JPH08239395A - Phosphazene derivative, resin composition and its cured material - Google Patents

Abstract

PURPOSE: To provide a new derivative useful as a coating compound, an adhesive, etc., having coupling function and curing resin function, comprising a reactive double bond, a Si-containing hydrolyzable group and an alkoxy group or an alkylmercapto group from which active hydrogen is eliminated, etc. CONSTITUTION: This new phosphazene derivative is shown by formula I ((n) is an integer of >=3; 2n×A are each independently an organic group containing one or more reactive double bond, a hydrolyzable group containing one or more silicon atoms in the skeleton, a 1-6C alkoxyl group, the residue drived from a 1-4C alkylmercapto group by removal of an active hydrogen; at least one A among 2n×A is an organic group containing one or more reactive double bond and at least one is a hydrolyzable group containing one or more silicon atoms in the skeleton) and has both coupling function and curing resin function. The compound is obtained by subjecting a cyclic phosphazene compound of formula II (B is a halogen), a reactive double bond-containing compound and a compound containing a hydrolyzable group containing Si to nucleophilic addition reaction.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a phosphazene derivative useful as a curable resin composition, a binder such as a paint or an adhesive, and an additive such as a coupling agent, a resin composition containing the same, and a cured product thereof.

Conventionally, for the purpose of improving the functions (physical mechanical strength, adhesiveness, heat resistance, electrical characteristics, weather resistance, etc.) of composite materials composed of inorganic materials such as metals and glass and organic materials, surface treatment, A coupling agent is used. For example, silane coupling agents are widely used in a wide range of fields such as paints, adhesives, and sealing materials. (Less than,
This is simply called a silane coupling agent. ) The paints, adhesives, encapsulants, etc. listed above generally contain a curable resin as a main component (matrix) and a resin composition containing various admixtures such as organic or inorganic fillers, pigments, and ultraviolet absorbers. It is a thing. In this case, since the silane coupling agent used as an additive has a functional group having an affinity for an organic substance (mainly a curable resin) and a functional group having an affinity for an inorganic substance, various silane coupling agents are used in the matrix. It has a function of uniformly dispersing the admixture and a function of increasing the affinity between the matrix and the admixture and preventing internal cracks during curing, for example.

[0003]

However, a silane coupling agent is generally an additive used for the purpose of improving the mechanical strength of a cured product containing the silane coupling agent or improving the compatibility between an inorganic substance and an organic substance. , There is no function as a matrix. Therefore, it has been desired to develop a compound having a function as a matrix itself and a function (coupling function) of compatibilizing or uniformly dispersing an inorganic substance and an organic substance.

[0004]

Means for Solving the Problems As a result of intensive studies aimed at solving the above problems, the present inventors have introduced both a reactive double bond and a silicon atom-containing hydrolyzable group into one molecule of a phosphazene compound. By doing so, they have found that a compound having both a coupling function and a matrix function can be obtained, and have completed the present invention.

That is, the present invention is based on the equation (1) (1)

[0006]

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(In the formula, n represents an integer of 3 or more, 2n A's each independently represent (a) an organic group having at least one reactive double bond, and (b) silicon in the skeleton. A hydrolyzable group having at least one atom, or (c) a residue obtained by removing active hydrogen from a linear or branched alkoxyl group having 1 to 6 carbon atoms or an alkylmercapto group having 1 to 4 carbon atoms. Represents any of at least 1 of 2n A
One is (a) and at least one is (b). ), A phosphazene derivative represented by the formula (2), the formula (1)
The value of n in 3 is 4 or 3, the phosphazene derivative according to (1) above, (3) the resin composition containing the phosphazene derivative according to (1) or (2) above, and (4) above (3) above. The present invention relates to a cured product of the resin composition.

In the present invention, a compound having a reactive double bond in a cyclic phosphazene compound represented by the following formula (2) and a compound having a hydrolyzable group having a silicon atom in the skeleton are subjected to a nucleophilic addition reaction. The phosphazene derivative of the present invention can be obtained by introducing

[0009]

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(In the formula, n represents an integer of 3 or more, and B represents a halogen atom.) Among these cyclic phosphazene compounds, a preferable specific example that can be used is hexachlorocyclotriphosphazene (in the formula (2), B = Cl). , N = 3) and octachlorocyclotetraphosphazene (B = Cl, n = 4).

The reactive double bond contained in the phosphazene derivative of the present invention is not particularly limited as long as it is a functional group which is cured by a heating operation, irradiation with ultraviolet rays, electron beams or the like, and an acryl group, a methacryl group, a vinyl group or an allyl group. Examples of groups include groups. Hereinafter, compounds having these functional groups will be referred to as reactive double bond-containing compounds.

The hydrolyzable group having a silicon atom in the skeleton of the phosphazene derivative of the present invention means a functional group which is hydrolyzed in the presence of an acid and an alkali catalyst to form a siloxane bond, for example, an alkoxysilyl group. , Acetoxysilyl group and the like.

In the above, the compound having a reactive double bond and the compound having a hydrolyzable group having a silicon atom in the skeleton (hereinafter abbreviated as a silicon-containing compound) are represented by the formula (2).
A compound having a functional group further having active hydrogen in the same molecule is used in order to bind to the P atom of the compound. Specific examples of these functional groups having active hydrogen include a hydroxyl group, a mercap group, a primary amino group and a secondary amino group.

Specific examples of the silicon-containing compound which can be used in the present invention include N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane. ,
3-aminopropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, (3-mercaptopropyl) methyldimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like can be mentioned, and it is also possible to use two or more of them in combination. . The amount of these compounds used is usually 1 to 5 equivalents, preferably 1 to 3 equivalents (active hydrogen equivalents) per 1 equivalent of the halogen atom of the cyclic phosphazene compound.
Is.

Specific examples of the reactive double bond-containing compound used in the present invention include allyl alcohol, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxyethylacrylamide and allyl. Phenol, allyl mercaptan, allylamine, acrylamide, aminomethyl (meth) acrylate, aminoethyl (meth) acrylate, aminopropyl (meth) acrylate, N-methylallylamine, N-ethylallylamine, N-propylallylamine, N-methylaminoethyl (Meth) acrylate, N-ethylaminomethyl (meth) acrylate, N-methylaminoethyl (meth) acrylate, N-ethylaminoethyl (meth) acrylate, - methylaminopropyl (meth) acrylate, N- ethyl-aminopropyl (meth)
Acrylate and the like can be mentioned, and it is also possible to use two or more of them together.

Further, in addition to the above compounds, by reducing the active sites of the phosphazene derivative finally obtained, the crosslink density of the cured product is lowered, the brittleness of the cured product is improved, and the melting point is lowered. Non-reactive groups may be introduced into the compound of formula (2). In this case, the compound to be used is not limited as long as it is a compound having only one functional group having active hydrogen in the same molecule, but a compound having 6 or less carbon atoms is preferable. Specific examples of such compounds that can be used include alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, n-heptanol, n-hexanol and cyclohexanol, propylamine, Examples include amines such as butylamine, heptylamine, hexylamine, cyclohexylamine, diethylamine, dipropylamine, and alkyl mercaptans such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, and butyl mercaptan. These are used in combination of two or more. Things are possible. Such a compound having only one functional group having active hydrogen in the same molecule is hereinafter referred to as a non-reactive group-containing compound. These compounds are used in an amount of 4 equivalents or less in active hydrogen equivalent to 1 equivalent of halogen atom of the cyclic phosphazene compound, if necessary.

The above silicon-containing compound, reactive double bond-containing compound and non-reactive group-containing compound can be reacted with the compound of formula (2) as follows. For example, the compound of formula (2) is dissolved in a solvent, these compounds are added thereto, and the mixture is stirred at 40 to 100 ° C. for 1 to 48 hours. In this case, it is particularly preferable to replace the inside of the reaction vessel with nitrogen. Further, these compounds can be directly reacted with the compound of the formula (2), but if necessary, they may be converted to sodium salts with sodium hydride, metallic sodium or the like. In the above, the solvent is not particularly limited as long as it does not have active hydrogen, but specific examples that can be used include tetrahydrofuran, methyl isobutyl ketone, ethyl ether and the like. The amount of the solvent used is usually 200 to 1000 parts by weight based on 100 parts by weight of the total weight of the raw materials used.

The reaction can also be carried out by dropping these compounds and the compound of formula (2) with a hydrohalic acid trapping agent such as trimethylamine, triethylamine or pyridine while stirring with a solvent such as tetrahydrofuran or toluene. Can be done. The reaction at this time is 50
It is performed by heating and stirring at -100 ° C for 1 hour to 48 hours. In this case, the amount of the solvent used is usually 200 to 2000 parts by weight based on 100 parts by weight of the total weight of the raw material compounds. The amount of the hydrohalic acid trapping agent used is usually 1 to 1.5 equivalents relative to 1 equivalent of active hydrogen in the raw material.

The resin composition of the present invention optionally contains a polymerization initiator suitable for the phosphazene derivative obtained as described above, depending on the curing method. For example, when a curing method using ultraviolet rays or visible rays is used, as the photopolymerization initiator, 1-hydroxycyclohexyl phenyl ketone, dibenzoyl, benzoyl methyl ether, p-chlorobenzophenone, p-methoxybenzophenone, benzoyl peroxide, dibenzoyl peroxide -T
Specific examples that can be used include ert-butyl peroxide. These photopolymerization initiators may be used alone or
Two or more kinds can be used in combination. The amount of these photopolymerization initiators used is 0.05 to 10 parts by weight, preferably 0.1 to 6 parts by weight, based on 100 parts by weight of the phosphazene derivative.

Further, examples of the polymerization initiator when the heat curing method or the room temperature curing method are used include peroxide compounds and amine compounds. Examples of peroxide compounds include benzoyl peroxide, p-chlorobenzoyl peroxide, and 2. , 4-dichlorobenzoyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, t-butyl peroxyacetate, t-butyl peroxybenzoate and the like can be mentioned as specific examples. .

The amine compounds include N, N-diethanol-p-toluidine, dimethyl-p-toluidine, p-toluidine, methylamine, t-butylamine, methylethylamine, diphenylamine, 4,4 '.
-Dinitrodiphenylamine, o-nitroamine, p-
Specific examples that can be used include bromoaniline and 2,4,6-tribromoaniline. These peroxides,
The amount of the amine-based compound used is usually 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the phosphazene derivative.

The resin composition of the present invention may contain a filler in addition to the phosphazene derivative and the polymerization initiator, if necessary. Examples of the filler include silica,
Examples thereof include powdery or fibrous inorganic or organic fillers such as glass, metals, ceramics, and organic fibers. The amount of these fillers used is 10
It is usually 1 to 200 parts by weight, preferably 2 to 100 parts by weight, relative to 0 parts by weight.

Furthermore, the resin composition of the present invention contains various additives such as an organic solvent, an antistatic agent, an ultraviolet absorber, a polymerization inhibitor, a dye, a sensitizer, and a leveling agent, if necessary. May be. The amount of these additives used is 3 parts by weight per 1 part by weight of the phosphazene derivative in the case of an organic solvent.
To 30 parts by weight, and in the case of other additives, it is usually 0.01 to 10 parts by weight with respect to 100 parts by weight of the phosphazene derivative.
Parts by weight, preferably 0.05 to 5 parts by weight. The resin composition of the present invention can be obtained by uniformly mixing the respective components in a predetermined ratio.

[0024]

EXAMPLES The present invention will be described in more detail with reference to the following examples.

Example 1 A 500 ml four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a condenser was replaced with nitrogen, and then 27.8 g of hexachlorocyclophosphazene and 87.5 NaH.
g and 300 ml of THF (tetrahydrofuran) were added, and the mixture was stirred and dissolved at room temperature. Then, 14.4 g of propyl alcohol was gradually added dropwise from the dropping funnel. After completion of dropping, the mixture was heated and stirred at 60 ° C. for 3 hours. Next, after returning the temperature to room temperature, 9.6 g of allyl alcohol was gradually added dropwise from the dropping funnel. After completion of dropping, the mixture was heated and stirred at 60 ° C. for 3 hours. Next, the temperature was returned to room temperature, 8.2 g of triethylamine was added, and then 17.6 g of 3-aminopropyltriethoxysilane was gradually added dropwise from the dropping funnel. After the dropping, the reaction was performed at 60 ° C. for 6 hours. After the reaction was completed, the reaction solution was transferred to a separating funnel, 200 ml of methyl isobutyl ketone was added as an extraction solvent, and the mixture was washed with water several times. After the solution was dehydrated with anhydrous magnesium sulfate, the solvent was distilled under reduced pressure to obtain a pale yellow viscous body (phosphazene derivative (A-1) of the present invention) represented by the following formula (3).

[0026]

[Chemical 4]

The resulting viscous稠体an infrared absorption spectrum analysis of the results, 1040 cm ^-1, absorption derived from P-O-C bond to a position of 1070 cm ^-1, Si in 1080 cm ^-1
Absorption derived from —O—C bond, P = N at 1240 cm ⁻¹
Absorption derived from binding, absorption derived from C═C at 1640 cm ^−1, and absorption derived from NH—C at 3220 cm ⁻¹ were observed.

Example 2 A 500 ml four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooling tube was replaced with nitrogen, and then 27.8 g of hexachlorocyclophosphazene, 52.6 g of triethylamine and 300 ml of THF were charged at room temperature. It was stirred and dissolved. Then, 26.6 g of hydroxyethyl methacrylate was gradually added dropwise from the dropping funnel. After completion of the dropping, the mixture was heated and stirred at 60 ° C. for 12 hours. Next, after returning the temperature to room temperature, 14.2 g of propylamine was gradually added dropwise from the dropping funnel. After completion of dropping, the mixture was heated and stirred at 60 ° C. for 3 hours. Next, after returning the temperature to room temperature, 3-
17.6 g of aminopropyltriethoxysilane was gradually added dropwise from the dropping funnel. After the dropping, the reaction was performed at 60 ° C. for 6 hours. After the reaction was completed, the reaction solution was transferred to a separating funnel, 200 ml of methyl isobutyl ketone was added as an extraction solvent, and the mixture was washed with water several times. After the solution was dehydrated with anhydrous magnesium sulfate, the solvent was distilled under reduced pressure to obtain a light brown viscous body (phosphazene derivative (A-2) of the present invention) represented by the following formula (4).

[0029]

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The resulting viscous稠体an infrared absorption spectrum analysis of the results, 1040 cm ^-1, absorption derived from P-O-C bond to a position of 1070 cm ^-1, Si in 1080 cm ^-1
Absorption derived from —O—C bond, P = N at 1240 cm ⁻¹
From binding to absorption, absorption derived from C = C to 1640 cm ^-1, absorption derived from C = O to 1680 cm ^-1, 32
Absorption derived from NH—C was observed at 20 cm ⁻¹ .

Example 3 A 500 ml four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooling tube was replaced with nitrogen, and then 27.8 g of hexachlorocyclophosphazene, 52.6 g of triethylamine and 300 ml of THF were charged at room temperature. It was stirred and dissolved. Then, 14.1 g of allylamine was gradually added dropwise from the dropping funnel. After completion of dropping, the mixture was heated and stirred at 60 ° C. for 3 hours. Next, after returning the temperature to room temperature, 14.2 g of propylamine was gradually added dropwise from the dropping funnel. After completion of dropping, the mixture was heated and stirred at 60 ° C. for 3 hours. Next, after returning the temperature to room temperature, 17.6 g of 3-aminopropyltriethoxysilane was gradually added dropwise from the dropping funnel. After the dropping, the reaction was performed at 60 ° C. for 6 hours. After the reaction was completed, the reaction solution was transferred to a separating funnel, 200 ml of methyl isobutyl ketone was added as an extraction solvent, and the mixture was washed with water several times. After dehydrating the solution with anhydrous magnesium sulfate,
The solvent was distilled under reduced pressure to obtain a pale yellow viscous body (phosphazene derivative (A-3) of the present invention) represented by the following formula (5).

[0032]

[Chemical 6]

The resulting viscous稠体an infrared absorption spectrum analysis of the results, 1040 cm ^-1, absorption derived from P-O-C bond to a position of 1070 cm ^-1, Si in 1080 cm ^-1
Absorption derived from —O—C bond, P = N at 1240 cm ⁻¹
Absorption due to binding, 930, 1420, 2930 cm
^-1 absorption derived from C = C, 1650, 3220 cm ^-1
The absorption derived from NH-C was observed.

Example 4 Using the phosphazene derivative (A-1) obtained in Example 1, a resin composition (B-1) of the present invention having the following composition was prepared. Phosphazene derivative (A-1) 10 g Benzophenone 0.3 g Methyl ethyl ketone 100 g This resin composition (B-1) was applied on a glass plate using a bar coater, dried, and then exposed to ultraviolet rays of 90 mj / cm using a high pressure mercury lamp. ² The cured product of the present invention (C
-1) was obtained. The film thickness of the obtained cured product (C-1) was 0.1.
It was 1 mm.

Example 5 Using the phosphazene derivative (A-2) obtained in Example 2, a resin composition (B-2) of the present invention having the following composition was prepared. Phosphazene derivative (A-2) 10 g Benzophenone 0.3 g Methyl ethyl ketone 100 g This resin composition (B-2) was applied on a glass plate using a bar coater, dried, and then irradiated with ultraviolet rays of 90 mj / cm using a high pressure mercury lamp. ² The cured product of the present invention (C
-2) was obtained. The film thickness of the obtained cured product (C-2) was 0.
It was 1 mm.

Example 6 Using the phosphazene derivative (A-3) obtained in Example 3, a resin composition (B-3) of the present invention having the following composition was prepared. Phosphazene derivative (A-3) 10 g Benzophenone 0.3 g Methyl ethyl ketone 100 g This resin composition (B-3) was applied on a glass plate using a bar coater, dried, and then exposed to ultraviolet rays of 90 mj / cm using a high pressure mercury lamp. ² The cured product of the present invention (C
-3) was obtained. The film thickness of the obtained cured product (C-3) was 0.1.
It was 1 mm.

Test Example The surface hardness and adhesion of the cured products obtained in Examples 4 to 6 were tested. Adhesion test: A peeling test using an adhesive tape was performed 100 times to determine the number of times that peeling did not occur. (The test body is Example 4)
The adhesives of the cured product of the present invention and the glass plate obtained in ~ 6 were used as they were. ) Measurement of surface hardness: The pencil hardness according to JIS K-5401 was determined. The test results are shown in Table 1 below.

[0038]

[Table 1] Table 1 Pencil hardness Number of times that peeling did not occur Cured product (C-1) 2H 100 Cured film (C-2) 5H 100 Cured film (C-3) 1B 100

As is clear from Table 1, the cured product obtained from the resin composition containing the phosphazene derivative of the present invention has excellent adhesion, and the phosphazene derivative of the present invention functions as a coupling agent and a curable resin. It also has the function as.

[0040]

The phosphazene derivative of the present invention is a compound having both a coupling agent function and a matrix (curable resin) function, and is extremely useful in the fields of adhesives, encapsulants and the like.

Claims (4)

[Claims] 1. A formula (1): (In the formula, n represents an integer of 3 or more, 2n A's each independently represent (a) an organic group having at least one reactive double bond, and (b) a silicon atom in the skeleton. One or more hydrolyzable groups, or (c) a linear or branched alkoxyl group having 1 to 6 carbon atoms or a residue of the alkylmercapto group having 1 to 4 carbon atoms excluding active hydrogen. The phosphazene derivative represented by at least one of 2n A is (a) and at least one is (b). 2. The phosphazene derivative according to claim 1, wherein the value of n in the formula (1) is 3 or 4. 3. A resin composition containing the phosphazene derivative according to claim 1. 4. A cured product of the resin composition according to claim 3.