JP2002241383A - Method for producing 3,4-alkylenedioxyfuran, method for producing polymer thereof and photothermographic image-forming material using the same polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a new monomer and a method for polymerizing the new monomer and to obtain a photothermographic image- forming material having high antistatic performances due to an electroconductive polymer produced by the method for polymerization further without adversely affecting fogging, sensitivity and shelf life. SOLUTION: This method for producing a 3,4-dialkylenedioxyfuran is characterized by producing a 2,5-dialkyl-3,4-dihydroxyfurancarboxylic acid ester from a diglycolic alkyl ester and a dialkyl oxalate, then producing a 3,4- alkylenedioxy-2,5-dialkylcarboxyfuran and finally carrying out hydrolysis and decarboxylation in the presence of an alkali. The method for producing the polymer thereof is provided and the photothermographic image-forming material uses the resultant polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel poly (3,3)
4-alkylenedioxyfuran), its polymerization method, and a photothermographic image-forming material which forms an image by thermal development after exposure, to which an antistatic treatment having a high visible light transmittance is imparted, and fog, sensitivity and The present invention relates to a photothermographic image forming material which forms an image without adversely affecting the storage stability.

[0002]

2. Description of the Related Art A technique using polyaniline as an antistatic agent as an organic conductive polymer is disclosed in U.S. Pat. No. 3,963,4.
No. 98, No. 4,025, 691, No. 4,025
No. 704 and JP-A-2-282245. U.S. Patent Nos. 5,674,654 and 5,665,498 disclose polypyrrole,
European Patents 779,539 and 1,031,875
A1 discloses a polythiophene. The conductive polymer is made by polymerizing an organic low molecular weight compound having a conjugated double bond. For example, mention may be made of polyaniline, polypyrrole and polythiophene derived from aniline, pyrrole and thiophene, respectively. However, although they are conductive, they have the drawback that when used in a photothermographic image forming material, they are strongly black and have high fog density. In particular, polyaniline has high conductivity, but is not suitable for a photosensitive material having high black density and requiring transparency. The polypyrrole and polythiophene described above have been studied to improve it. However, in all cases, the polymer has a high black density, and satisfactory products have not been obtained. The polyfuran compound was a compound expected to have a low black density, but it was difficult to obtain a furan compound as a monomer, and it was difficult to obtain conductivity with a commercially available furan derivative. It was not enduring. The reactivity of the furan compound was determined by simulation based on the ab initio molecular orbital method "Q-Chem version 2.0" manufactured by Kyuchem Co., Ltd., and the reactivity at the 2-position and 5-position was high. If a certain furan derivative is used and is designed to be polymerized at empty 3 and 4 positions, it becomes difficult to obtain a polymer. To overcome this, the 2- and 5-positions are left unsubstituted, leaving active sites for polymerization, substituents are introduced at the 3- and 4-positions, and the active sites 2- and 5-positions are blocked in advance. There is a need. As a blocking method, a method of introducing a carboxyalkyl ester group at the 2-position and 5-position and subjecting the carboxyalkyl ester to alcoholysis and decarboxylation in an alkaline atmosphere can be considered, but satisfactory reaction conditions could not be found.

On the other hand, in recent years, in the medical field, photographic materials which form an image by light or heat treatment which does not generate waste liquid due to wet processing have been strongly desired from the viewpoint of environmental protection and workability. Particularly, both light and heat are used. The technology relating to photothermographic image forming materials for photographic technology, which can form a high-resolution and clear black image by the development, has been commercialized and rapidly spread. Since these photothermographic image forming materials are usually developed at a temperature of 80 ° C. or higher, they are called photothermographic image forming materials to be distinguished from conventional wet photosensitive materials which are liquid-developed in the range of 25 ° C. to 45 ° C.

Conventionally, this type of photothermographic image forming material has a problem in that it tends to be charged with static electricity due to friction and peeling, and all of them tend to form static marks and dust which cause image defects. One solution to this problem is to coat inorganic fine particles such as conductive tin oxide and indium oxide between the support and the photosensitive layer. However, in this method, in order to obtain conductivity, it is necessary to contain the fine particles up to a density at which the fine particles come into contact with each other. Conventionally, these problems have been solved by using a tough binder or a crosslinkable hardener to enhance the film strength, but it has been difficult to obtain satisfactory performance.

The use of organic conductive polymers has also been considered, but there is no suitable solvent for dissolving the polymer, and it is difficult to apply them. There were drawbacks such as easiness, and it was difficult to put it to practical use. As a technique for solving this problem, European Patent 440,95
Nos. 7A3 and 1,031,875 A1 disclose the use of water-dispersible polythiophene compounds as water-soluble dopants. However, the use of a small amount of a weak doping agent or a doping agent has a weak antistatic effect, and the use of a large amount of a strong doping agent or a doping agent enhances the antistatic effect. Photographic performance such as storability was impaired.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to achieve a novel method for producing a monomer required for producing a novel conductive polymer, to achieve the polymerization method, and to provide a conductive polymer produced by the polymerization method. It is an object of the present invention to provide a photothermographic image-forming material which can be used to obtain high antistatic performance and at the same time does not adversely affect fog, sensitivity and storage stability.

[0007]

The above object of the present invention has been attained by the following constitutions.

[0008] 1. 2,5-dialkyl-3,4 from diglycolic alkyl ester and dialkyl oxalate
3,4-alkylenedioxy-2,5-dialkylcarboxyfuran, followed by hydrolysis and decarboxylation in the presence of an alkali. -A method for producing an alkylenedioxyfuran.

[0009] 2. 2. The method for producing 3,4-alkylenedioxyfuran as described in 1 above, wherein hydrolysis and decarboxylation are simultaneously performed in the presence of an alkali.

[0010] 3. 2. The method for producing 3,4-alkylenedioxyfuran as described in 1 above, wherein the alkali to be hydrolyzed and decarboxylated is an alkali metal salt or an alkaline earth metal salt.

4. The alkali to be hydrolyzed and decarboxylated is at least one selected from alkali metal salts, alkaline earth metal salts and alkaline earth metal oxides;
The method for producing 3,4-alkylenedioxyfuran as described in any one of the above items 1 to 3, wherein the method is produced by heating to 00 to 250 ° C.

5. In the hydrolysis and decarboxylation, 100 in the presence of an alkali and a mono- or polyalkylene glycol
The method for producing 3,4-alkylenedioxyfuran according to any one of the above items 1 to 4, wherein the method is produced by heating the mixture to a temperature of from 250C to 250C.

6. The 3,4-alkylenedioxyfuran according to any one of the above 1 to 5, is polymerized in the presence of at least one compound selected from gelatin, polyvinyl alcohol, a polyacetal compound, a polyacrylate derivative, and a polyester derivative. A process for producing poly (3,4-alkylenedioxyfuran), characterized in that:

7. 6. Poly (3,4-alkylenedioxyfuran), which is obtained by polymerizing 3,4-alkylenedioxyfuran according to any one of 1 to 5 in the presence of polystyrenesulfonic acid or a derivative thereof. Production method.

[8] Silver halide, organic silver salt,
A photothermographic image forming material having a photosensitive layer containing a reducing agent and a binder, and containing the poly (3,4-alkylenedioxyfuran) compound described in 6 or 7 above.

The present invention will be described in more detail. The present invention
The present invention relates to a method for obtaining a conductive polymer and a photothermographic image forming material using the conductive polymer. In order to obtain the conductive polymer of the present invention, 3,4-alkylenedioxyfuran is produced, and this is polymerized to produce poly (3,4-alkylenedioxyfuran). The process for producing 3,4-alkylenedioxyfuran comprises, as a first step, reacting an alkyl ester of diglycolic acid with an alkyl ester of oxalic acid to provide a carboxyalkyl ester at the 2- and 5-positions of the furan ring. A 2,5-dicarboxyalkyl-3,4-dihydroxyfuran having a hydroxyl group at the 2-position is synthesized. The furan ring is formed by reacting the diglycolic alkyl ester with the oxalic acid dialkyl ester in a solution obtained by adding metal sodium to an alcohol solvent such as methanol or ethanol and alcoholating it. The temperature is 60 ° C in the temperature range where the alcohol solvent reflux
-100 ° C is preferred. The reflux time of the alcohol solution is 1
Time to 8 hours are preferred. The alkyl group of the diglycolic alkyl ester and the alkyl ester of oxalic acid is
Although carbon numbers of 1 to 6 are preferred, both are particularly preferably methyl and ethyl groups.

In the second step, 1,2-dichloroalkane is introduced into 2,5-dicarboxyalkyl ester-3,4-dihydroxyfuran in the presence of an alkali metal salt, an alkaline earth metal salt or an amine. Preferred dichloroalkanes include dichloromethane, 1,2-dichloroethane, and 1,3-dichloropropane. Hydrochloric acid by-produced is preferably removed as a hydrochloride of amines. Examples of the amine include triethylamine, tributylamine, pyridine, 2,6-dimethylpyridine, 2,5-dimethylpicoline, and 2,5-diethylpicoline. As the solvent, ketones such as acetone, methyl ethyl ketone or methyl isobutyl ketone, and organic solvents such as acetonitrile, tetrahydrofuran and dioxane can be used.
The reaction temperature is 60 ° C. to 1 which is the reflux temperature range of the above solvent.
00 ° C is preferred. The reaction time is preferably 1 hour to 8 hours, and can be increased or decreased depending on the reaction temperature.

As a third step, hydrolysis or alcoholysis of 2,5-dicarboxyalkylester-3,4-alkylenedioxyfuran and decarboxylation are carried out simultaneously or sequentially in an alkaline solvent. Alcolysis is
Alcohols having 1 to 4 carbon atoms such as methanol, ethanol, propanol and butanol are preferred. For decarboxylation, alkanolamines such as monoethanolamine, diethanolamine and triethanolamine, and glycols such as ethylene glycol, diethylene glycol and triethylene glycol are preferable. When glycols are used, it is preferable to add an alkali metal salt or an alkaline earth metal salt such as sodium hydroxide, potassium hydroxide, calcium hydroxide, and magnesium hydroxide.

The obtained compound can be purified by a method of dissolving it in water or an organic solvent for recrystallization, an extraction method of separating into an aqueous phase and an oil phase, a distillation method and the like.

The reaction scheme from the first step to the third step is shown below.

[0021]

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In the formula, R ₁ and R ₂ represent an alkyl group having 1 to 5 carbon atoms, and R ₃ represents an alkylene group having 1 to 5 carbon atoms. Particularly preferred carbon numbers are those in which R ₁ and R ₂ have 1 carbon atom.
And 2 and R ₃ is 2. X represents a halogen atom such as chlorine, bromine and iodine, and a chlorine atom is particularly preferable.

The polymerization of 3,4-alkylenedioxyfuran is carried out by ordinary radical polymerization using ammonium persulfate, potassium persulfate, sodium persulfate, azobisisobutyronitrile or the like, or by ferrous sulfate, hydrogen peroxide, Redox polymerization using cerium sulfate or the like can be employed. In the polymerization, polymerization may be performed in the presence of polyanions such as polystyrenesulfonic acid, polyacrylic acid and polyacrylamidepropanesulfonic acid, such as low molecular perchlorate ions, halogen ions and boron tetrafluoride ions as anions. preferable. Gelatin, polyacrylic acid, polystyrene sulfonic acid, polyacrylamide propane sulfonic acid, polyvinyl alcohol, styrene-maleic acid copolymer, styrene-methyl methacrylate-ethyl acrylate-acrylic acid, polyvinyl butyral, polyvinyl Formal and the like can be mentioned. The polymerization temperature is 3
A range from 5C to 100C is preferred. The polymerized poly (3,4-alkylenedioxyfuran) can be used in the following photothermographic image forming materials.

The photothermographic image forming material of the present invention contains a reducing agent and an organic silver salt as essential components in addition to the photosensitive silver halide, and the image forming reaction is based on the principle of dissolution physical development by heating. In the case of using inorganic fine particles such as conductive tin oxide and indium oxide, since these act as physical development nuclei, they cause fog not depending on silver halide, lower sensitivity, deterioration of color tone, and the like. Conceivable. In the present invention, in order to enhance the antistatic performance (antistatic effect) of the photothermographic image forming material, poly (3,3) is used.
By using a conductive polymer compound composed of a (4-alkylenedioxyfuran) compound, the antistatic performance is improved.

The layer containing the conductive polymer compound comprising the poly (3,4-alkylenedioxyfuran) compound of the present invention may be any layer. Usually, a photothermographic image forming material is provided with at least a photosensitive layer and a protective layer on one surface of a support, and B on the side of the support opposite to the side having the photosensitive layer.
The configuration is such that a protective layer of a C layer or further a BC layer is provided. The photosensitive layer contains photosensitive silver halide grains which may be sensitized, an organic silver salt serving as a silver source, and a reducing agent for developing a silver salt to form a silver image. The polyfuran compound used in the present invention may be added to any of the above layers, and when it is added to these layers, it is particularly preferable to add it to the protective layer. In addition, these conductive polymer compounds may be added to an intermediate layer adjacent to the photosensitive layer, an undercoat layer, or the like, separately from these layers, or may be added to a layer via an intermediate layer. I can do it. Further, it can be added to the backing layer, or the antistatic performance of the back surface of the photothermographic image forming material can be enhanced by a backing protective layer or the like.

The amount of the poly (3,4-alkylenedioxyfuran) compound to be added is preferably in the range of 1 microgram to 10 grams per unit area (per square meter) of the photothermographic image forming material. The addition method is water,
Dissolving or dispersing in fine particles in an alcohol (eg, methanol, ethanol, isobutyl alcohol, etc.), ketones (eg, acetone, methyl ethyl ketone, isobutyl ketone, etc.), or an aromatic organic solvent (eg, toluene, xylene, etc.) Methods can be mentioned.
The average particle diameter when the fine particles are dispersed is 1 nm to 300 nm.
Is preferred.

In the present invention, these polyfuran compounds are used as an antistatic agent in a photothermographic image forming material (preferably in a protective layer or undercoating), so that they are used in the photothermographic image forming material. Without compromising the effects of the following additives, it is possible to effectively combine these effects with the antistatic effect (antistatic effect) (that is, to exert the effects of these additives effectively). I can do it.

(Photosensitive Silver Halide) The photosensitive silver halide contained in the photosensitive layer of the photothermographic image-forming material of the present invention may be any known one in the field of photographic technology such as a single jet or double jet method. , And is prepared in advance by any method such as an ammonia method, a neutral method, and an acidic method. The photosensitive silver halide preferably has a small grain size in order to suppress white turbidity after image formation and to obtain good image quality. The average particle size is 0.1 μm or less, preferably 0.01 to 0.1 μm, particularly preferably 0.02 to 0.08 μm. The shape of the silver halide is not particularly limited, and may be cubic, octahedral, so-called normal crystals, or non-normal crystals, such as spherical, rod-shaped, or tabular grains. The silver halide composition is not particularly limited, and may be any of silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide, and silver iodide.

The amount of the silver halide is 50% by mass or less, preferably 25 to 0.1% by mass, more preferably 15 to 0.1% by mass, based on the total amount of the silver halide and the organic silver salt described below. It is.

The silver halide of the present invention is also disclosed in US Pat. Nos. 4,009,039, 3,457,075, 4,003,749 and British Patent 1,498,95.
No. 6, each specification and JP-A-53-27027, 53-
No. 25420, inorganic halogen compounds, onium halides, halogenated hydrocarbons, N
-It can be produced by converting a part of the organic silver salt into silver halide using a silver halide forming component such as a halogen compound or another halogen-containing compound. Various conditions such as a reaction temperature, a reaction time, and a reaction pressure in the step of converting into silver halide can be appropriately set according to the purpose of production, but usually, the reaction temperature is -23 ° C to 74 ° C, and the reaction time is usually It is 0.1 second to 72 hours, and the reaction pressure is preferably set to the atmospheric pressure.

The photosensitive silver halide prepared by the various methods described above includes, for example, a sulfur-containing compound, a gold compound,
Platinum compounds, palladium compounds, silver compounds, tin compounds,
Chemical sensitization can be performed by a chromium compound or a combination thereof. The method and procedure of the chemical sensitization are described in, for example, U.S. Pat. No. 4,036,650, British Patent No. 1,518,850, and the like.
No. 22430, No. 51-78319, No. 51-811
No. 24 and the like.

The silver halide used in the present invention can be sensitized with a spectral sensitizing dye, if necessary. For example, JP-A-63-159814, JP-A-60-140335, JP-A-6-140335
Nos. 3-231437, 63-259651 and 63
-304242, 63-15245, etc.,
U.S. Pat. Nos. 4,639,414 and 4,740,4
No. 55, No. 4,741,966, No. 4,751,
Sensitizing dyes described in each specification such as 175 and 4,835,096 can be used. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected. For example, JP-A-9-
Nos. 34078, 9-54409 and 9-806
The compounds described in No. 79 are preferably used.

(Organic Silver Salt) The organic silver salt contained in the photothermographic image forming material of the present invention is a reducible silver source, and an organic acid, heteroorganic acid and acid polymer containing a reducible silver ion source. Silver salts of the like are used. Also, the ligand is
Organic or inorganic silver salt complexes having a total stability constant for silver ions of 4.0 to 10.0 are also useful. Preferred organic acids used for the preferred organic silver salts include, for example, gallic acid, oxalic acid, behenic acid, stearic acid, palmitic acid and lauric acid. The organic silver salt is prepared by mixing the alkali metal salt of the organic acid and silver nitrate, and may be added by a controlled double jet method at the time of mixing, or may be added at a different timing. The silver salt may be added all at once or in several stages at any stage to form a silver salt.

(Reducing Agent) Examples of preferred reducing agents contained in the photothermographic image-forming material of the present invention are described in US Pat.
70,448, 3,773,512, 3,59
No. 3,863 and the like, and the following are mentioned. (K1) 1,1-bis (2-hydroxy-3,5-dimethylphenyl) -3,5,5-trimethylhexane (K2) bis (2-hydroxy-3-t-butyl-5)
-Methylphenyl) methane (K3) 2,2-bis (4-hydroxy-3-methylphenyl) propane (K4) 4,4-ethylidene-bis (2-t-butyl-6-methylphenol) (K5) 2 , 2-Bis (3,5-dimethyl-4-hydroxyphenyl) propane The compound shown above is used by dispersing in water or dissolving in an organic solvent. As the organic solvent, alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, and aromatic solvents such as toluene and xylene can be arbitrarily selected. The amount of the reducing agent to be used is 1 × 10 ⁻³ to 10 mol, preferably 1 × 10 ⁻² to 1 mol per mol of silver.
5 moles.

(Binder) As the polymer binder used in the photosensitive layer or the non-photosensitive layer of the photothermographic image forming material of the present invention, polyvinyl butyral, polyacrylamide, polystyrene, polyvinyl acetate, polyurethane, polyacrylic ester Styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, vinyl chloride-vinyl acetate copolymer, styrene-butadiene-acryl copolymer, and the like. After drying and forming a film,
Those having a low equilibrium water content of the coating film are preferred, and examples of those having a particularly low water content include, for example, organic solvent-based cellulose acetate, cellulose acetate butyrate and polyacetal. Preferred polyacetals for the present invention include polybutyral acetalized with butyraldehyde and polyacetal acetalized with acetaldehyde (polyacetal in a narrow sense). The degree of acetalization theoretically exists from 1% to 100%, but practically preferably from 20% to 95%. If the degree of acetalization is low, the number of hydroxyl groups is increased, and the photographic performance is weak against humidity. If the degree of acetalization is high, the reaction temperature and time are severe, and the cost and productivity are reduced. The degree of polymerization of the polymer can be freely selected from about 10 to about 10,000, but 100 to 6,000 is preferable from the viewpoint of applicability and productivity in synthesis.

(Crosslinking agent) The binder alone can maintain the adhesion to the lower layer and the upper layer and can provide a film strength that is hardly damaged by forming a film alone. Film adhesion and film strength can be increased. However, when the crosslinking reaction is slow, the photographic performance is not stable and the storage stability is deteriorated. As a quick-acting and preferred crosslinking agent used in the present invention, a polyfunctional crosslinking agent having at least two isocyanate groups can be exemplified. Preferred crosslinking agents are shown below. (H1) hexamethylene diisocyanate (H2) trimer of hexamethylene diisocyanate (H3) tolylene diisocyanate (H4) phenylene isocyanate (H5) xylylene diisocyanate (H6) 1,3-bis ( Isocyanatomethyl) cyclohexane (H7) tetramethylene xylylene diisocyanate (H8) m-isopropenyl-α, α-dimethylbenzyl isocyanate

[0037]

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The crosslinking agent may be added by dissolving in water, alcohols, ketones, non-polar organic solvents,
It may be added as a solid to the coating solution. The amount of addition is preferably equivalent to the crosslinking group of the binder, but may be increased up to 10 times or reduced to 1/10 or less. If the amount is too small, the crosslinking reaction does not proceed. If the amount is too large, the unreacted crosslinking agent deteriorates photographic properties, which is not preferable.

(Dye optionally used in AH layer or BC layer) The photothermographic image-forming material of the present invention may optionally contain A for preventing halation of the photothermographic image-forming material.
An H layer or a BC layer is provided. The dye used in the AH layer or the BC layer may be any dye that absorbs light used for image exposure.
No. 140, No. 7-13295, No. 7-11432,
Dyes described in U.S. Pat. No. 5,380,635 can be exemplified.

(Support) The support is preferably a support such as polyethylene terephthalate, polyethylene naphthalate or syndiotactic polystyrene.
A film having a thickness of 50 μm to 400 μm, which is axially stretched and heat-fixed, has high optical isotropy, and has good dimensional stability is preferred.

(Image Exposure) As an exposure method, see
JP-A-304869, JP-A-9-311403 and JP-A-2
000-10230 can be used for laser exposure. In the exposure of the photothermographic image forming material of the present invention, it is desirable to use a light source appropriate for the color sensitivity imparted to the image forming material. For example, when the image forming material is made to be able to feel infrared light,
Although it can be applied to any light source in the infrared light range, an infrared semiconductor laser (780) can be used because the laser power is high and the image forming material can be made transparent.
nm, 820 nm) are more preferably used.

(Thermal Developing Apparatus) An apparatus for developing a photothermographic image forming material is disclosed in JP-A-11-65067 and JP-A-11-7.
The apparatus described in each of Nos. 2897 and 11-84619 can be used.

[0043]

EXAMPLE 1 (Synthesis of 2,5-dicarboxymethyl-3,4-dihydroxyfuran) Sodium 49.5 g (2.21 mol)
And 351 ml of methanol to prepare a sodium methoxide solution. In this solution, 190.2 g (1 mol) of diglycolic diethyl ester and diethyl oxalate 14 were added.
After adding 6.1 g (1 mol) and refluxing for 5 hours, the mixture was adjusted to pH 5 with glacial acetic acid and poured into 1.75 L of ice water. The obtained precipitate was collected by filtration, washed with pure water, and purified by recrystallization with pure water. Yield 125 g (58% yield). The physical properties of the obtained compound are as follows.

The measurement of the mass spectrum was carried out by using Mardi (MA).
The LDI method and the measuring device were used by PHI
HI) Trif-2 (TRIFT-II), a nitrogen laser as an excitation light source, 2,5-dihydroxybenzoic acid as a matrix, and methyl ethyl ketone as a solvent. The peak value 216 (molecular weight 216.145) was confirmed. Elemental analysis was quantified using the combustion method. Theoretical analysis value C = 44.
46%, H = 3.73%, O = 51.81%, measured values are C = 44.52%, H = 3.70%, O = 51.7.
9%. OH-based stretching vibration absorption 32 by Fourier transform infrared spectroscopy (FTIR-8300 manufactured by Shimadzu Corporation)
00cm ^-1, C = O stretching vibration 1720 cm ^-1, using a nuclear magnetic resonance apparatus (Hitachi R-1100), proton NMR (60MHz, CDCl ₃₎ on carboxymethyl hydrogen chemical shift [delta] = 3.82, Hydrogen chemical shift δ of the hydroxyl group was 6.60.

(Synthesis of 3,4-methylenedioxy-2,5-dicarboxymethylfuran)
Dissolve 21.6 g (0.1 mol) of 4-dihydroxy-2,5-dicarboxymethylfuran, 20.2 g (0.2 mol) of triethylamine and 16.99 of dichloromethane.
g (0.2 mol) was added and refluxed for 3.5 hours. The reaction solution was poured into pure water, extracted with ethyl acetate, and purified by distillation. Yield 9.1 g (42% yield). The physical properties of the obtained compound are as follows.

The peak value 228 of the mass spectrometer (molecular weight 22
8.156) was confirmed. Elemental analysis was quantified using the combustion method. Theoretical analysis value C = 47.38%, H = 3.53
%, O = 49.09%, measured value was C = 47.40%,
H = 3.53% and O = 50.91%. Fourier transform infrared spectroscopy (FTIR-830 manufactured by Shimadzu Corporation)
0), C = O stretching vibration of 1710 cm ^-1 , using a nuclear magnetic resonance apparatus, proton NMR (60 MHz, CDCl ₃ )
The hydrogen chemical shift value of carboxymethyl δ = 3.85,
The hydrogen chemical shift δ of the methylenedioxy group was 4.30.

(Synthesis of 3,4-ethylenedioxy-2,5-dicarboxymethylfuran)
21.6 g (0.1 mol) of 4-dihydroxy-2,5-dicarboxymethylfuran was dissolved, and 20.2 g (0.2 mol) of triethylamine and 1,2-dichlorotan 1
9.8 g (0.2 mol) was added and refluxed for 3.5 hours. The reaction solution was poured into pure water, extracted with ethyl acetate, and purified by distillation. Yield 9.1 g (42% yield). The physical properties of the obtained compound are as follows.

The peak value 242 of the mass spectrometer (molecular weight 24
2.183) was confirmed. Elemental analysis was quantified using the combustion method. Theoretical analysis value C = 49.59%, H = 4.16
%, O = 46.24%, measured value C = 49.40%,
H = 4.13% and O = 46.25%. Fourier transform infrared spectroscopy (FTIR-830 manufactured by Shimadzu Corporation)
0), C = O stretching vibration of 1710 cm ^-1 , using a nuclear magnetic resonance apparatus, proton NMR (60 MHz, CDCl ₃ )
The hydrogen chemical shift value of carboxymethyl δ = 3.85,
The hydrogen chemical shift δ of the ethylenedioxy group was 4.10.

(Synthesis of 3,4-methylenedioxyfuran (abbreviation MDF1)) 2,5-dicarboxymethyl-3.
4-Methylenedioxyfuran (0.03 mol) was added to monoethanolamine (0.6 mol), and after keeping the atmosphere of nitrogen at 72 ° C for 3 hours, the solution temperature was raised to 170 ° C and 5 hours. Held. This solution was poured into ice water,
-Extracted with dichloroethane. The yield (0.018 mol) was 60%. The physical properties of the obtained compound are as follows.

The peak value 112 of the mass spectrometer (molecular weight 11
2.084). Elemental analysis was quantified using the combustion method. Theoretical analysis value C = 53.58%, H = 3.60
%, O = 42.82%, measured value C = 53.60%,
H = 3.58% and O = 42.82%. Fourier transform infrared spectroscopy (FTIR-830 manufactured by Shimadzu Corporation)
0), C = C stretching vibration of 1587 cm ⁻¹ , using a nuclear magnetic resonance apparatus, hydrogen chemical shift δ of methylenedioxy group =
4.3.

(Synthesis of 3,4-ethylenedioxyfuran (abbreviation: EDF1))
As in the synthesis of 3,4-methylenedioxyfuran,
-Dicarboxymethyl-3,4-ethylenedioxyfuran was synthesized by alcoholysis and decarboxylation. The physical properties of the obtained compound are as follows.

The mass spectrometer peak value 126 (molecular weight 12
6.111) was confirmed. Elemental analysis was quantified using the combustion method. Theoretical analysis value C = 57.14%, H = 4.80
%, O = 38.06%, measured value was C = 57.18%,
H = 4.80% and O = 38.02%. Fourier transform infrared spectroscopy (FTIR-830 manufactured by Shimadzu Corporation)
0), C = C stretching vibration of 1587 cm ⁻¹ , using a nuclear magnetic resonance apparatus, hydrogen chemical shift of ethylenedioxy group δ =
It was 4.12.

Example 2 In the synthesis of MDF1 and EDF1 in Example 1, monoethanolamine was used in place of diethanolamine and triethanolamine in an equimolar manner (MDF2, EDF2, and triethanol, respectively, were synthesized from diethanolamine). Those synthesized from amines are abbreviated as MDF3 and EDF3). The C = C value of the infrared spectroscopic analysis value, the peak value of the mass spectrometer, and the proton chemical shifts of methylenedioxy group and ethylenedioxy group of nuclear magnetic resonance of the obtained compound were the same as those in Example 1.

Example 3 The 3,4-methylenedioxyfuran of Example 2 and 3,3
In the synthesis of 4-ethylenedioxyfuran, ethylene glycol, diethylene glycol and triethylene glycol were used in place of monoethanolamine in equimolar amounts, and 0.2 mol of sodium hydroxide was added as an alkali for synthesis. MDF4 and EDF4 are used when ethylene glycol is used, MDF5 and EDF5 are used when diethylene glycol is used, and MDF6 is used when triethylene glycol is used.
And EDF6. The C = C value of the infrared spectroscopic analysis value, the peak value of the mass spectrometer, and the proton chemical shift of the ethylenedioxy group in nuclear magnetic resonance of the obtained compound were the same.

Further, potassium hydroxide (compounds which can be synthesized are abbreviated as MDF7 and EDF7) instead of sodium hydroxide as an alkali, lithium hydroxide (also MDF7)
8 and EDF8) and 0.18 mol of calcium hydroxide (also abbreviated as MDF9 and EDF9). The obtained infrared analysis value, the peak value of the mass spectrometer, and the chemical shift of the proton of ethylenedioxy in the proton nuclear magnetic resonance apparatus were the same.

Example 4 At the time of the reaction using triethanolamine of Example 2, the condition of 170 ° C. was changed to 80 ° C., 100 ° C., 140 ° C., 1
The synthesis was performed by changing the temperature to 60 ° C, 220 ° C, 250 ° C, and 270 ° C. In addition, ethanolamine was set at 220 ° C, 250 ° C and 270 ° C, and diethanolamine was set at 270 ° C.
Was not performed. In each case, the desired 3,4-methylenedioxyfuran could not be obtained by the reaction at 80 ° C., but 8% at 100 ° C., 12% at 140 ° C., 160 ° C.
At 40 ° C, 60% at 220 ° C, 52% at 250 ° C, 27%
43% yield at 0 ° C.

Example 5 During the reaction using ethylene glycol, diethylene glycol and triethylene glycol of Example 3,
The alkali metal salt is changed to sodium hydroxide, potassium hydroxide and the alkaline earth metal salt to calcium hydroxide.
The condition of 170 ° C. is maintained at 80 ° C., 100 ° C. and 140 ° C.
C, 160, 220, 250 and 270 ° C. The reaction conditions of 220 ° C. and 250 ° C. were not used for ethylene glycol, and the temperature condition of 250 ° C. was not used for diethylene glycol. 80 ° C for all
The desired 3,4-ethylenedioxyfuran could not be obtained under the conditions of the above reaction, but 9% at 100 ° C. and 1% at 140 ° C.
4%, 43% at 160 ° C, 63% at 220 ° C, 250 ° C
At a yield of 54% at 270 ° C.

Example 6 Synthesis of poly (3,4-ethylenedioxyfuran) Prior to the experiment, a 10% by mass aqueous solution of gelatin (dp1), a 10% by mass aqueous solution of polyvinyl alcohol (dp2), and methyl ethyl ketone of polyvinyl butyral (PVB-1) were used. Solution 10% by mass (dp3), 10% of poly (butyl acrylate-acrylic acid) copolymer (copolymerization ratio 98: 2)
Mass% aqueous solution (dp4), poly (styrene-methyl methacrylate-butyl acrylate-ethyl acrylate)
Copolymer (copolymerization ratio 25%: 25%: 30%: 20)
%) And a 10% by weight aqueous solution (dp6) of a copolymer of poly (terephthalic acid-ethylene glycol-sodium sulfonate of metaphthalic acid) (copolymerization ratio 40:40:20). did.

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In 1 L of pure water, 20 g of each of 3,4-methylenedioxyfuran and 3,4-ethylenedioxyfuran shown in Table 1 and synthesized in Examples 1 to 3,
Dispersion or solution of dp1 to dp6 (described in Table 1)
Was added, 2 g of sodium polystyrenesulfonate and 2 g of ammonium persulfate were added, and polymerization was carried out at 57 ° C. for 3 hours in a nitrogen atmosphere. The resulting dispersion or solution was coated on a transparent 175 micron thick polyethylene terephthalate support to a thickness of 1 μm and dried. After leaving for 8 hours in a room at a relative humidity of 20% and a temperature of 25 ° C., the surface resistivity was measured. Table 1 shows the obtained results.

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[Table 1]

Example 7 (Preparation of Subbed Support) A 175 μm-thick polyethylene terephthalate support was subjected to a corona discharge treatment of 12 W / m ² · min on both surfaces, and one surface was coated with the following subbing coating solution a- 1
Is applied to a dry film thickness of 0.6 μm and dried to form an undercoat layer A-1.
-1 was applied to a dry film thickness of 0.6 μm and dried to form an undercoat layer B-1.

Preparation of Subbing Coating Solution a-1 Butyl acrylate (30% by mass), t-butyl acrylate (20% by mass), styrene (25% by mass), 2-
A copolymer latex liquid (solid content: 30%) of hydroxyethyl acrylate (25% by mass) is diluted 15-fold.

Preparation of Undercoat Coating Solution b-1 A 15-fold copolymer latex liquid (solid content: 30%) of butyl acrylate (40% by weight), styrene (20% by weight), and glycidyl acrylate (40% by weight) was prepared. Dilute.

Subsequently, the undercoat layer A-1 and the undercoat layer B-1
A 12 W / m ² · min corona discharge is applied to the upper surface of the undercoating layer A-1. The undercoat layer B-1 (for the BC layer) was provided by applying and drying the following undercoat upper layer coating solution b-2 on the undercoat layer B-1.

Preparation of Undercoating Upper Layer Coating Solution a-2 1: 2 copolymer of styrene and butadiene 0.4 g / m ² butyl acrylate (30 mass%), t-butyl acrylate (20 mass%), styrene (25 mass%) Mass%), copolymer latex liquid of 2-hydroxyethyl acrylate (20 mass%), methacrylic acid (5 mass%) (solid content 30%) 0.3 g / m ² crosslinking agent (hexamethylene diisocyanate) 0 Preparation of 0.1 g / m ² lower undercoat coating solution b-2 1: 2 copolymer of styrene and butadiene 0.4 g / m ² butyl acrylate (30% by mass), t-butyl acrylate (20% by mass), styrene (25% by mass), copolymer latex liquid of 2-hydroxyethyl acrylate (20% by mass), methacrylic acid (5% by mass) (solid content: 30%) 0.3 g / m ² crosslinking Agent (Hexamethylene diisocyanate) 0.1 g / m ² (Preparation of photothermographic image forming material) First, silver halide was prepared before coating, and then an organic silver salt was prepared using the prepared silver halide. .

Preparation of silver halide grain emulsion A 7.5 g of inert gelatin and 10 mg of potassium bromide were dissolved in 900 ml of water, the temperature was adjusted to 28 ° C., the pH was adjusted to 3.0, and 370 ml of an aqueous solution containing 74 g of silver nitrate was added. 370 ml of an aqueous solution containing equimolar amounts of potassium bromide and potassium iodide in a molar ratio of (98/2) and silver nitrate was added over 10 minutes by a controlled double jet method while maintaining the pAg at 7.7. Synchronously with the addition of silver nitrate, the sodium salt of hexachloroiridium was added at 1 × 10 ^-6 mol / mol of silver. Thereafter, 4-hydroxy-6-methyl-1,
0.3 g of 3,3a, 7-tetrazaindene was added and Na was added.
Adjust the pH to 5 with OH and adjust the average particle size to 0.036μ.
m, coefficient of variation of projected diameter area 8%, [100] face ratio 8
7% of cubic silver iodobromide grains were obtained. The particles are coagulated and settled using a gelatin coagulant and desalted.
Finished to 60 ml.

Preparation of water-dispersed organic silver salt 111.4 g of behenic acid, 83.8 g of arachidic acid and 54.9 g of stearic acid were dissolved in 3980 ml of pure water at 80 ° C. Next, while stirring at a high speed, 540.2 ml of a 1.5 mol sodium hydroxide aqueous solution was added, and 6.9 m of concentrated nitric acid was added.
After adding 1, the mixture was cooled to 55 ° C. to obtain a sodium organic acid solution. While maintaining the temperature of the organic acid sodium acid solution at 55 ° C., the silver halide grain emulsion A (silver 0.03
8 mol) and 420 ml of pure water were added and stirred for 5 minutes. Next, 760.6 ml of a 1 mol silver nitrate solution was added over 2 minutes, the mixture was further stirred for 20 minutes, and water-soluble salts were removed by filtration. Thereafter, the filtrate was repeatedly washed with deionized water and filtered until the conductivity of the filtrate reached 2 μS / cm, and finally dried after centrifugal dehydration.

Coating of photosensitive layer and BC layer On the surface having the undercoating upper layer B-2 of the undercoated support, the following layers on the back surface side, and then the undercoating upper layer A
An AH layer, a photosensitive layer and a surface protective layer having the following compositions were simultaneously coated on the surface having No. -2. The drying was performed at 45 ° C. for 1 minute on both the BC side and the photosensitive layer side.

Coating of Back Surface Side On the back surface side, a coating solution having the following composition (indicated by the amount added) was simultaneously applied in multiple layers and dried to form a BC layer.

(Coating of BC Layer) Binder (PVB-1) 1.8 g / m ² Glycidyltrimethoxysilane 1 × 10 ⁻⁴ mol / m ² Dye (C1) 2.2 × 10 ⁻⁵ mol / m ² ( BC protective layer coating) Binder (cellulose acetate butyrate) 1.1 g / m ² Cross-linking agent (hexamethylene diisocyanate) 1 × 10 ^-4 mol / m ^{2 <<} Coating on photosensitive layer side >> (Coating of AH layer) Binder (PVB-1) 0.4 g / m ² Dye (C1) 1.3 × 10 ⁻⁵ mol / m ² (coating of photosensitive layer) For forming a photosensitive layer, a coating solution of the following composition was prepared. Coating and drying were performed so that the following amounts were obtained.
However, a preparation of the organic silver salt in an amount of 1.36 g / m ² in terms of silver was mixed with the polymer binder. Binder (PVB-1) 2.6 g / m ² Crosslinker (hexamethylene diisocyanate) 2 × 10 ⁻³ mol / m ² Spectral sensitizing dye (A1) 2 × 10 ⁻⁵ mol / m ² Antifoggant (Pyridinium hydrobromide perbromide) 0.3 mg / m ² Antifoggant (isothiazolone) 1.2 mg / m ² Reducing agent (K1) 3 × 10 ^-4 mol / m ²

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(Surface Protective Layer) A coating solution prepared by adding the following composition was applied onto the photosensitive layer so as to have the following coating amount and dried to form a surface protective layer. Binding agents: Table 2 wherein 1.2 g / m ² crosslinker: poly (3,4-alkylenedioxy furan described in Table 2 10 ^-4 mol / m ² tetrachlorophthalic anhydride 0.5 g / m ² the invention ) Compound: described in Table 2 (The number of the polyfuran compound indicates the polyfuran NO. In Example 6.) 0.1 g / m ² PVB-1 used as a binder was dissolved in methyl ethyl ketone (MEK) before use. did. PVB-1 is BC
It was also used as a binder in the layer. CAB is cellulose acetate butyrate. Comparative 1 as comparative polymer
Is the poly (3,4-ethylenedioxythiophene) of EP 10331875A1 and Comparative 2 is U.S. Pat.
Poly (3,4-ethylenedioxypyrrole) described in US Pat. No. 65,498 was used.

(Evaluation of photographic performance)
The film was exposed to light at 810 nm in an atmosphere of 48% relative humidity at ℃ in a semiconductor laser exposure sensitometer, heated at 120 ° C. for 8 seconds after exposure, and the fog and sensitivity of the obtained sample were determined. Fog is the density value of the unexposed portion itself, and the sensitivity is the reciprocal of the exposure amount that gives a density of 0.2, and is expressed as a relative sensitivity with reference sample 701 being 100.

(Evaluation of storage stability)
After storing for 7 days in an atmosphere of 80% relative humidity,
Exposure was performed using a 0 nm semiconductor laser exposure sensitometer, and after exposure, heating was performed at 120 ° C. for 8 seconds, and fog of the obtained sample was determined.

(Evaluation of antistatic effect) After leaving the above unexposed sample in a room at a relative humidity of 20% for 18 hours, the sample was rubbed five times with a synthetic fiber cloth (60% nylon, 40% polyester) and styrene The beads were held over 100 beads (average particle diameter: 3 mm) (approach distance: 15 mm) to evaluate the degree of adsorption of the beads. The level without adsorption is 5 ~ 3 ~
4 for 8 adsorptions, 3 for 9 to 15 adsorptions, 2 from 16
The level of adsorption of 5 pieces was set to 2, and the level of adsorption of 26 pieces or more was set to 1.

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[Table 2]

Table 2 shows that the use of the polyalkylenedioxyfuran compound of the present invention provides an antistatic effect and is excellent in photographic characteristics and storage stability.

Example 8 Poly (3,4-alkylenedioxyfuran) was added to an undercoat layer or a BC protective layer to evaluate the antistatic effect.
When added to the undercoat layer, it was added to the undercoat a-2 or b-2 coating solution. The effect of preventing static electricity was performed in the same manner as in Example 7. Comparative compounds used in Comparative Examples 1 and 2 of Example 7 were used. 602 to 606 of polyfuran compounds
No. is the polyfuran No. prepared in Example 6. Indicates that was used. All the binders of the BC protective layer were coated using gelatin. Crosslinking agents are H7 and H11
^Was used in an amount of 1 × 10 ⁻⁴ mol / m ² . Table 3 shows the results
Shown in

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[Table 3]

Table 3 shows that the use of the polyalkylenedioxyfuran compound of the present invention is excellent in the antistatic effect.

[0082]

Industrial Applicability According to the present invention, a method for producing a novel monomer required for producing a novel conductive polymer, a method for polymerizing the same, and high antistatic performance using the conductive polymer produced by this polymerization method. At the same time, a photothermographic image forming material which does not adversely affect the photographic performance of the photothermographic material, that is, fog, sensitivity and storage stability, was obtained.

Claims (8)

[Claims] (1) a 2,5-dialkyl-3,4-diglycolic alkyl ester and a dialkyl oxalate ester;
3,4-alkylenedioxy-2,5-dialkylcarboxyfuran, followed by hydrolysis and decarboxylation in the presence of an alkali. A method for producing an alkylenedioxyfuran. 2. The method for producing 3,4-alkylenedioxyfuran according to claim 1, wherein hydrolysis and decarboxylation are simultaneously performed in the presence of an alkali. 3. The method for producing 3,4-alkylenedioxyfuran according to claim 1, wherein the alkali to be hydrolyzed and decarboxylated is an alkali metal salt or an alkaline earth metal salt. 4. The alkali to be hydrolyzed and decarboxylated is at least one selected from alkali metal salts, alkaline earth metal salts and alkaline earth metal oxides, and
The method for producing 3,4-alkylenedioxyfuran according to any one of claims 1 to 3, wherein the method is produced by heating to 0 ° C to 250 ° C. 5. Hydrolysis and decarboxylation in the presence of an alkali and a mono- or polyalkylene glycol at 100 ° C.
The method for producing a 3,4-alkylenedioxyfuran according to any one of claims 1 to 4, wherein the method is produced by heating the composition to a temperature of about 250C. 6. The compound according to claim 1, wherein the 3,4-alkylenedioxyfuran is at least one compound selected from gelatin, polyvinyl alcohol, a polyacetal compound, a polyacrylate derivative and a polyester derivative. A method for producing poly (3,4-alkylenedioxyfuran), which comprises polymerizing in the presence of: 7. A poly (3,4-characteristic) comprising polymerizing the 3,4-alkylenedioxyfuran according to claim 1 in the presence of polystyrenesulfonic acid or a derivative thereof. A method for producing alkylenedioxyfuran). 8. The poly (3,4-alkylenedioxyfuran) according to claim 6, which has a photosensitive layer containing a silver halide, an organic silver salt, a reducing agent and a binder on a support. A) a photothermographic image-forming material comprising a compound.