JPH0684384B2 - Phosphazene compound and curable composition using the compound - Google Patents

Description

TECHNICAL FIELD The present invention relates to a novel phosphazene compound, and a curable composition in which a cured product using the compound has good ionic conductivity.

[Problems to be Solved by Prior Art and Invention]

The phosphazene compound is a compound whose main chain is composed of phosphorus and nitrogen. In recent years, it has been attempted to use the phosphazene compound as a coating material or a flame retardant by selecting a substituent on the side chain. In addition, various studies have been carried out on its use for polymer solid electrolytes in electrochromic display devices, batteries, etc., and a highly viscous mixture of a specific chain polymer type polyphosphazene and an alkali metal salt,
It has been proposed as having good ionic conductivity.

However, for use as the polymer solid electrolyte, the above high-viscosity mixture must be once formed into a film by a method such as casting and then formed into a required shape,
The work was extremely complicated. Further, in the molding method in which the film is once obtained and then molded, there is a defect that the solid electrolyte is often peeled off because of poor adhesion to the electrochromic display element, the electrode of the battery and the like.

Therefore, it has been desired to develop a solid electrolyte that can be directly cured at the application site in a liquid state and then cured to form a solid electrolyte, and it has been expected that a phosphazene compound that can be used therefor will appear.

[Means for Solving the Problems]

The present inventors have conducted extensive studies to solve the above problems. As a result, they have found that such a purpose can be achieved by a phosphazene compound in which a polymerizable group is introduced into a specific cyclic phosphazene compound, and completed the present invention.

That is, the present invention provides (a) the general formula Is a phosphazene compound.

In the cyclic phosphazene compound represented by the above general formula of the present invention, X is not particularly limited as long as it is selected from a group having an acryloyl group or a methacryloyl group represented by the above general formulas (i) to (iii). Absent. Specific examples of particularly preferably used ones are as follows.

In the present invention, the group represented by the general formula (i) is (However, R ₁ , R ₂ and R ₃ are an acryloyl group, a methacryloyl group or a hydrogen atom, and all of R ₁ , R ₂ and R ₃ must not be hydrogen atoms). Specific examples of the group represented by the general formula (i) include pentaerythritol triacrylate, pentaerythritol trimethacrylate,
Examples include residues of pentaerythritol diacrylate and pentaerythritol dimethacrylate.

Further, the group represented by the above general formula (ii) is (However, R ₄ and R ₅ are an acryloyl group and a methacryloyl group, and both R ₄ and R ₅ must not be hydrogen atoms). If the group represented by the general formula (ii) is specifically shown,
There are residues of glycerol diacrylate, glycerol dimethacrylate, glycerol monoacrylate and glycerol monomethacrylate.

Furthermore, the group represented by the general formula (iii) above is (However, R ₆ , R ₇ and R ₈ are a methyl group or a hydrogen atom, and m ₁
And m ₂ are integers, and m ₁ and m ₂ cannot both be 0). In the general formula (iii), m ₁ and m ₂ are not particularly limited as long as the effects of the present invention are exerted, and integers can be used, but generally m ₁ + m ₂ = 1 to 10 It is preferable. Specific examples of the group represented by the general formula (iii) include polyethylene glycol monoacrylate (ethylene oxide group repeating number 2 to 10), polyethylene glycol monomethacrylate (ethylene oxide group repeating number 2 to 10), polyethylene glycol polypropylene glycol methacrylate. (Ethylene oxide group repeating number 7, Propylene oxide group repeating number 3),
There are residues of 2-hydroxyethyl methacrylate and 2-hydroxyethyl methacrylate.

Among the groups represented by the above general formulas (i) to (iii),
Particularly preferred groups are residues of pentaerythritol triacrylate, polyethylene glycol monomethacrylate (number of repeating ethylene oxide groups 4 to 7), and 2-hydroxyacrylate.

In the phosphazene compound, n ₁ , n ₂ , n ₃ , n ₄ and n ₅ are the same or different integers. However,
If this _{n 1, n 2, n 3} , n 4 and n ₅ is 21 or more, the viscosity of the phosphazene compound is high, generally because workability of the curable composition using the compound tends to decrease Is 1
An integer of 20 is preferable, and an integer of 2 to 8 is preferable.

The method for producing the specific cyclic phosphazene compound represented by the above general formula in the present invention is not particularly limited, but the following methods are shown as preferable methods. That is,
First, as shown above, the residues are represented by the general formulas (i) to (ii).
Metal sodium is reacted with the compound which becomes the group represented by i) to synthesize sodium alkoxide of acrylic acid ester or methacrylic acid ester. Similarly, a sodium alkoxide of polyethylene glycol monomethyl ether is synthesized by reacting polyethylene glycol monomethyl ether alone or a mixture of polyethylene glycol monomethyl ether having different repeating numbers of ethylene oxide groups with sodium metal.

Next, 1 mol of hexachlorocyclotriphosphazene is reacted with 1 mol of the sodium alkoxide of the above acrylic acid ester or methacrylic acid ester. The specific cyclic phosphazene compound can be obtained by reacting 1 mol of the finally obtained reaction product with 5 mol of the sodium alkoxide of polyethylene glycol monomethyl ether.

These reactions are usually performed in an organic solvent. Examples of the organic solvent used include tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane and the like, and these can be used alone or in combination. Further, since these reactions are carried out in the absence of water, a dehydrated organic solvent is used.

The specific cyclic phosphazene compound represented by the general formula used in the present invention is a yellow viscous liquid at room temperature and normal pressure, and by gel permeation chromatography,
The molecular weight can be calculated. The structure of the phosphazene compound can be confirmed by infrared absorption spectrum, ¹ H-nuclear magnetic resonance spectrum and elemental analysis. That is, by measuring the infrared absorption spectrum,
The phosphazene compound, a peak derived from the 1040 cm ^-1 to PO-CH _2, peaks derived from C = C to 1630 cm ^-1, 1705 cm ^-1
A peak derived from C = O and a peak derived from P = N are observed at 1250 cm ^-1 . Further, by measuring the ¹ H-nuclear magnetic resonance spectrum, each proton species belonging to the molecular structure can be detected from the chemical shift value. Furthermore,
By performing elemental analysis, the weight% of carbon, hydrogen, and nitrogen constituting the compound can be obtained. The above weight% of the phosphazene compound used in the present invention is 40 to 40% carbon.
50% by weight, 5-10% by weight hydrogen, 0.1-3.5% by weight nitrogen.

By combining the specific cyclic phosphazene compound represented by the above general formula of the present invention with an alkali metal salt and a polymerization initiator, the cured product can be used for a curable composition having good ionic conductivity.

Therefore, the present invention provides (a) the general formula Also provided is a curable composition comprising 100 parts by weight of a phosphazene compound represented by (b) 1 to 50 parts by weight of an alkali metal salt and (c) 0.1 to 10 parts by weight of a polymerization initiator.

The alkali metal salt used in the curable composition is not particularly limited. Typical alkali metal salts include perchlorates such as LiClO ₄ and KClO ₄ , LiBF ₄ and
Examples thereof include borofluoric acid salts such as KBF ₄ , thiocyanic acid salts such as LiSCN and KSCN, and among these, LiClO ₄ is particularly preferably used. The amount of the alkali metal salt added is 1 to 50 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the phosphazene compound. When the amount of the alkali metal salt added is less than 1 part by weight, the ionic conductivity of the cured product of the resulting curable composition is insufficient, and even when it is greater than 50 parts by weight, the ionic conductivity is rather lowered. .

As the polymerization initiator used in the curable composition, known ones are used without particular limitation. For example,
Photo-curable polymerization initiators such as acetophenone, benzophenone, benzyl, 2-chlorothioxanthone and allyl ketone compounds, and thermosetting polymerization initiators such as benzoyl peroxide and azobisisobutyronitrile are generally used. Among them, allocylketone compounds, and Darocur 1664 (Merck Japan KK) as a product name are particularly preferable.
The amount of the polymerization initiator added is the above-mentioned phosphazene compound.
It is used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight, but the preferred amount is in the range of 0.2 to 5 parts by weight. If the amount of the polymerization initiator added is less than 0.1 parts by weight, curing will not proceed sufficiently, and if it is more than 10 parts by weight, yellowing will occur after curing.

The curable composition of the present invention is cured by being subjected to a treatment such as irradiation with light or heating depending on the curing type of the polymerization initiator to be added.

Further, the curable composition may be blended with other additives such as polyethylene glycol, polypropylene glycol, pigments, curing agents, defoaming agents, etc. within a range that does not significantly deteriorate the characteristics.

〔effect〕

The curable composition using the specific cyclic phosphazene compound of the present invention, the cured product has good ionic conductivity of 10 ^-4 ~ 10 ^-5 s / cm, various fields in which a solid electrolyte is desired. It is used without particular limitation. In particular, when used when forming an electrolyte layer on an electrode of an electrochromic display element or a battery, while having excellent electric characteristics, the electrode can be used after being cured after being adjusted with a viscous liquid, so that workability, The fine formability and the adhesiveness of the cured product to the electrode are also good, which is extremely useful.

〔Example〕

Examples are shown below for specifically explaining the present invention, but the present invention is not limited to these examples.

Example 1 In a 1 liter flask equipped with a thermometer, a stirrer, a dropping funnel and a condenser, 50 ml of dehydrated tetrahydrofuran, 11.6 g of 2-hydroxyethyl acrylate (manufactured by Tokyo Kasei Co., Ltd.) and 2.3 g of metallic sodium were added and stirred. Then reacted. After all the metal sodium had reacted, 34.8 g of hexachlorocyclotriphosphazene (3PNC manufactured by Nippon Soda Co., Ltd.) was dissolved in 200 ml of dehydrated tetrahydrofuran in this reaction solution, and the solution was gradually added dropwise using a dropping funnel. did. After dropping, heat to reflux under stirring for 24 hours.
Reacted for hours. After this, the precipitated sodium chloride crystals were filtered off. All the above reactions were performed under a nitrogen stream. Next, in another 1-liter flask equipped with a thermometer, a stirrer, a dropping funnel and a condenser, 50 ml of dehydrated tetrahydrofuran, 82.1 g of triethylene glycol monomethyl ether (manufactured by Tokyo Kasei Co., Ltd.) and sodium metal 11.
8 g was added, and the mixture was stirred and reacted under a nitrogen stream. After all the sodium metal had reacted, the reaction product of hexachlorocyclotriphosphazene and 2-hydroxyethyl acrylate described above was gradually added dropwise to this reaction solution using a dropping funnel. After the dropping, the mixture was heated under reflux with stirring and reacted for 72 hours. The following reactions were all performed under a nitrogen stream.
After that, the precipitated sodium chloride crystals were filtered off, the organic solvent in the filtrate was removed by concentration under reduced pressure, and the residue was dried to obtain a yellow liquid.

When the molecular weight of the obtained yellow liquid was measured by gel permeation chromatography, it was about 1000.

In addition, when the infrared absorption spectrum was measured, it was 1040 cm ^-1.
Peak derived from P-OCH ₂ , 1630 cm ⁻¹ derived from C═C, 1705 cm ⁻¹ derived from C═O, 1250 cm
A peak derived from P = N was observed at ^-1 . A proton species assigned to the following molecular structure was detected from its chemical shift value by ¹ H-nuclear magnetic resonance spectrum.

CH ₂ =: 5.9 to 6.1ppm (2H) C = CH-6.2ppm (1H) -COOCH ₂ -and -POCH _2- : 4.1 to 4.4ppm (14H) -OCH ₃ : 3.4ppm (15H) -CH ₂ : 3.7-4.0ppm (60H) Elemental analysis showed that C: 43.8wt%, H; 6.9wt%,
N: 4.2% by weight.

From the above results, the obtained yellow liquid, Was confirmed.

Example 2 Using the reaction apparatus shown in Example 1, 50 ml of dehydrated 1,2-dimethoxyethane, 11.6 g of pentaerythritol acrylate (Osaka Organic Co., Ltd. viscoat # 300) and 2.3 g of metallic sodium were added and stirred to react. It was After the reaction of all metallic sodium was completed, hexachlorocyclotriphosphazene (3PNC manufactured by Nippon Soda Co., Ltd.) 3 was added to the reaction solution.
A solution prepared by dissolving 4.8 g in 200 ml of dehydrated 1,2-dimethoxyethane was gradually added dropwise using a dropping funnel. After the dropping, the mixture was heated under reflux with stirring and reacted for 24 hours. After this, the precipitated sodium chloride crystals were filtered off. All the above reactions were performed under a nitrogen stream. Next, in another 1 liter flask equipped with a thermometer, a stirrer, a dropping funnel and a condenser, dehydrated 1,2-dimethoxyethane 150 ml, polyethylene glycol monomethyl ether (average molecular weight 350, made by Aldrich) 175 g and metallic sodium 11.8 g was added and the mixture was stirred and reacted under a nitrogen stream. After all the sodium metal had reacted, the reaction product of hexachlorocyclotriphosphazene and pentaerythritol triacrylate described above was gradually added dropwise to this reaction solution using a dropping funnel. After the dropping, the mixture was heated under reflux with stirring and reacted for 72 hours. All the above reactions were performed under a nitrogen stream. After that, the precipitated sodium chloride crystals were filtered off, the organic solvent in the filtrate was removed by concentration under reduced pressure, and the residue was dried to obtain a yellow liquid.

The molecular weight of the obtained yellow liquid was measured by gel permeation chromatography and found to be about 2,000.

In addition, when the infrared absorption spectrum was measured, it was 1040 cm ^-1.
Peak derived from P-OCH ₂ , 1630 cm ⁻¹ derived from C═C, 1705 cm ⁻¹ derived from C═O, 1250 cm
A peak derived from P = N was observed at ^-1 . A proton species belonging to the following molecular structure was detected from its chemical shift value by ¹ H-nuclear magnetic resonance spectrum.

CH ₂ =: 5.8 to 6.3ppm (2H) C = CH-: 6.1ppm (1H) -COOCH ₂ -and -POCH _2- : 4.1 to 4.4ppm (14H) -OCH ₃ : 3.4ppm (15H) -CH ₂ : 3.5-3.7ppm (135H) Elemental analysis showed C: 48.4wt%, H; 7.8wt%,
N: 2.3% by weight.

From the above results, the obtained yellow liquid is a compound in which 6 chlorine atoms of hexachlorocyclotriphosphazene are substituted with 1 pentaerythritol triacrylate residue and 5 polyethylene glycol monomethyl ether residues. It was confirmed.

Example 3 Using the reactor shown in Example 1, 50 ml of dehydrated 1,2-dimethoxyethane, polyethylene glycol monomethacrylate (molecular weight 261 to 303, NOF CORPORATION Blemmer PE) were used.
350) 30.3 g and sodium metal 2.3 g were added, and the mixture was stirred and reacted. After all the metallic sodium had reacted, 34.8 g of hexachlorocyclotriphosphazene (3PNC manufactured by Nippon Soda Co., Ltd.) was dissolved in 200 ml of dehydrated 1,2-dimethoxyethane, and a dropping funnel was added to the reaction solution. It was gradually added dropwise. After the dropping, the mixture was heated under reflux with stirring and reacted for 24 hours. After this, the precipitated sodium chloride crystals were filtered off. All the above reactions were performed under a nitrogen stream. Next, in another 1 liter flask equipped with a thermometer, a stirrer, a dropping funnel and a condenser, dehydrated 1,2-dimethoxyethane 150 ml, polyethylene glycol monomethyl ether (average molecular weight 350, made by Aldrich) 175 g and metallic sodium 11.8 g was added and the mixture was stirred and reacted under a nitrogen stream.
After all the sodium metal had reacted, the reaction product of hexachlorocyclotriphosphazene and polyethylene glycol monomethacrylate described above was gradually added dropwise to the reaction solution using a dropping funnel. After the dropping, the mixture was heated under reflux with stirring and reacted for 72 hours. All the above reactions were performed under a nitrogen stream. After that, the precipitated sodium chloride crystals were filtered off, the organic solvent in the filtrate was removed by concentration under reduced pressure, and the residue was dried to obtain a yellow liquid.

When the molecular weight of the obtained yellow liquid was measured by gel permeation chromatography, the molecular weight was about
It was 2000.

In addition, when the infrared absorption spectrum was measured, it was 1040 cm ^-1.
Peak derived from P-OCH ₂ , 1630 cm ⁻¹ derived from C═C, 1705 cm ⁻¹ derived from C═O, 1250 cm
A peak derived from P = N was observed at ^-1 . A proton species belonging to the following molecular structure was detected from its chemical shift value by ¹ H-nuclear magnetic resonance spectrum.

_{CH 2 =: 5.6~6.1ppm (2H)} C = CH-CH 3: 2.0ppm (3H) -COOCH 2 - and _{-POCH 2 -: 4.1~4.4ppm (14H)} -OCH 3: 3.4ppm (15H) - CH ₂ −: 3.7ppm (151H) Elemental analysis showed that C: 46.8wt%, H; 8.5wt%,
N: 2.3% by weight.

From the above results, the obtained yellow liquid is a compound in which 6 chlorine atoms of hexachlorocyclotriphosphazene are substituted with 1 polyethylene glycol monomethacrylate residue and 5 polyethylene glycol monomethyl ether residues. It was confirmed.

Example 4 Using the reaction apparatus shown in Example 1, 50 ml of dehydrated 1,2-dimethoxysilane, polyethylene glycol polypropylene glycol methacrylate (molecular weight 567 ethylene oxide group repeating number 7 propylene oxide group repeating number 3 manufactured by NOF Corporation) 57PEP-350B) 57 g and metallic sodium 2.3 g were added and reacted with stirring. After all the metal sodium has reacted, hexachlorocyclotriphosphazene (3PNC manufactured by Nippon Soda Co., Ltd.) is added to the reaction solution.
A solution prepared by dissolving 34.8 g in 200 ml of dehydrated 1,2-dimethoxyethane was gradually added dropwise using a dropping funnel. After dropping
The mixture was heated under reflux with stirring and reacted for 24 hours. After this, the precipitated sodium chloride crystals were filtered off. All the above reactions were performed under a nitrogen stream. Next, in another 1 liter flask equipped with a thermometer, a stirrer, a dropping funnel and a condenser, dehydrated 1,2-dimethoxyethane 150 ml, polyethylene glycol monomethyl ether (average molecular weight 550, made by Aldrich) 375 g and metallic sodium 11.8 g was added and the mixture was stirred and reacted under a nitrogen stream. After all the metallic sodium had reacted, the reaction product of hexachlorocyclotriphosphazene (3PNC manufactured by Nippon Soda Co., Ltd.) and polyethylene glycol polypropylene glycol methacrylate was gradually added to this reaction solution using a dropping funnel. Was added dropwise. After the dropping, the mixture was heated under reflux with stirring and reacted for 72 hours. All the above reactions were performed under a nitrogen stream. After that, the precipitated sodium chloride crystals were filtered off, the organic solvent in the filtrate was removed by concentration under reduced pressure, and the residue was dried to obtain a yellow liquid.

When the molecular weight of the obtained yellow liquid was measured by gel permeation chromatography, the molecular weight was about
It was 3500.

In addition, when the infrared absorption spectrum was measured, it was 1040 cm ^-1.
Peak derived from P-OCH ₂ , 1630 cm ⁻¹ derived from C═C, 1705 cm ⁻¹ derived from C═O, 1250 cm
A peak derived from P = N was observed at ^-1 . A proton species belonging to the following molecular structure was detected from its chemical shift value by ¹ H-nuclear magnetic resonance spectrum.

_{CH 2 =: 5.6~6.1ppm (2H)} C = CH-CH 3: 2.0ppm (3H) -C-CH 3: 1.2ppm (9H) -COOCH 2 - and -POCH ₂ -: 4.1~4.4ppm (14H ) −OCH ₃ : 3.4ppm (15H) −CH ₂ −: 3.7〜4.0ppm (253H) Elemental analysis showed C: 51.8wt%, H; 8.6wt%,
N: 0.8% by weight.

From the above results, the obtained yellow liquid is a compound in which 6 chlorine atoms of hexachlorocyclotriphosphazene are substituted with 1 polyethylene glycol polypropylene glycol methacrylate residue and 5 polyethylene glycol monomethyl ether residues. I confirmed that there is.

Example 5 The curable composition was obtained by blending the polyphosphazene compounds obtained in Examples 1 to 4, the alkali metal salt and the polymerization initiator in the proportions shown in Table 1. Regarding the obtained curable compositions, Nos. 1 to 6 and Nos. 8 and 9 were photocured between ITO electrodes, and the ionic conductivity was measured using an Impedice Analyzer (manufactured by Hewlett Packard, 4192A). In addition, No7 is cured by heating between ITO electrodes at 80 ℃ for 30 minutes,
The ionic conductivity was measured using the above impedance analyzer. The results are shown in Table 1.

Example 6 An electrochromic display device was prepared using the phosphazene compound obtained in Example 2.

A glass plate with ITO having a sheet resistance of 20 Ω / cm ² was used as a display electrode, and 5 × 5 mm square tungsten oxide was vacuum-deposited to a thickness of about 4500 Å to form an electrochromic material layer (hereinafter referred to as an EC layer). Abbreviated) was formed.

To 100 parts by weight of the phosphazene compound obtained in Example 2, 10 parts by weight of lithium perchlorate was added and dissolved. 3 parts by weight of Darocur 1664 (manufactured by Merck Japan Ltd.) was added to this and mixed uniformly. Furthermore, titania (product name A-220
30 parts by weight of Ishihara Sangyo Co., Ltd. was added and dispersed evenly.
A white paste composition was obtained.

As a counter electrode, 100 parts by weight of white conductive powder W-1 (product name, Mitsubishi Metals Co., Ltd.) and 25 parts by weight of epoxy binder Epicoat 828 (product name, Yuka Shell Epoxy Co., Ltd.)
0.4 parts by weight of an epoxy resin curing agent, Curesol-2MZ (product name, Shikoku Chemicals Co., Ltd.) was added, and terpineol for adjusting the viscosity was further added and mixed well to obtain a paste composition.

As a current collector, carbon paste FTU-20 (product name,
Asahi Chemical Laboratory Co., Ltd. was used.

First, the above-mentioned electrolyte is screen-printed on the EC layer in a square shape of 5 × 5 mm and cured by light to form an electrolyte layer, and then the above-mentioned counter electrode is formed on the electrolyte layer in a square shape of 5 × 5 mm. Screen printing was carried out, and the film was dried and cured by heating at 80 ° C. for 30 minutes to form a counter electrode layer. Finally, the above-mentioned current collector was screen-printed on the counter electrode layer in a square shape of 5 × 5 mm to form a current collector layer, thereby preparing an ECD element. When a square wave voltage of ± 1.5 V was applied between both electrodes of the above element for a period of 1 second, a bright blue to white color fading was observed, and this vivid color fading continued 1 × 10 ⁶ times or more. did. During that time, peeling did not occur between the electrolyte layer and the EC layer and between the electrolyte layer and the counter electrode layer.

Claims (2)

[Claims] 1. A general formula: A phosphazene compound represented by. 2. (a) General formula 100 parts by weight of the phosphazene compound represented by (b) 1 to 50 parts by weight of alkali metal salt, and (c) 0.1 to 10 parts by weight of a polymerization initiator.