JP3532002B2 - Foamable polyorganosiloxane composition and flame-retardant foam - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel foamable polyorganosiloxane composition, and more specifically, it has excellent foam stability, high expansion ratio, low apparent density and excellent flame retardancy. And a foamable polyorganosiloxane composition capable of forming a foam having the same. The present invention also relates to a flame-retardant foam obtained by foaming and curing such a composition.

[0002]

2. Description of the Related Art Various types of foamable liquid polyorganosiloxane compositions are already known. The foaming mechanism is to obtain a sponge-like cured product by curing the polyorganosiloxane composition having a curing mechanism involving a dehydrogenation reaction during curing and taking in hydrogen gas generated at that time into the system. However, since the foaming agent is not separately added, the composition is simple, and there are many advantages such as no generation of toxic decomposition products as in the case of using the foaming agent. Therefore, in addition to the heat resistance, cold resistance and weather resistance inherent to polysiloxane, it is easy to handle, and it is easy to obtain a flame-retardant material. Insulation, sound absorbing material,
Widely used as a vibration isolator.

The following are known as such foamable liquid polyorganosiloxane composition.

JP-A-51-46352 discloses that a silanol group-containing polyorganosiloxane and a polyorganohydrogensiloxane are cured with a platinum-based catalyst.
A foamable polyorganosiloxane composition having a mechanism of forming a foam by hydrogen gas generated at that time is disclosed. Further, proposals have been made to improve this foaming mechanism. That is, in JP-A-4-88034, the silanol group-containing polyorganosiloxane described above is
Expandable polyorgano using a linear polyorganosiloxane having hydroxyl groups bonded to silicon atoms at both ends, a linear polyorganosiloxane having hydroxyl groups bonded only to the intermediate silicon atom, and a branched polyorganosiloxane containing silanol groups A siloxane composition is disclosed, and Japanese Patent Application Laid-Open No. 5-1169 discloses a polyorganosiloxane composition in which the above and are used in combination with an alcohol.

In JP-A-54-135865, a rubber-like elastic material is crosslinked by a reaction mechanism in which an alkenyl group-containing polyorganosiloxane and a polyorganohydrogensiloxane are hydrosilylated in the presence of a platinum catalyst. Disclosed is a foamable polyorganosiloxane composition in which water is allowed to coexist and a foam is formed by hydrogen gas generated by a reaction between the polyorganohydrogensiloxane and water when obtained. As an improved foaming mechanism, JP-A-5-70692 discloses a foamable polyorganosiloxane composition in which a liquid alcohol is used instead of water and a fluorinated silicone cell stabilizer is blended.

Japanese Unexamined Patent Publication No. 57-180641 discloses a foamable polyorganosiloxane composition containing a silanol group-containing polyorganosiloxane, a polyorganohydrogensiloxane and an aminoxy compound.

In all of these foamable polyorganosiloxane compositions, the bubbles that take in the generated hydrogen gas become large and the foam-stabilizing property is poor, and the apparent density of the resulting foam is lowered. If you generate a lot of hydrogen gas,
There is a problem that the generated gas cannot be fully taken in, the foam is easily broken, and a low-density uniformly foamed product cannot be obtained. Further, since the flame retardancy is not sufficient, there is a limitation in using it as a cushioning material for aircrafts, vehicles, etc., as a heat insulating material and a sound absorbing material for a portion of a house that requires high flame retardancy.

It is known that the use of a platinum catalyst causes flame retardancy in silicone rubber due to the presence of the catalyst remaining after curing. It is also known to use flame retardants such as iron oxide, aluminum hydroxide, manganese carbonate, zinc carbonate, carbon black, azo compounds, and triazole compounds in order to impart flame retardancy to silicone rubber. However, even if such a flame retardant is applied to a foam obtained from an addition reaction type polyorganosiloxane composition, a satisfactory flame retardant foam has not been obtained yet.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a foamable polyorganosiloxane which is excellent in foam control, has a high expansion ratio, a low apparent density, and a foam having excellent flame retardancy. It is to provide a composition. Another object of the present invention is to provide a polyorganosiloxane foam which is obtained by foaming and curing such a composition, has a low density, is excellent in foam control and has flame retardancy.

[0010]

The inventors of the present invention have conducted extensive studies to achieve the above-mentioned object, and as a result, in the foaming mechanism for allowing alcohol to coexist in the hydrosilylation reaction, the alkenyl group-containing polyorgano which is the base polymer has been found. It is possible to achieve the purpose by allowing siloxane to have a phenyl group bonded to a silicon atom and selecting carbon black and titanium oxide as flame retardants that also serve as fillers and by using specific amounts thereof in combination. The present invention has been completed and the present invention has been completed.

That is, the expandable polyorganosiloxane composition of the present invention comprises (A) the general formula:

[Chemical 3] (In the formula, R ¹ represents an alkenyl group, R ² may be the same or different from each other, and represents a substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond, and a is Represents an integer of 1 or 2, b represents an integer of 0 to 2, a
+ B is an integer of 1 to 3) and an alkenyl group-containing polyorganosiloxane having at least two units represented by the formula (B) and having at least one phenyl group bonded to a silicon atom in the molecule; ) General formula:

[Chemical 4] (In the formula, R ^{3 s} may be the same or different from each other, and are substituted or unsubstituted 1 having no aliphatic unsaturated bond.
Represents a valent hydrocarbon group, c represents an integer of 0 to 2, d represents an integer of 1 or 2, and c + d is an integer of 1 to 3). Polyorganohydrogensiloxane, an amount in which the amount of hydrogen atoms bonded to silicon atoms per alkenyl group of component (A) is 3 to 1,000; (C) catalyst selected from platinum or platinum compound; A)
Amount of platinum atom of 0.1 to 1,000 ppm by weight based on the components; (D) 1 to 12 carbon atoms having no aliphatic unsaturated bond
Of the monohydric or polyhydric alcohol, the number of hydroxyl groups per hydrogen atom bonded to the silicon atom of the component (B) is 0.01
10 to 10 parts; (E) 0.1 to 20 parts by weight of carbon black; and (F) 0.1 to 20 parts by weight of titanium dioxide.

The component (A) used in the present invention has a general formula:

[Chemical 5] An alkenyl having at least two units represented by the formula (in the formula, R ¹ , R ² , a and b are as described above) and having at least one phenyl group bonded to a silicon atom in the molecule. It is a group-containing polyorganosiloxane. The component (A) is the base polymer of the composition of the present invention, and the alkenyl group bonded to the silicon atom is crosslinked by the hydrosilylation reaction with the hydrogen atom bonded to the silicon atom in the component (B), It is a component that imparts strength to the foam by cooperating with other components.

The component (A) is an alkenyl group-containing polyorgano having at least two units represented by the above formula (I) in the molecule and at least one phenyl group bonded to a silicon atom in the molecule. The molecular structure of siloxane is not particularly limited, and those having a linear, cyclic, or branched siloxane skeleton may be used, but they are easy to synthesize and have excellent rubber elasticity and mechanical properties in the composition. From the viewpoint of imparting specific properties, it is preferable to use a straight chain type or a straight chain and branched chain alkenyl group-containing polyorganosiloxane in combination. The degree of polymerization is not particularly limited, but is 10 to 3,
000 is preferable, and 50 to 2,000 is more preferable. If the degree of polymerization is less than 10, the mechanical properties of the foam obtained by curing are not sufficient, and if it exceeds 3,000,
Handling in the uncured state becomes difficult.

Examples of R ¹ include vinyl, allyl, butenyl and the like, and a vinyl group is preferred because of easy synthesis. R ² is an alkyl group such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl; a cycloalkyl group such as cyclohexyl; an aralkyl group such as 2-phenylethyl, 2-phenylpropyl; phenyl, etc. Examples of the aryl group are as follows; and substituted monovalent hydrocarbon groups such as chloromethyl, 3,3,3-trifluoropropyl, and chlorophenyl. Preferably there is. Each of a and b is as described above, and a is preferably 1 because of easy synthesis.

The unit represented by the formula (I) may be present at either the molecular end or the molecular middle, but it is necessary to impart good mechanical properties to the foam obtained by curing. ,
At least a part of it is at the molecular end, for example R ¹ R ² ₂ S
It is preferably present in a form such as iO _1/2 units.

In the siloxane unit other than the unit represented by the formula (I) in the component (A), the organic groups bonded to the silicon atom may be the same or different, and R ²
Examples of monovalent substituted or unsubstituted hydrocarbon groups similar to those exemplified as, and easy synthesis, heat resistance,
Since it imparts the characteristics of polyorganosiloxane such as cold resistance to the cured foam, the phenyl group described later is excluded,
It is preferably a methyl group.

Due to the presence of the phenyl group bonded to the silicon atom, the surface tension of the component (A) becomes high, the generated hydrogen gas is retained in the system, and a large amount of fine and uniform particles are formed without breaking bubbles. It allows the formation of low density foams with various cells. At least one such phenyl group is present in one molecule of the component (A), and is preferably 0.1 to 30 mol%, more preferably 1 to 15 mol% in all organic groups bonded to silicon atoms. Occupy Such a phenyl group may be present in any of the unit represented by the formula (I), the other unit, or both, but since it is easy to synthesize, the phenyl group is (CH ₃ )
(C ₆ H ₅ ) SiO unit and / or (C ₆ H ₅ ) ₂
It is preferable that SiO units are present in the form of SiO units. If the amount of the phenyl group is less than 0.1 mol%, a fine and uniform foam having a large expansion ratio cannot be obtained, and if it exceeds 30 mol%, it is difficult to synthesize the polysiloxane used as the component (A). In addition, the compatibility with the component (B), which will be described later, deteriorates, so that the generated bubbles become coarse and the expansion ratio decreases rather.

The component (B) used in the present invention has a general formula:

[Chemical 6] (Wherein R ³ , c and d are as described above) is a polyorganohydrogensiloxane having at least 3 units in one molecule, wherein the hydrogen atom bonded to the silicon atom is the component (A). Contributes as a cross-linking agent to the hydrosilyl reaction with the alkenyl group in (D)
It has the function of reacting with the hydroxyl groups in the components to generate hydrogen gas.

The component (B) is not particularly limited in its molecular structure as long as it has three or more hydrogen atoms directly bonded to a silicon atom in one molecule, and may have a linear, cyclic or branched structure. Although those having a siloxane skeleton can be used,
For ease of synthesis, straight-chain or R ³ ₂ HSi
Polyorganohydrogensiloxanes consisting of O _1/2 units and SiO ₂ units are preferred.

R ^{3 s} may be the same or different from each other and are a substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond. Examples of such groups include methyl and ethyl. , Alkyl groups such as propyl, butyl, hexyl, octyl, decyl, dodecyl; cycloalkyl groups such as cyclohexyl; aryl groups such as phenyl; as well as chloromethyl, 3,3,3-trifluoropropyl, chlorophenyl Examples of such substituted monovalent hydrocarbon groups are preferable, and a methyl group is preferable from the viewpoint of ease of synthesis.

In the siloxane unit other than the unit represented by the formula (II) in the component (B), the organic groups bonded to the silicon atom may be the same or different, and R ³
Examples thereof are the same as, and a methyl group is preferable from the viewpoint of ease of synthesis.

The component (B) is blended in an amount of 3 to 1,000 hydrogen atoms bonded to silicon atoms, preferably 5 to 10 per alkenyl group of the component (A).
It is the amount of 0 pieces. When the number of hydrogen atoms is less than 3, the amount of hydrogen gas generated is small, and the amount of cross-linking is small, resulting in weak mechanical strength. When the number of hydrogen atoms is more than 1,000, changes in physical properties (particularly heat resistance) after curing become large. Is.

The component (C) used in the present invention is (A)
By the hydrosilylation reaction between the alkenyl group in the component and the hydrogen atom bonded to the silicon atom in the component (B), the composition of the present invention is cured and the hydrogen atom and the hydroxyl group in the component (D) are combined. Is a catalyst used for causing the dehydrogenative condensation reaction between the two. This includes platinum compounds such as chloroplatinic acid, complexes obtained from alcohol and chloroplatinic acid, platinum olefin complexes, platinum ketone complexes, platinum vinylsiloxane complexes; and alumina, platinum supported on silica carriers, platinum black, etc. A simple substance of platinum having a shape exemplified by can be used. The component (C) is used in a necessary amount as a catalyst, and this amount is 0.1 to 1,000 ppm in terms of platinum atom, based on the component (A).
The amount is preferably 0.5 to 200 ppm. 0.1
Below ppm, the catalyst concentration is low, resulting in insufficient foaming and curing. Further, even if the amount exceeds 1,000 ppm, there is no further effect, and since the component (C) contains a noble metal and is generally expensive, it is not economically preferable.

The component (D) used in the present invention is an alcohol having 1 to 12 carbon atoms and having no aliphatic unsaturated bond, may be monovalent or polyvalent, and the carbon chain may be linear or branched. However, it may have an aromatic ring to which a hydroxyl group is not directly bonded. Examples of such alcohol include monohydric alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, tert-butanol, n-octanol and benzyl alcohol; and ethylene glycol, propylene glycol and glycerin. Polyhydric alcohols such as trimethylolpropane are exemplified, and since the hydroxyl equivalent is large, addition of a small amount is effective, and the heat resistance and weather resistance of the cured foam are little affected, the number of carbon atoms is 1 ~
A monohydric alcohol having 4 or a dihydric alcohol having 2 to 4 carbon atoms is preferable.

The blending amount of the component (D) is such that one hydrogen atom bonded to a silicon atom in the component (B) is 0.01 to 10 hydroxyl groups in the component (D). , Preferably 0.1 to 5 pieces. When the number of hydroxyl groups is less than 0.01, the amount of hydrogen generated is small and a low density foam cannot be obtained. Further, when the number exceeds 10, the amount of hydrogen atoms bonded to the silicon atom in the component (B), which contributes to the cross-linking reaction between the components (A) and (B), is relatively reduced and the curing The mechanical strength of the resulting foam may be low, or the foam may break during foaming.

The component (E) used in the present invention contributes as a filler, and when used in combination with the component (F), the foam obtained by foaming and curing the composition of the present invention is flame retardant. Is a component that imparts. Carbon black is used as the component (E). Examples of the carbon black include furnace black, channel black, thermal black and the like depending on the production method, and gas black, oil black, acetylene black and the like depending on the difference in the starting materials, all of which are used in the present invention. can do. Since the dispersibility is good, the smoothness of the foam surface is maintained, and the flame-retardant effect is good, the particle size is preferably 1 μm or less. Considering the flame-retardant effect and economical efficiency, 1-100 nm is more preferable. preferable.

The blending amount of the component (E) is 100 parts of the component (A).
The amount is 0.1 to 20 parts by weight, and preferably 1.0 to 10 parts by weight. If it is less than 0.1 part by weight, it is impossible to impart excellent flame retardancy to the foam. Again 2
Even if it is blended in an amount of more than 0 parts by weight, there is no effect of further improving the flame retardancy, and the component (C) tends to be poisoned to impair the curability, which is not preferable.

The component (F) used in the present invention contributes as a filler, and when used in combination with the component (E), the foam obtained by foaming and curing the composition of the present invention is flame retardant. Is a component that imparts. Titanium dioxide is used as the component (F). Titanium dioxide has a rutile type and an anatase type depending on the difference in crystal structure,
Although the production method includes a sulfuric acid method and a chlorine method, a powder having a particle diameter of 10 μm or less is preferable, and a particle diameter of 10 μm or less is preferable because the dispersibility is good, the surface of the foam is smooth and the flame retarding effect is good. More preferable, considering the flame retardant effect and economical efficiency,
1-100 nm is particularly preferred. As long as the titanium dioxide powder is in this range, it can be used in the present invention having any crystal structure and any manufacturing method. In addition, even if only one of the component (E) or the component (F) is blended, the obtained foam does not show excellent flame retardancy.

The blending amount of the component (F) is 100 parts of the component (A).
The amount is 0.1 to 20 parts by weight, and preferably 1.0 to 10 parts by weight. If it is less than 0.1 part by weight, it is impossible to impart excellent flame retardancy to the foam. Again 2
Even if it is blended in an amount of more than 0 parts by weight, there is no effect of further improving the flame retardancy.

In the expandable polyorganosiloxane composition of the present invention, unless necessary for the purpose of the present invention, a terminal triorganosilyl which does not correspond to the component (A) or the component (B) is used as a diluent, if necessary. A polyorganosiloxane closed with a base or a silanol group can be blended.
In addition, if necessary, other than the component (E) and the component (F),
One or more fillers or pigments, ie fumed silica, precipitated silica, quartz powder, diatomaceous earth, aluminum oxide, zinc oxide, iron oxide, cerium oxide, mica, clay, calcium carbonate, metal powder One or two or more of graphite can be blended. further,
A flame retardant other than the component (E) and the component (F) such as zinc carbonate and manganese carbonate; a heat resistance improver such as cerium hydroxide can be added.

The expandable polyorganosiloxane composition of the present invention comprises, as a first embodiment, a first package containing the component (A), the component (C) and the component (D), and the component (B). Two packaging forms consisting of the second packaging may be prepared and stored, and may be mixed, stirred and reacted at the time of use to allow curing and foaming to proceed simultaneously. Further, as a second embodiment, instead of the above-mentioned second packaging, a second packaging containing a part of the component (A) and the component (B) may be prepared and used.
When the additives such as the component (E), the component (F) and other fillers are compounded, they are generally compounded in the first package, but they may be separately compounded at the time of use, and the above-mentioned second compound may be added. In embodiments, it may be included in the second packaging as long as there is no risk of reaction progressing during storage. The mixing temperature is
The component (D) is not particularly limited as long as it does not volatilize, but it is generally mixed at 0 to 60 ° C. in consideration of workability and the like.

[0032]

By using the expandable polyorganosiloxane composition of the present invention to simultaneously cure and foam,
It is possible to obtain a low-density rubber-like foam having a high foaming ratio, exhibiting an excellent foam control effect, excellent flame retardancy, and having fine and uniform cells.

The flame-retardant foam of the present invention thus obtained has the heat resistance, cold resistance, moisture resistance, touch feeling of silicone,
Uses low-density and high-performance heat insulating materials, sound absorbing materials, anti-vibration agents, cushioning agents, packings, gaskets, pads, airtight sealing materials, etc. that take advantage of features such as safety, especially excellent flame retardancy is required Insulation materials and pipe sealing materials for construction,
It is suitable for home electric appliances.

[0034]

The present invention will be further described below with reference to Examples and Comparative Examples. In these examples, all parts are parts by weight and viscosities represent viscosities at 25 ° C. In addition,
The invention is not limited by these examples.

The chain polysiloxanes (A-1 to A-4 and B-1) having the following average structural formulas and viscosities as the component (A) and the component (B) are used in Examples and Comparative Examples of the present invention. Was used. Note that the structural formulas having a plurality of intermediate siloxane units do not represent block copolymers, but merely indicate the number of siloxane units, and these polysiloxanes are random copolymers. In the formula, the following abbreviations were used. Me: Methyl group; Vi: Vinyl group; Ph: Phenyl group

A-1: α, ω-divinylpolymethylphenylsiloxane

[Chemical 7] Viscosity: 3,000 cP; A-2: α, ω-divinylpolymethylphenylsiloxane

[Chemical 8] Viscosity: 3,500 cP; A-3: α, ω-divinylpolymethylphenylsiloxane

[Chemical 9] Viscosity: 2,500 cP; A-4: α, ω-divinylpolydimethylsiloxane

[Chemical 10] Viscosity: 3,000 cP; B-1: Polymethyl hydrogen siloxane

[Chemical 11] Viscosity: 25 cSt.

Further, as the component (C), a platinum vinyl siloxane complex (C-1) obtained from chloroplatinic acid and polymethylvinyl siloxane containing 1% by weight of platinum atom.
Was used.

As the component (D), methanol, n-propanol or 2-butanol was used.

The carbon black used as the component (E) has a specific surface area of 36 m ² / g, a primary particle diameter of 50 nm and a bulk density of 1
It is 60 g / L of acetylene black.

The titanium dioxide used as the component (F) is
Specific surface area 50 m ² / g, primary particle size 21 nm, bulk density 130
It is g / L rutile type fumed titanium dioxide.

Examples 1 to 5 and Comparative Examples 1 to 4 The components were mixed at the compounding ratios shown in Table 1 to prepare respective compositions. That is, as the component (A), an alkenyl group-containing polyorganosiloxane having a phenyl group was used in Examples 1 to 5, and an alkenyl group-containing polyorganosiloxane having no phenyl group was used in Comparative Examples 1 and 2. In Comparative Examples 3 and 4, as the component (A), the same alkenyl group-containing polyorganosiloxane A-1 having a phenyl group as in Examples 1 to 3 was used.
Either component (F) or component (E) in the examples
An amount corresponding to the total amount of the component and the component (F) was blended. Table 1 shows the OH / H ratio and the H / Vi ratio in the composition. However,
OH represents a hydroxyl group of the blended alcohol, and H and Vi represent a hydrogen atom and a vinyl group bonded to a silicon atom in the blended polysiloxane.

By mixing, foaming and curing proceeded at room temperature, and after leaving for 30 minutes, a foam having rubber elasticity except for Comparative Example 1 was obtained. The expansion ratio and the size of bubbles (cells) of the foam thus obtained were measured. Further, using a foam having a thickness of 10 mm, the flame retardancy of the foam was evaluated according to the flame retardancy test method (vertical method) defined by UL94. The results are as shown in Table 1.

[0043]

[Table 1]

In each of Examples 1 to 5 according to the present invention, an excellent foam having excellent flame retardancy, a high expansion ratio, and fine and uniform cells was obtained. On the other hand, in Comparative Example 1, when the same OH / H ratio as in Example 1 was used, even when foaming, the foam was broken during the curing, and a foam could not be obtained. In Comparative Example 2, OH / H
Although the foam was obtained by lowering the ratio and the flame retardancy was excellent, the expansion ratio was low and the cell size was coarse as compared with the foams obtained in Examples 1 to 5. In Comparative Examples 3 and 4, foams having a high expansion ratio and fine and uniform cells were obtained, but excellent flame retardancy was not obtained.

Claims (2)

(57) [Claims] 1. (A) General formula: (In the formula, R ¹ represents an alkenyl group, R ² may be the same or different from each other, and represents a substituted or unsubstituted monovalent hydrocarbon group having no aliphatic unsaturated bond, and a is Represents an integer of 1 or 2, b represents an integer of 0 to 2, a
+ B is an integer of 1 to 3) in the molecule, and at least one phenyl group bonded to a silicon atom in the molecule, wherein the phenyl group is a silicon atom. Alkenyl group-containing polyorganosiloxane having 0.1 to 30 mol% of all organic groups bonded to
00 parts by weight; (B) General formula: (In the formula, R ^{3 s} may be the same or different from each other, and are substituted or unsubstituted 1 having no aliphatic unsaturated bond.
Represents a valent hydrocarbon group, c represents an integer of 0 to 2, d represents an integer of 1 or 2, and c + d is an integer of 1 to 3). Polyorganohydrogensiloxane, an amount in which the amount of hydrogen atoms bonded to silicon atoms per alkenyl group of the component (A) is 3 to 1,000; (C) a catalyst selected from platinum or a platinum compound; A)
Amount of platinum atom of 0.1 to 1,000 ppm by weight with respect to component; (D) Monohydric alcohol having 1 to 4 carbon atoms having no aliphatic unsaturated bond, (B) component of silicon atom Includes 0.01 to 10 parts by weight of hydroxyl groups per bonded hydrogen atom; (E) 0.1 to 20 parts by weight of carbon black; and (F) 0.1 to 20 parts by weight of titanium dioxide. A foamable polyorganosiloxane composition comprising: 2. A flame-retardant foam obtained by foaming and curing the foamable polyorganosiloxane composition according to claim 1.