JPH0770440A - Polysiloxane composition - Google Patents

Abstract

PURPOSE:To provide the sect composition comprising each specific polysiloxane and carboxylic acid at specified proportions, capable of improving the storage stability of room temperature-curing resin compositions by its incorporation therein without impairing their curability and the physical properties of the resultant cured products, thus useful for sealants, etc. CONSTITUTION:The composition comprising (A) 100 pts.wt. of a polysiloxane of the formula (R<1> is 1-6C hydrocarbon; R<2> is 1-30C hydrocarbon; m is >=0; n is >=1) and (B) 1-100 pts.wt. of a carboxylic acid of formula R<2>COOH such as acetic acid.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polysiloxane composition used as an additive for various room temperature curable resin compositions. More specifically, it relates to a polysiloxane composition that can be added to a room temperature curable resin composition to improve storage stability without adversely affecting curability and physical properties of the cured product.

[0002]

2. Description of the Related Art Conventionally, various room temperature curable resin compositions such as polyurethane resin compositions and epoxy resin compositions have been used.
It is widely used as a sealing agent, adhesive, primer, paint, waterproofing agent, flooring agent, etc.

These various room-temperature-curable resin compositions (hereinafter referred to as resin compositions) have various resins such as a curing agent, a plasticizer, a filler, an antioxidant, and various additives in addition to the matrix resin. It is produced by mixing a compounding agent. In such a resin composition, not only the cured product has excellent physical properties, but also excellent curability such as short curing time, excellent storage stability without viscosity change during storage, etc. Various characteristics of are required.

However, some of the above-mentioned various compounding agents may inevitably contain a small amount of water, and the curing reaction of the resin composition proceeds due to the water contained in the compounding agents. However, there is a problem in that the storage stability, curability and physical properties of the cured product are adversely affected, and a resin composition satisfying the required properties cannot be obtained.

It is very difficult to completely physically remove the water contained in the compounding agent. Therefore, chemical dehydration is performed by adding an additive for dehydration. Orthoformic acid, tetraethoxysilane and the like are known as dehydrating agents used for resin compositions. However, since these dehydrating agents react with water to form alcohol as a by-product, there is a problem that depending on the resin composition, the curability is reduced by the alcohol and the physical properties of the cured product are reduced. .

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art. When used as an additive for a room temperature curable resin composition, the curability and physical properties of the cured product are improved. It is an object of the present invention to provide a polysiloxane composition capable of realizing a room temperature curable resin composition having excellent storage stability without deteriorating the above.

[0007]

In order to achieve the above object, the present invention provides the following formula:

[Chemical 2] R ^{2 with} respect to 100 parts by weight of the polysiloxane represented by
A polysiloxane composition comprising 1 to 100 parts by weight of a carboxylic acid represented by COOH. (In the above formulas, R ¹ represents the same or different hydrocarbon group having 1 to 6 carbon atoms, R ² represents the same or different hydrocarbon group having 1 to 30 carbon atoms,
Furthermore, m is an integer of 0 or more, and n is an integer of 1 or more. )

The polysiloxane composition of the present invention will be described in detail below. INDUSTRIAL APPLICABILITY The polysiloxane composition of the present invention is used as a sealing agent, an adhesive, a primer, a paint, a waterproofing agent, a flooring agent, etc., and is used in various room temperature curable resin compositions such as polyurethane resin compositions and epoxy resin compositions ( Hereinafter, referred to as a resin composition) is a polysiloxane composition used as an additive.

The polysiloxane contained in the polysiloxane composition of the present invention has the following formula:

[Chemical 3] (In the above formula, R ¹ is the same or different carbon number 1
The 6 hydrocarbon group, R ² represents a hydrocarbon group having same or different carbon atoms of 1 to 30, respectively, further, m is an integer of 0 or more, n represents an integer of 1 or more. ) Is a poly (acyloxyalkyl) siloxane.

In the polysiloxane represented by the above formula, R ¹ is a hydrocarbon group having 1 to 6 carbon atoms. In the polysiloxane, R ¹ may be the same or different from each other. Specific examples of R ¹ include a methyl group, an ethyl group, and a phenyl group.

In the polysiloxane represented by the above formula, R ² is a hydrocarbon group having 1 to 30 carbon atoms. In the above polysiloxane, R ² may be the same or different from each other. Specific examples of R ² include methyl group, propyl group, butyl group, stearyl group, octyl group, lauryl group, behen group, palmityl group, eicosyl group, hexacosyl group, phenyl group, benzyl group, and the like. Various examples of the hydrocarbon group contained in the carboxylic acid described below used in the synthesis are exemplified.

Particularly, in terms of odor and reactivity of carboxylic acid,
A hydrocarbon group having 6 to 21 carbon atoms such as a stearyl group, a palmityl group, a lauryl group, an octyl group, an eicosyl group, a behen group, a phenyl group and a benzyl group is preferable.

In the polysiloxane represented by the above formula, m is an integer of 0 or more and n is an integer of 1 or more. Preferably, m is 0 to 200 and n is about 1 to 500.
When the content is within the above range, more preferable results can be obtained in terms of viscosity that is easy to synthesize.

In the polysiloxane represented by the above formula, the repeating units may be arranged randomly, arranged in blocks, or a mixture of the two. is there.

Such a polysiloxane uses a Group VIII transition metal catalyst such as a palladium-based, rhodium-based, nickel-based, or platinum-based catalyst, and has a corresponding structure having an acyloxyalkyl group of hydrogen. It can be synthesized by reacting gen siloxane with a carboxylic acid having R ² , preferably by reacting an equivalent or more carboxylic acid with respect to the SiH group of polyhydrogen siloxane.

As the polyhydrogen siloxane,
Preferable examples include one or a combination of two or more of poly (methylhydrogen) siloxane, poly (phenylhydrogen) siloxane, and copolymers thereof with polymethylsiloxane. The molecular weight of polyhydrogensiloxane is not particularly limited.

Examples of poly (methylhydrogen) siloxane and poly (phenylhydrogen) siloxane include the following formulas.

[Chemical 4] And the like are preferably exemplified (m and n are the same as the above polysiloxane).

On the other hand, as the carboxylic acid, acetic acid, butyric acid,
Caproic acid, caprylic acid, pelargonic acid, capric acid,
Undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melissic acid, and other straight chain saturated fatty acids; , Unsaturated acids such as sorbic acid, linoleic acid and linoleic acid; benzoic acid, phenylacetic acid, 3
-Aromatic carboxylic acids such as phenoxyundecanoic acid, terephthalic acid, isophthalic acid, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid; alicyclic carboxylic acids such as tetrahydrophthalic acid, nadic acid;
One or a combination of two or more other carboxylic acids is exemplified.

The polysiloxane composition of the present invention contains 1 to 100 parts by weight of a carboxylic acid represented by R ² COOH with respect to 100 parts by weight of such a polysiloxane.

Such a polysiloxane composition of the present invention reacts with water contained in a compounding agent such as a filler at room temperature to reduce the water content in the resin composition in a short time. Moreover, at that time, a relatively low-reactivity fatty acid (preferably a higher fatty acid) is released. Therefore, by adding the polysiloxane composition of the present invention, a resin composition excellent in storage stability can be realized without adversely affecting the curing time and the physical properties of the cured product.

Suitable examples of the carboxylic acid represented by R ² COOH include one or more of the carboxylic acids described in the section of the above-mentioned synthesis of polysiloxane. In particular, stearic acid, in terms of odor of carboxylic acid, reactivity, and melting point,
Carboxylic acids having 6 to 21 carbon atoms in R ² such as palmitic acid, lauric acid, octytic acid, behenic acid, eicosic acid, benzoic acid and phenylacetic acid are preferably used.

In the polysiloxane composition of the present invention, R ^{2 of the} polysiloxane and R of the carboxylic acid are used.
^Two may be the same or different.

In the polysiloxane composition of the present invention, the content of such carboxylic acid is 1 to 100 parts by weight based on 100 parts by weight of the above-mentioned polysiloxane. When the content of the carboxylic acid is less than 1 part by weight, the water contained in the compounding agent of the resin composition does not react rapidly with the polysiloxane composition of the present invention, and a sufficient effect as a storage stabilizer cannot be obtained. . On the contrary, when the amount is more than 100 parts by weight, the ratio of the hydrolyzable group (that is, acyloxyalkyl group) per unit weight of the polysiloxane composition becomes small, so that a sufficient effect as a storage stabilizer can be obtained. Therefore, it is necessary to add a large amount to the resin composition, and this causes the resin composition to react with a large amount of carboxylic acid.

The content of the carboxylic acid is preferably 5 to 30 parts by weight, more preferably 10 to 20 parts by weight, based on 100 parts by weight of the above-mentioned polysiloxane. By setting the content of the carboxylic acid in the above range, the storage stability,
A favorable result is obtained in terms of curability and the like.

In the polysiloxane composition of the present invention, the carboxylic acid may be added separately to the above-mentioned polysiloxane, or in the synthesis reaction of the above-mentioned polysiloxane, it may be added to the SiH group of the polyhydrogensiloxane. On the other hand, by reacting an equivalent amount or more of carboxylic acid, the excess carboxylic acid may be added to the polysiloxane composition. Further, it may contain both the separately added carboxylic acid and the reaction excess carboxylic acid.

The polysiloxane composition of the present invention as described above is added to various resin compositions as a storage stabilizer. Preferable examples of the resin composition include an epoxy resin composition, a urethane resin composition, a silicone resin composition, a modified silicone resin composition, and a polysulfide resin composition. Particularly, it is preferably added to a one-pack type moisture-curable polyurethane resin composition, an epoxy resin composition, a modified silicone resin composition and the like.

The amount of the polysiloxane composition of the present invention added to the resin composition may be appropriately determined according to the resin composition and is not particularly limited, but is usually 0 per 100 parts by weight of the resin composition. 0.5 to 30 parts by weight. By setting the compounding amount of the polysiloxane composition within the above range, the curability of the resin composition and the physical properties of the cured product are not adversely affected, and the storage stability of the resin composition can be favorably improved.

Particularly, the addition amount of the polysiloxane composition to the resin composition is 1 to 2 with respect to 100 parts by weight of the resin composition.
The storage stability of the resin composition,
Further preferable results are obtained in terms of curability and the like.

Although the polysiloxane composition of the present invention has been described in detail above, the present invention is not limited to the above examples, and various modifications and improvements can be made without departing from the scope of the present invention. Good.

[0030]

EXAMPLES The present invention will be described in more detail with reference to specific examples of the present invention. Needless to say, the present invention is not limited to the following examples.

<Comparative Example 1> Methyl hydrogen polysiloxane (L-31 SiH equivalent 6 manufactured by Nippon Unicar Co., Ltd.)
5) 90 g of a mixture of 100 g and stearic acid 438 g
After heating to ℃, add 100 μl of isopropyl alcohol solution of platinum chloride hydrate (100 mg / 10 ml), react at the same temperature for 5 hours, and further react at 120 ℃ for 2 hours under reduced pressure to obtain polysiloxane composition. Obtained. ^As confirmed by ¹ HNMR, SiH was not present in the product. Further, the amount of free stearic acid was 1 part by weight or less based on 100 parts by weight of polysiloxane.

Invention Example 1 A dimethylsiloxane-methylhydrogensiloxane copolymer (FZ manufactured by Nippon Unicar Co., Ltd.) was used instead of methylhydrogenpolysiloxane.
A polysiloxane composition of the present invention was obtained in the same manner as in Comparative Example 1 except that 100 g of -3805 SiH equivalent 100) was used and stearic acid was changed to 350 g. ¹ HNM
When confirmed by R, SiH was not present in the product. Further, free stearic acid was 17 parts by weight with respect to 100 parts by weight of polysiloxane.

<Invention Example 2> A polysiloxane composition of the present invention was obtained in the same manner as in Comparative Example 1 except that 474 g of palmitic acid was used instead of stearic acid. ^When confirmed by ¹ HNMR, the product was SiH.
Did not exist. Further, free palmitic acid was 16 parts by weight with respect to 100 parts by weight of polysiloxane.

<Invention Example 3> A polysiloxane composition of the present invention was obtained in exactly the same manner as in Comparative Example 1 except that the amount of stearic acid was changed to 525 g. ¹ H NMR
However, SiH did not exist in the product. Further, free stearic acid was 16 parts by weight with respect to 100 parts by weight of polysiloxane.

Comparative Example 2 A polysiloxane composition was obtained in exactly the same manner as in Comparative Example 1 except that the amount of stearic acid was changed to 1000 g. ^As confirmed by ¹ HNMR, SiH was not present in the product. In addition, free stearic acid was 105 parts by weight with respect to 100 parts by weight of polysiloxane.

Various kinds of urethane resin compositions shown in the following Table 1 by such various polysiloxane compositions (indicated as polysiloxane in Table 1), the following urethane prepolymer, dioctyl phthalate (plasticizer), and calcium carbonate. The product (indicated as composition in Table 1) was prepared.
In Table 1, the unit of each component is parts by weight. The method of synthesizing the urethane prepolymer is as follows.

[Synthesis of Urethane Prepolymer] 500 g of polypropylene glycol having a number average molecular weight of 3000 and polypropylene triol 200 having a number average molecular weight of 3000
3 g of 0 g and 250 g of xylylene diisocyanate
The mixture was placed in a neck flask and reacted at 80 ° C. to obtain a urethane prepolymer having an isocyanate group content of 1.5% by weight.

For each urethane resin composition obtained,
The viscosity immediately after kneading and after standing at 60 ° C. for 3 days was measured by a B-type viscometer. The results are shown in Table 1 below.

[0039]

[Table 1]

As shown in Table 1 above, the composition 1 containing the polysiloxane composition of the present invention (urethane resin)
Nos. 3 to 3 have little increase in viscosity even after being left at 60 ° C. for 3 days, and have excellent storage stability as compared with the conventional resin compositions 4 to 6. From the above results, the effect of the present invention is clear.

[0041]

As described in detail above, the addition of the polysiloxane composition of the present invention does not adversely affect the curing time or the physical properties of the cured product, and the room temperature curing excellent in storage stability. A mold resin composition can be realized. Therefore, the polysiloxane composition of the present invention can be preferably used as an additive for storage stability of a sealing agent, an adhesive, a primer, a paint, a waterproofing agent, a flooring agent, etc., which is composed of a room temperature curable resin composition.

Claims (1)

[Claims] 1. The following formula: A polysiloxane composition containing 1 to 100 parts by weight of a carboxylic acid represented by R ² COOH with respect to 100 parts by weight of the polysiloxane represented by (In the above formulas, R ¹ is the same or different hydrocarbon group having 1 to 6 carbon atoms, and R ² is the same or different hydrocarbon group having 1 to 30 carbon atoms.
And m is an integer of 0 or more, and n is an integer of 1 or more. )