 4, 5, 7, 1) in order to keep the conditions constant.
In 2), 6 parts of trimethylethylketoxime silane and 0.1 part of dibutyltin dilaurate were added to 100 parts of the base compound, and cured at 25 ° C. for 7 days to obtain a sheet having a thickness of 2 mm.

For the type whose ends are blocked with a methoxy group (Examples 2, 6 and Comparative Examples 2, 3, 6), 6 parts of methyltrimethoxysilane and 0.1 part of dibutyltin dilaurate are added to 100 parts of the base compound. One part was added and cured at 25 ° C. for 7 days to obtain a sheet having a thickness of 2 mm.

In the addition type (Examples 7, 8, 9 and Comparative Examples 8, 9, 10, 11), 4 parts of a crosslinking agent of the following formula was added to 100 parts of a base compound having the following structure, and a control agent was used. After adding 0.5 part of ethynylcyclohexanol and 0.2 part of a platinum complex, the mixture was cured at 120 ° C. for 1 hour.

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The physical properties of the obtained cured product were measured according to JIS A575.
8 was measured. The hardness and the storage state were evaluated as described below. The results are shown in Tables 1 to 3. Hardness: A sheet having a thickness of 2 mm was cured at 25 ° C. for 7 days, and the curability was measured according to JIS A5758. Storage state: The condensation type was filled in a 330 ml polycartridge, and the storage state after 55 days at 80 ° C. and 55% was observed.

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[Table 1]

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[Table 2]

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[Table 3]

Reference Example 1 α, ω-dihydroxydimethylpolysiloxane (viscosity at 25 ° C. of 20,000 cs) 1
After 00 parts and 10 parts of tetramethoxysilane were mixed and stirred for 1 minute with a Shinagawa mixer under a cutoff of moisture, the mixture was irradiated with high frequency (2,450 MHz) for 15 minutes by a high frequency output device to remove a fraction.

[Reference Example 2] α, ω-dihydroxydimethylpolysiloxane (viscosity at 25 ° C. of 20,000 cs) 1
00 parts, 10 parts of tetramethoxysilane and 0.5 parts of lithium hydroxide were mixed in a Shinagawa-type mixer in an amount of 1
After mixing and stirring for 2 minutes, high frequency (2, 4
(50 MHz) for 15 minutes to remove the distillate.

Reference Example 3 α, ω-dihydroxydimethylpolysiloxane (viscosity at 25 ° C. of 20,000 cs) 1
After mixing and stirring 1 part of 00 parts and 10 parts of methyltrimethoxysilane with a Shinagawa mixer under a cutoff of moisture for 1 minute, the mixture was irradiated with high frequency (2,450 MHz) for 15 minutes and 30 minutes by a high frequency output device, and fractionated. Was removed.

Reference Example 4 α, ω-dihydroxydimethylpolysiloxane (viscosity at 25 ° C. of 20,000 cs) 1
00 parts, 10 parts of methyltrimethoxysilane and 0.5 part of lithium hydroxide were mixed and stirred for 1 minute with a Shinagawa mixer under the cutoff of moisture, and then a high-frequency output device was used to apply high frequency (2,450 MHz) to 15 parts. For 30 minutes and 30 minutes to remove the fraction.

Reference Example 5 α, ω-dihydroxydimethylpolysiloxane (viscosity at 25 ° C. of 20,000 cs) 1
00 parts and 10 parts of tetramethoxysilane were mixed and stirred at 25 ° C. with a Shinagawa mixer under a cutoff of moisture. Samples were taken at each passage of time to remove distillates.

Reference Example 6 α, ω-dihydroxydimethylpolysiloxane (viscosity at 25 ° C. of 20,000 cs) 1
00 parts, 10 parts of tetramethoxysilane and 0.5 parts of lithium hydroxide were mixed with a Shinagawa mixer under a moisture cutoff of 25 parts.
The mixture was stirred at ℃. Samples were taken at each passage of time to remove distillates.

Reference Example 7 α, ω-dihydroxydimethylpolysiloxane (viscosity at 25 ° C. of 20,000 cs) 1
00 parts and 10 parts of methyltrimethoxysilane were mixed and stirred with a Shinagawa mixer at 25 ° C. while blocking moisture. Samples were taken at each passage of time to remove distillates.

Reference Example 8 α, ω-dihydroxydimethylpolysiloxane (viscosity at 25 ° C. of 20,000 cs) 1
00 parts, 10 parts of methyltrimethoxysilane, and 0.5 part of lithium hydroxide were mixed and stirred at 25 ° C. with a Shinagawa mixer under a moisture cutoff, and samples were taken at each time to distill fractions. Removed.

Reference Example 9 α, ω-dihydroxydimethylpolysiloxane (viscosity at 25 ° C. of 20,000 cs) 1
00 parts and 10 parts of methyltrimethoxysilane were mixed and stirred at 150 ° C. with a Shinagawa mixer under a cutoff of moisture. Samples were taken at each passage of time to remove distillates.

Reference Example 10 α, ω-dihydroxydimethylpolysiloxane (viscosity at 25 ° C. of 20,000 cs)
After 100 parts and 10 parts of tetramethoxysilane were mixed and stirred in a pressure vessel under the conditions of 150 ° C. and 2 atm under the exclusion of moisture, samples were collected at each elapse of time and fractions were removed.

The oil obtained in the above reference example was subjected to a test for confirming the increase in the terminal blocking ratio with tetraisopropoxytitanium by the following method. Table 4 shows the results. End-blocking thickening confirmation test method: As a method for measuring the end-blocking rate, theoretically, when tetraisopropoxytitanium is added to end-blocked trimethoxy or dimethoxydimethylpolysiloxane oil and the end-blocking rate is measured by Karl Fischer, It has been confirmed that the phenomenon of thickening can be suppressed when 90% or more is blocked. As a blank, an oil having terminal trimethoxydimethylpolysiloxane (viscosity at 25 ° C. of 20,000 cs) was used.

The results of the thickening test were measured at 15 minutes, 30 minutes, 1 hour, 6 hours, 12 hours, and 24 hours.

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[Table 4]

──────────────────────────────────────────────────続 き Continuing on the front page (51) Int.Cl. ⁶ Identification symbol FI C08L 83/04 C08L 83/04 (72) Inventor Kenichi Kimura 2-13-1, Isobe, Annaka-shi, Gunma Shin-Etsu Chemical Co., Ltd. Inside Gunma Office

Claims (5)

[Claims] When producing a base compound comprising an organopolysiloxane and an inorganic filler as essential components, the organopolysiloxane and / or the inorganic filler component,
Alternatively, a process for irradiating the obtained base compound with high frequency using a high frequency output device is performed. 2. The method according to claim 1, wherein high-frequency irradiation is performed on the inorganic filler. 3. The production method according to claim 1, wherein the inorganic filler is at least one selected from calcium carbonate, silica, and titanium oxide having photocatalytic ability. 4. The method according to claim 1, wherein the organopolysiloxane composition is a silicone rubber composition. 5. The method according to claim 4, wherein the organopolysiloxane composition is a moisture-curable silicone rubber composition.