JPH11255832A - Phosphorus atom-containing polymerizable compound, preparation thereof and photocurable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide phosphorus atom-containing polymerizable compounds, a method for preparing the same and photocurable compositions. SOLUTION: Desired phosphorus atom-containing polymerizable compounds are represented by the formula (wherein R<1> is phenyl, phenoxy or propyl; R<2> is 1-4C alkyl; and X is Cl, chlorophenoxy or nitrophenoxy). These compounds can be prepared by the addition reaction of a 1-alkenyl glycidyl ether to an phosphonic acid ester. Polycondensation reaction products of these phosphorus atom-containing polymerizable compounds with dicarboxylic acids or (meth) acrylic acid are included in these phosphorus atom-containing polymerizable compounds. Photocurable compositions comprise said phosphorus atom-containing polymerizable compounds and a photo-acid generator which generates an acid with light.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a phosphorus atom-containing polymerizable compound, a method for producing the same, and a photocurable composition.

[0002]

2. Description of the Related Art At present, in the field of surface processing technology such as ink and photoresist, the use of an ultraviolet curing reaction is widely performed. In the technology utilizing this ultraviolet curing reaction, conventionally, photoradical polymerization using an acrylic monomer as a polymerizable component has been used, but in photoradical polymerization, the polymerization reaction is inhibited by oxygen in the atmosphere. There is a problem. From such a viewpoint, use of photocationic polymerization without polymerization inhibition by oxygen has recently been proposed and studied. In this cationic photopolymerization, an epoxy compound, a vinyl ether compound, or the like is used as a polymerizable compound, and a vinyl ether compound is particularly advantageous because it has a high curing rate by irradiation with ultraviolet rays.

On the other hand, in a photocurable composition, it is required that a polymer after curing has flame retardancy.
Since such a polymer has the advantage of being photocurable and can be advantageously used as an electrically insulating material or a heat-resistant material used in a high-temperature atmosphere, particularly a flame-retardant coating forming material, It is a very useful material.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made based on the above circumstances, and its object is to provide:
A polymerizable compound having good photocurability and a cured product having flame retardancy, specifically, a phosphorus atom-containing polymerizable compound which contains a phosphorus atom and can be cured by photocationic polymerization. It is to provide a compound. Another object of the present invention is to provide a method for producing such a phosphorus atom-containing polymerizable compound. Another object of the present invention is to
An object of the present invention is to provide a photocurable composition containing the polymerizable compound containing a phosphorous atom.

[0005]

The first of the phosphorus atom-containing polymerizable compounds of the present invention is a compound represented by the following general formula 1.

[0006]

Embedded image In the formula, R ¹ represents a phenyl group, a phenoxy group or a propyl group; R ² represents an alkyl group having 1 to 4 carbon atoms;
Represents a halogen atom, a chlorphenoxy group, a phenoxy group or a nitrophenoxy group. Examples of the alkyl group having 1 to 4 carbon atoms represented by R ² include a methyl group, an ethyl group, n
Examples thereof include -propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group and the like, preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

[0007] The above-mentioned phosphorus atom-containing polymerizable compound is 1-
It can be produced by an addition reaction of alkenyl glycidyl ether and phosphonic acid ester.

[0008] The phosphorus atom-containing polymerizable compound of the present invention is characterized by having a structural unit represented by the following general formula 2.

[0009]

Embedded image In the formula, R ¹ represents a phenyl group, a phenoxy group or a propyl group; R ² represents an alkyl group having 1 to 4 carbon atoms;
³ represents a phenylene group, a butylene group, -CH = CH-, or -CH = CH-CH = CH-, and n is an integer of 1 or more. Among the alkyl groups represented by R ² , preferred are a methyl group and an ethyl group, and particularly preferred is a methyl group.

The above-mentioned phosphorus atom-containing polymerizable compound is 1-
The addition reaction product obtained by the addition reaction between the alkenyl glycidyl ether and the phosphonic acid ester can be produced by a polycondensation reaction with a dicarboxylic acid.

[0011] The phosphorus atom-containing polymerizable compound of the present invention is a compound represented by the following general formula 3.

[0012]

Embedded image In the formula, R ¹ represents a phenyl group, a phenoxy group or a propyl group; R ² represents an alkyl group having 1 to 4 carbon atoms;
Represents a hydrogen atom or a methyl group. Examples of the alkyl group having 1 to 4 carbon atoms represented by R ² include a methyl group, an ethyl group,
n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group and the like,
It is preferably a methyl group or an ethyl group, and particularly preferably a methyl group.

The above phosphorus atom-containing polymerizable compound is 1-
It can be produced by a method in which an addition reaction product obtained by an addition reaction between an alkenyl glycidyl ether and a phosphonic acid ester is subjected to a condensation reaction with acrylic acid or methacrylic acid.

The photocurable composition of the present invention contains a phosphorus atom-containing polymerizable compound represented by the above general formula 1, 2 or 3 and a photoacid generator which generates an acid by light. It is characterized by becoming.

According to the present invention, a novel phosphorus atom-containing polymerizable compound is provided. By mixing the photoacid generator with the polymerizable compound, a photocurable composition that is cured by photocationic polymerization by irradiation with ultraviolet light is obtained.
The cured product of this photocurable composition becomes flame-retardant due to the inclusion of phosphorus atoms. Further, according to the production method of the present invention, the above-mentioned phosphorus atom-containing polymerizable compound can be produced.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the phosphorus atom-containing polymerizable compound of the present invention, a method for producing the same, and a photocurable composition will be specifically described. In the present invention, as shown in the following reaction formula 1, 1-alkenyl glycidyl ether (AGE) and an appropriate phosphonic acid ester (PA
An addition reaction with E) takes place. By this addition reaction, the phosphorus atom-containing monomer of the present invention is obtained.

[0017]

Embedded image Here, R ¹ , R ² and X are the same as in the above-mentioned general formula 1.

This addition reaction is carried out in an appropriate solvent
This can be achieved by using a quaternary onium salt as a catalyst. Here, specific examples of the solvent include toluene, chlorobenzene, anisole, ethyl acetate, methyl cellosolve acetate, N-methylpyrrolidone, N,
N-dimethylacetamide, dimethylsulfoxide, o
-Dichlorobenzene and others. Specific examples of the quaternary onium salt used as a catalyst include, for example, tetra-n-butylammonium bromide (TBA
B), tetra-n-butylphosphonium chloride (T
BPC), tetrabutylammonium chloride (TB
AC), tetrapropylammonium bromide (TPA
B), benzyltriethylammonium chloride (B
TEAC) and others. Also, 18
-Crown-6-ether and a salt such as potassium bromide, potassium chloride, cesium chloride, potassium phenoxide, sodium phenoxide, potassium benzoate and the like can also be used as a catalyst. The amount of these catalysts used is usually 1 to 20% by weight, preferably 5 to 10% by weight, based on the total amount of 1-alkenyl glycidyl ether and phosphonic acid ester. The reaction temperature of this addition reaction is usually 60 to 180 ° C, preferably 80 to 180 ° C.
The temperature is 150 ° C, more preferably 80 to 120 ° C, and the reaction time is usually 6 to 96 hours.

By the above addition reaction, a first phosphorus atom-containing polymerizable compound represented by the general formula 1 (hereinafter referred to as "phosphorus atom-containing monomer") is obtained. This phosphorus atom-containing monomer has two propenyl groups having a polymerizable double bond.
It is a so-called polyfunctional polymerizable monomer because it contains a photocurable composition which is cured by irradiation with ultraviolet rays by mixing an appropriate photoacid generator, as described later.

The above-mentioned phosphorus atom-containing monomer can be further subjected to a polycondensation reaction with a dicarboxylic acid as shown in the following reaction formula 2. By this polycondensation reaction, the phosphorus atom-containing oligomer of the present invention is obtained.

[0021]

Embedded image Here, R ³ is the same as in the general formula 2.

This polycondensation reaction can be carried out in a suitable solvent using a suitable condensing agent. Here, as the solvent, those similar to those in the above-mentioned addition reaction can be used. Specific examples of the condensing agent include, for example, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) and 1,5-diazabicyclo [4.3.0] non-5-ene (DBN). ) And others.

By this polycondensation reaction, a second phosphorus atom-containing polymerizable compound represented by the general formula 2 according to the present invention (hereinafter referred to as "phosphorus atom-containing oligomer") is obtained. This phosphorus atom-containing oligomer is a so-called polyfunctional polymerizable monomer because it contains two propenyl groups having a polymerizable double bond, like the above-mentioned phosphorus atom-containing monomer. By mixing a suitable photoacid generator, a photocurable composition that is cured by irradiation with ultraviolet light can be obtained.

A photocurable composition comprising the above-mentioned phosphorous atom-containing monomer or phosphorous atom-containing oligomer and an appropriate photoacid generator is prepared by photocationic polymerization by ultraviolet irradiation and curing. Having. The cured product obtained here has excellent flame retardancy due to being a polymer containing a phosphorus atom, and is therefore an electrically insulating material or a heat-resistant material used under a high-temperature atmosphere. Can be used advantageously.

The photoacid generator generates an acid upon irradiation with light. As a photoacid generator for the above-mentioned phosphorus atom-containing monomer or phosphorus atom-containing oligomer, a Bronsted-type acid is irradiated with light. Those generated are preferred, and specific examples thereof include bis [4- (diphenylsulfoniophenyl) sulfide-bis (hexafluorophosphate) (DPSP), triphenylsulfonium-hexafluorophosphate, triphenylsulfonium-tetrafluoroborate, Triphenylsulfonium-hexafluoroantimonate, etc. The photoacid generator may be used in an amount of 1 to 3 in the phosphorus atom-containing monomer or the phosphorus atom-containing oligomer.
The amount thereof is 0.01 to 5 mol%, preferably 0.1 to 1 mol%, based on the propenyl ether group.

Further, as shown in the following reaction formula 3, the third phosphorus atom-containing polymerizable compound of the present invention (hereinafter referred to as “phosphorus Called "atom-containing hybrid monomer").

[0027]

Embedded image Here, R ¹ , R ² , X and Y are the same as defined above.

The conditions for this condensation reaction are the same as those for the polycondensation reaction according to the above-mentioned reaction formula 2, and the reaction is carried out in the presence of an appropriate condensing agent. A photocurable composition can also be obtained by mixing a phosphorus-containing hybrid monomer obtained here with a photoacid generator that generates an acid by light. Here, as the photoacid generator, those which generate the Bronsted-type acid described above are preferable.

In particular, it is preferable to coexist a photoradical polymerization agent together with the photoacid generator for the phosphorus atom-containing hybrid monomer. Specific examples of the photoradical polymerization agent include, for example, 2-methyl-1- [4- (methylthio)
Phenyl] -2-morpholinopropane-1 (MMP),
Benzophenone, benzoin alkyl ether, 2-alkylanthraquinone, benzyl and others can be mentioned. The compounding amount of the photoradical polymerization agent with respect to the phosphorus atom-containing hybrid monomer is preferably 1 to 10 mol%, particularly preferably 3 to 8 mol%, based on the (meth) acryloyl group of the phosphorus atom-containing hybrid monomer.

[0030]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. In addition, 1-propenyl glycidyl ether used below is, for example, using allyl glycidyl ether as a raw material, which is used in a nitrogen gas atmosphere in the presence of tris (triphenylphosphine) ruthenium (II) dichloride, for example, at a temperature of 120 ° C By heating for 30 minutes.

EXAMPLE 1A Tetra-n-butylammonium bromide (TBAB), a quaternary onium salt, was placed in an ampoule tube as a catalyst.
After adding 5 mmol and drying, 10 mmol of 1-propenyl glycidyl ether and 5 mmol of phenylphosphonic dichloride (PPDC) were added together with 5 ml of toluene as a solvent. After the sample in the ampule tube was degassed, the sample was reacted in an oil bath at a temperature of 90 ° C. for 24 hours. The obtained reaction product was diluted with ethyl acetate, washed three times with distilled water, dried and concentrated, and then subjected to silica gel column chromatography using a 1: 3 mixed solvent of methyl ethyl ketone (MEK) and n-hexane as a developing solvent. By isolation and purification by chromatography, 1.74 g of a colorless transparent viscous liquid was obtained. The yield is 82%. The addition reaction products, infrared absorption spectrum, nuclear magnetic resonance absorption and elemental analysis, the general formula 1, R ¹ is a phenyl group, R ² is a methyl group, X is bis phosphorus atom-containing monomer is a chlorine atom [ 1- (chloromethyl) -2- (1-propenyloxy) ethyl] phenylphosphonate. This is referred to as Monomer 1.

Example 1B Photoacid generator bis [4- (diphenylsulfonio) phenyl] sulfide-bis (hexafluorophosphate) was added to the above monomer 1 in an amount of 1 mol% based on the 1-propenyl ether group. ) (DPSP) was added and mixed to prepare a photocurable composition 1. This photocurable composition 1 was applied to a potassium bromide plate, and the power consumption of the coating was 250 W
UV light from a high-pressure mercury lamp was irradiated for 60 seconds under the condition that the irradiation intensity at a wavelength of 360 nm was 6.8 mW / cm ² , the coating film was cured, and the conversion of 1-propenyl ether group measured by an infrared absorption method was confirmed. The rate was 84%. Also, a photocurable composition was prepared in the same manner except that the addition ratio of the photoacid generator to the 1-propenyl ether group was changed to 0.1 mol% and 0.5 mol%, and a similar curing experiment was performed. As a result, the conversion of the 1-propenyl ether group was 39% and 74%, respectively.

Example 2A 0.5 mmol of tetra-n-butylphosphonium chloride (TBPC) as a quaternary onium salt was used as a catalyst, and 10 mmol of 1-propenyl glycidyl ether and 5 mmol of phenyldichlorophosphate (PDCP) were used. The same treatment as in Example 1A described above was carried out in the same manner as in Example 1A, except that the mixture was used and the reaction was carried out at a temperature of 90 ° C. for 48 hours, to obtain 1.05 g of a colorless and transparent viscous liquid. The yield is 48%. According to the infrared absorption spectrum, nuclear magnetic resonance absorption and elemental analysis, the addition reaction product showed that in the general formula 1, R ¹ was a phenoxy group, R ² was a methyl group,
Bis [1- [1] of a phosphorus atom-containing monomer in which X is a chlorine atom
(Chloromethyl) -2- (1-propenyloxy) ethyl] phenyl phosphate. This is called monomer 2.

Example 2B The above-mentioned monomer 2 was used in the same manner as in Example 1B above.
A photocurable composition 2 was prepared by adding and mixing a photoacid generator in an amount of 1 mol% based on 1-propenyl ether group. When a light irradiation experiment was performed on this photocurable composition 2 in the same manner as in Example 1B, the coating film was cured, and the conversion of the 1-propenyl ether group measured by infrared absorption was 81%. .

Example 3A 0.5 mmol of tetra-n-butylammonium bromide (TBAB) as a quaternary onium salt was used as a catalyst, 10 mmol of 1-propenyl glycidyl ether and propyl phosphonic dichloride (PrPDC) were used.
Except that 5 mmol was used and the reaction was carried out at a temperature of 90 ° C. for 24 hours, the same treatment as in Example 1A described above was carried out to obtain 1.12 g of a colorless transparent viscous liquid. The yield is 57%. The addition reaction product was analyzed by infrared absorption spectrum, nuclear magnetic resonance absorption and elemental analysis to obtain a bis-phosphorus-containing monomer represented by the general formula 1 wherein R ¹ is a propyl group, R ² is a methyl group and X is a chlorine atom. 1- (chloromethyl) -2- (1-propenyloxy) ethyl] propylphosphonate was confirmed. This is designated as monomer 3.

Example 3B In the same manner as in Example 1B, except that the above monomer 3 was used.
A photocurable composition 3 was prepared by adding and mixing a photoacid generator in an amount of 1 mol% based on 1-propenyl ether group. When a light irradiation experiment was performed on this photocurable composition 3 in the same manner as in Example 1B, the coating film was cured, and the conversion of 1-propenyl ether group measured by infrared absorption was 33%. .

EXAMPLE 4 Tetra-n-butylphosphonium chloride (TBPC), a quaternary onium salt, was used as a catalyst in an ampoule tube.
After 0.5 mmol was added and dried, 15 mmol of 1-propenyl glycidyl ether and 5 mmol of bis (4-chlorophenyl) phenylphosphonate (BCPP) were added together with 5 ml of N-methylpyrrolidone (NMP) as a solvent. . After the sample in the ampule tube was degassed, the sample was reacted in an oil bath at a temperature of 110 ° C. for 48 hours. The obtained reaction product was diluted with ethyl acetate, washed three times with distilled water, dried and concentrated, and then subjected to silica gel column chromatography using a 2: 5 mixed solvent of ethyl acetate and n-hexane as a developing solvent. By isolation and purification, a yellow transparent viscous liquid 1.88 was obtained.
g was obtained. The yield is 62%. According to the infrared absorption spectrum, nuclear magnetic resonance absorption and elemental analysis, the addition reaction product thus obtained has, in general formula 1, R ¹ is a phenyl group, R ² is a methyl group, and X is a p-chlorophenoxy group. It was confirmed that the monomer was a phosphorus atom-containing monomer. This is designated as monomer 4. Example 1 was added to the monomer 4 described above.
Photocurable composition 4 prepared by adding and mixing a photoacid generator in an amount of 1 mol% in the same manner as in B, produced a cured film by the same ultraviolet irradiation.

Example 5 Bis (4-chlorophenyl) phenylphosphonate (B
An addition reaction was carried out in the same manner as in Example 4 except that diphenylphenylphosphonate (DPP) was used instead of (CPP), to obtain 1.17 g of a yellow transparent viscous liquid. The yield is 43%. The addition reaction product obtained here was analyzed by infrared absorption spectrum, nuclear magnetic resonance absorption and elemental analysis to find that in the general formula 1, R ¹ was a phenyl group,
It was confirmed that the monomer was a phosphorus atom-containing monomer in which R ² was a methyl group and X was a phenoxy group. This is designated as monomer 5. The above monomer 5 was replaced with 1 in the same manner as in Example 1B.
The photocurable composition 5 prepared by adding and mixing the photoacid generator in an amount of mol% produced a cured film by the same ultraviolet irradiation.

Example 6 Bis (4-chlorophenyl) phenylphosphonate (B
An addition reaction was carried out in the same manner as in Example 4 except that bis (4-nitrophenyl) phenylphosphonate (BNPP) was used instead of (CPP), to obtain 1.26 g of a yellow transparent viscous liquid. The yield is 34%. The addition reaction product obtained here was analyzed by infrared absorption spectrum, nuclear magnetic resonance absorption and elemental analysis to obtain R ¹
Is a phenyl group, R ² is a methyl group and X is a p-nitrophenoxy group. This is designated as monomer 6. In the above monomer 6,
The photocurable composition 6 prepared by adding and mixing a photoacid generator in an amount of 1 mol% in the same manner as in Example 1B produced a cured film by the same ultraviolet irradiation.

Example 7A 2 mmol of the monomer 1 obtained in Example 1A, 1 mmol of terephthalic acid, and 2,8-diazabicyclo [5.4.0] undecene-7 (DBU) as a condensing agent
Mmol and dimethyl sulfoxide (DMS
O) was placed in an eggplant flask, and the temperature was 70
The reaction was carried out for 48 hours in an oil bath at ℃. The reaction mixture was diluted with chloroform, washed with water six times, and concentrated by drying to obtain 0.90 g of a transparent yellow solid. The yield is 94%. Here, the charged molar ratio of the monomer 1 and the terephthalic acid is 2: 1. This polycondensation reaction product is
Infrared absorption spectrum, nuclear magnetic resonance absorption and elemental analysis, the general formula 2, R ¹ is a phenyl group, R ² is a methyl group, a phosphorus-containing oligomer R ³ is p- phenylene group, ¹ H- The average molecular weight calculated by NMR is 940, the number average molecular weight by gel permeation chromatography is about 3700, and the molecular weight distribution is 1.0
3 was confirmed. This is oligomer 1
And

Example 7B The above-mentioned oligomer 1 was prepared by adding a photoacid generator bis [4- (diphenylsulfonio) phenyl] sulfide-bis (hexafluorophosphate) in an amount of 1 mol% based on the 1-propenyl ether group. ) (DPSP) was added and mixed to prepare a photocurable composition 7. The oligomer 1
The number of moles of the -propenyl ether group can be determined from the degree of polymerization calculated from ¹ H-NMR. Using this photocurable composition 7, a power consumption of 250 was used in the same manner as in Example 1B.
When UV light from a high-pressure mercury lamp of W was irradiated for 300 seconds under the condition that the irradiation intensity at a wavelength of 360 nm was 6.8 mW / cm ² , the coating film was cured, and the conversion of 1-propenyl ether group measured by infrared absorption. The rate was 78%.

Example 8 1 mmol of terephthalic acid was replaced by 1 of isophthalic acid
Except for using mmol, the same treatment as in Example 7A was carried out to obtain 0.87 g of a transparent yellow solid. The yield is 92%.
This polycondensation reaction product is represented by the following general formula 2 by infrared absorption spectrum, nuclear magnetic resonance absorption and elemental analysis.
R ¹ is a phenyl group, R ² is a methyl group, a phosphorus-containing oligomer is R ³ is m- phenylene group, ¹ H-
The average molecular weight calculated from NMR is 940, and the number average molecular weight determined by gel permeation chromatography is about 35.
00, it was confirmed that the molecular weight distribution was 1.03. This is designated as oligomer 2. A light irradiation experiment was performed on the photocurable composition 8 prepared in the same manner as in Example 7B except for using the oligomer 2 in the same manner as in Example 7B. The coating film was cured and measured by infrared absorption. The conversion of the obtained 1-propenyl ether group was 80%.

Example 9 The procedure of Example 7A was repeated, except that 1 mmol of adipic acid was used instead of 1 mmol of terephthalic acid, to obtain 0.81 g of a yellow transparent solid. The yield is 87%. This polycondensation reaction product was represented by the following general formula 2 by the infrared absorption spectrum, nuclear magnetic resonance absorption and elemental analysis.
¹ is a phenyl group, R ² is a methyl group, a phosphorus atom-containing oligomer R ³ is a butylene group, the average molecular weight calculated by ¹ H-NMR is 920, the number average molecular weight by gel permeation chromatography is about 3900, It was confirmed that the molecular weight distribution was 1.03. This is designated as oligomer 3. A light irradiation experiment was performed in the same manner as in Example 7B on the photocurable composition 9 prepared in the same manner as in Example 7B except that this oligomer 3 was used. As a result, the coating film was cured and measured by infrared absorption. Done 1
The conversion of the propenyl ether groups was 80%.

Example 10 The procedure of Example 7A was repeated, except that 1 mmol of fumaric acid was used instead of 1 mmol of terephthalic acid, to obtain 0.67 g of a transparent yellow solid. The yield is 74%. This polycondensation reaction product was represented by R ¹ in the general formula 2 by infrared absorption spectrum, nuclear magnetic resonance absorption and elemental analysis.
Is a phenyl group, R ² is a methyl group, R ³ is —CH ＝ CH—
¹ H-NMR
The average molecular weight calculated from the above is 843, the number average molecular weight by gel permeation chromatography is about 3600,
It was confirmed that the molecular weight distribution was 1.03.
This is designated as oligomer 4. Photocurable composition 8 prepared in the same manner as in Example 7B except that oligomer 4 was used.
Was subjected to a light irradiation experiment in the same manner as in Example 7B. As a result, the coating film was cured, and the conversion of the 1-propenyl ether group measured by infrared absorption was 50%.

Example 11 The procedure of Example 7A was repeated except that 1 mmol of terephthalic acid was replaced by 1 mmol of muconic acid to obtain 0.87 g of a yellow transparent solid. The yield is 94%. This polycondensation reaction product was represented by R ¹ in the general formula 2 by infrared absorption spectrum, nuclear magnetic resonance absorption and elemental analysis.
Is a phenyl group, R ² is a methyl group, R ³ is —CH ＝ CH—
A phosphorus atom-containing oligomer wherein CH = CH-,
It was confirmed that the average molecular weight calculated from ¹ H-NMR was 670, the number average molecular weight by gel permeation chromatography was about 5500, and the molecular weight distribution was 1.22. This is designated as oligomer 5. The photocurable composition 8 prepared in the same manner as in Example 7B except that this oligomer 5 was used was subjected to a light irradiation experiment in the same manner as in Example 7B. The coating film was cured and measured by infrared absorption. The conversion of the 1-propenyl ether group thus obtained is 22.
%Met.

EXAMPLE 12A 6 mmol of methacrylic acid, a trace amount of phenothiazine, 6 mmol of 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) as a condensing agent, and dimethyl sulfoxide as a solvent were placed in an eggplant flask. DMSO) 5
After adding milliliter and stirring at room temperature for 30 minutes, 2 mmol of the monomer 1 obtained in Example 1A was added and reacted in an oil bath at a temperature of 70 ° C. for 24 hours. The reaction mixture was diluted with chloroform, washed six times with water, dried and concentrated, and then used as a developing solvent in chloroform and acetone.
Isolation and purification by silica gel column chromatography using a 0: 1 mixed solvent gave 0.51 g of a colorless and transparent liquid. The yield is 48%. The addition reaction product was confirmed by infrared absorption spectrum, nuclear magnetic resonance absorption and elemental analysis to be a phosphorus atom-containing hybrid monomer in which R ^{1 in} Formula 3 was a phenyl group and R ² was a methyl group. This is designated as hybrid monomer 1.

Example 12B The above-mentioned hybrid monomer 1 was added to the above-mentioned mixed monomer 1 in an amount of 5 mol% based on the 1-propenyl ether group of the photoacid generator bis [4-
(Diphenylsulfonio) phenyl] sulfide-bis (hexafluorophosphate) (DPSP) and a photo-radical polymerizing agent 2-methyl-1- [4- (methylthio) phenyl in an amount of 5 mol% based on the methacryloyl group ] -2-morpholinopropane-1 (MMP) was added and mixed to prepare a photocurable composition 12. Using this photocurable composition 12, a power consumption of 250 was used in the same manner as in Example 1B.
When irradiated with ultraviolet light from a high-pressure mercury lamp of W under the condition that the irradiation intensity at a wavelength of 360 nm was 6.8 mW / cm ² for 180 seconds, the coating film was cured, and the 1-propenyl ether group of the 1-propenyl ether group measured by an infrared absorption method was cured. Conversion rate is 13%,
The conversion of the methacryloyl group was 68%.

[0048]

As described above, according to the present invention, there is provided a novel phosphorus atom-containing polymerizable compound having a polymerization reactivity which contains a phosphorus atom and can be cured by cationic photopolymerization. Since this compound has flame retardancy as its characteristic, it can be advantageously used for forming a flame retardant coating. Further, according to the present invention, there is provided a method capable of advantageously producing the above-mentioned phosphorus atom-containing polymerizable compound. Further, according to the present invention, it is possible to provide a photocurable composition which is polymerized and cured by irradiation of ultraviolet rays with the above-mentioned phosphorus atom-containing polymerizable compound and photoacid generator.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // C08G 79/04 C08G 79/04 C09D 4/00 C09D 4/00

Claims (7)

[Claims] 1. A phosphorus atom-containing polymerizable compound represented by the following general formula 1. Embedded image In the formula, R ¹ represents a phenyl group, a phenoxy group or a propyl group; R ² represents an alkyl group having 1 to 4 carbon atoms;
Represents a halogen atom, a chlorphenoxy group, a phenoxy group or a nitrophenoxy group. 2. A method for producing a phosphorus atom-containing polymerizable compound according to claim 1, wherein the 1-alkenyl glycidyl ether and a phosphonic acid ester are subjected to an addition reaction to obtain the phosphorus atom-containing polymerizable compound according to claim 1. . 3. A phosphorus atom-containing polymerizable compound having a structural unit represented by the following general formula 2. Embedded image In the formula, R ¹ represents a phenyl group, a phenoxy group or a propyl group; R ² represents an alkyl group having 1 to 4 carbon atoms;
³ represents a phenylene group, a butylene group, -CH = CH-, or -CH = CH-CH = CH-, and n is an integer of 1 or more. 4. The phosphorus atom-containing polymerizable compound according to claim 3, which is obtained by subjecting an addition reaction product obtained by addition reaction between 1-alkenyl glycidyl ether and phosphonic acid ester to polycondensation reaction with dicarboxylic acid. A method for producing a phosphorus atom-containing polymerizable compound, comprising: 5. A phosphorus atom-containing polymerizable compound represented by the following general formula 3. Embedded image In the formula, R ¹ represents a phenyl group, a phenoxy group or a propyl group; R ² represents an alkyl group having 1 to 4 carbon atoms;
Represents a hydrogen atom or a methyl group. 6. The phosphorus atom-containing polymerizable compound according to claim 5, wherein the addition reaction product obtained by the addition reaction of the 1-alkenyl glycidyl ether and the phosphonic acid ester is subjected to a condensation reaction with acrylic acid or methacrylic acid. A method for producing a phosphorus atom-containing polymerizable compound, comprising: 7. Photocuring comprising the phosphorus atom-containing polymerizable compound according to claim 1, 3 or 5, and a photoacid generator that generates an acid by light. Composition.