JPS642582B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to phenylene bis(α-cyanobutadienecarboxylic acid) or its ester derivative useful as a raw material for a new photocrosslinkable polyester sensitive to visible light, and a method for producing the same. Conventionally, various polymers having cinnamate ester, chalcone, benzylidene acetone, chemerin, etc. on their side have been known as photosensitive resins that are insolubilized by ultraviolet rays for photocrosslinking reaction (photoduplexing reaction), among which polyvinyl thinner is used. Mate has been put to practical use as a resist resin or an offset PS plate. In addition, polyester containing phenylene diacrylic acid as an acid component is known as a material in which a photosensitive group is incorporated into the main plate, and is used in practical use as a PS plate with excellent abrasion resistance and oil sensitivity. On the other hand, in recent years, printing technology using laser beams has been permeating the newspaper printing field. Laser light sources used in such plate-making apparatuses are mainly used as light sources that emit visible light with relatively long wavelengths, such as argon ion lasers and helium neon lasers. Although it is possible to use light in the ultraviolet region of an argon laser, it is much weaker than the light intensity in the visible range, and a high-output laser light source is required to use ultraviolet light. Therefore, conventional ultraviolet-type photosensitive resins can only be used in a very limited manner in the field of laser platemaking. From this point of view, there is an increasing demand for photosensitive materials that are sensitive to visible light. The present inventors focused on the fact that the absorption spectrum significantly shifts to longer wavelengths by increasing the number of conjugations of unsaturated carboxylic acid esters, and as a result of intensive research on acid components suitable for visible light-sensitive polymers, phenylene bis(α -cyanobutadienoic acid)
The present invention was achieved by discovering that the polyester obtained by using the acid component as an acid component is sensitized to light in the visible range of an argon laser. That is, the present invention has the following general formula [] [However, in the formula, R is the same or different, and is a group selected from the group consisting of a hydrogen atom and a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and Ar is a m-phenylene group or a p-phenylene group. represent. ] Phenylene bis(α-cyanobutadienecarboxylic acid) or its ester derivative represented by the following general formula [] OCH-CH=CH-Ar-CH=CH-CHO
...[] [[However, in the formula, Ar is m-phenylene group or p-
Represents a phenylene group. ] Phenylene bis-acrolein represented by and the following general formula [] [However, in the formula, R' is a hydrogen atom and a carbon atom number of 1
A group selected from the group consisting of ~10 monovalent aliphatic hydrocarbon groups. ] The following general formula [] is characterized by dehydration condensation with α-cyanoacetic acid or its ester derivative represented by [However, Ar and R are as defined above. ] A method for producing phenylenebis(α-cyanobutadienecarboxylic acid) or its ester derivative represented by the following general formula [] [However, in the formula, Ar represents m-phenylene or p-phenylene group. ] Phenylene bis(α-cyanobutadienecarboxylic acid) represented by the following general formula [] ROH ... [] [However, in the formula, R represents a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms. ] The following general formula [] is characterized by causing an esterification reaction with an alcohol represented by [However, in the formula, Ar and R are as defined above. ] This is a method for producing an ester derivative of phenylene bis(α-cyanobutadienecarboxylic acid) represented by the following. Phenylenebis(α-cyanobutadienecarboxylic acid) or its ester derivative represented by the above formula [] used in the present invention will be described in detail. In the formula, R is a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms. Preferably used aliphatic hydrocarbon groups include 1 to 8 linear or branched alkyl groups, and specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and n-amyl. , isoamyl, 2-ethylhexyl group, and the like. On the other hand, Ar is m-phenylene and p-phenylene groups. Next, a method for producing phenylene bis(α-cyanobutadienecarboxylic acid) or its ester derivative represented by the above formula [], which is another aspect of the present invention, will be described. Phenylene bis (α-
Cyanobutadienecarboxylic acid) or its ester derivative can be obtained by dehydration condensation of phenylenediacrolein represented by the above formula [] and α-cyanoacetic acid represented by the above formula [] or its ester derivative. Phenylenediacrolein and α-cyanoacetic acid and their ester derivatives used as raw materials are commercially available. A general embodiment of the reaction is at least 2 moles of α per mole of phenylenediacrolein.
- Cyanoacetic acid or ester derivatives are reacted at room temperature or by heating, preferably in a solvent in the presence of a catalyst (reaction promoter). The number of moles of α-cyanoacetic acid used is generally in the range of 2 to 10 moles, preferably 2 to 8 moles, per mole of phenylenediacrolein. If it is less than that, unreacted aldehyde remains, which is not preferable because the raw material phenylenediacrolein remains in the reaction product, or a by-product resulting from dehydration condensation of one of the aldehyde groups is produced. Further, if it is more than that, not only is there no point in adding excess α-cyanoacetic acid or ester, but also a large amount of excess unreacted α-cyanoacetic acid or ester must be removed, which is not preferable. In the reaction, an inorganic or organic base catalyst is preferably used. The former includes alkali metals or alkaline earth metals such as lithium, sodium, potassium, calcium, barium, and magnesium; or their hydroxides; oxides; hydrides; inorganic and organic salts such as carbonates and acetates; Examples include alkoxides. The latter include ammonia, methylamine, ethylamine,
Primary amines such as butylamine and cyclohexylamine; Secondary amines such as diethylamine, dibutylamine, piperidine, pipolidine, and morpholine; triethylamine, tributylamine, N-
3 such as methylpiperidine, N-methylmorpholine, etc.
Class amines: Examples include amines such as pyridine (derivatives), and inorganic and organic salts such as carbonates and acetates. Further, basic solvents such as N-methylpyrrolidone and N,N-dimethylformamide can also serve as catalysts. Generally, under mild conditions, the catalyst is not consumed, so the amount of catalyst, i.e. phenylenediacrolein 1
0.001 to 1 mole, preferably 0.01 to 1 mole
It is used in a range of 0.5 mol. In this case, R' of α-cyanoacetic acid or its ester derivative represented by the above formula [] used as a raw material does not undergo chemical change.
Therefore, R in the product phenylene bis(α-cyanobutadienecarboxylic acid) or its ester derivative represented by the above formula [] is the same as R'. On the other hand, when the reaction is carried out in water using conditions that involve ester hydrolysis, for example, using an alkali metal, the product R is obtained in the form of a hydrogen atom, in other words, in the form of a carboxylic acid. In such a case, the accelerator is consumed as the reaction progresses, so it is added in an equivalent or more amount to the aldehyde group. The reaction solvent used in the present invention is
Water; Alcohols such as methanol, ethanol, propanol, butanol; Diethyl ether,
diisopropyl ether, tetrahydrofuran,
Ethers such as dioxane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone; halogenated hydrocarbons such as dichloromethane, chlororum, tetrachloroethane, trichloroethane; n-hexane, n-heptane, cyclohexane, benzene, toluene, xylene, etc. Hydrocarbon solvents; ester solvents such as ethyl acetate and butyl acetate; aprotic polar solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, hexamethylphosphoramide, and tetramethylurea, etc. are used. The solvent may be used alone or in a mixed solvent system. The reaction temperature is -30°C to 80°C, preferably -
It is carried out in the range of 10°C to 50°C. Below that, the reaction progresses slowly and is not substantial. If it exceeds this range, by-products will be produced, which is not preferable. The reaction time is 1 minute to 72 hours, preferably 5 minutes to 36 hours, although it depends on the reaction temperature.
If it is less than that, the reaction will not be completed, which is not preferable, and if it is more than that, there is no point in prolonging the time, and it is also not preferable from the viewpoint of industrial production. In the present invention, the process may proceed in a homogeneous system depending on the type of solvent, but it may also be carried out in a heterogeneous system. Even in such a case, the phenylenediacrolein represented by the above formula [] used as a raw material is partially dissolved and subjected to the reaction, and the product is precipitated again. Next, according to another production method of the present invention, phenylene bis(α-cyanobutadienecarboxylic acid) represented by the above formula [] and the alcohol represented by the above formula [] are subjected to an esterification reaction to produce the above formula []. The method for producing the phenylene bis(α-cyanobutadiene carboxylic acid) ester shown will be described in detail. A common embodiment involves thermally reacting a carboxylic acid in an alcohol in the presence of an esterification catalyst. In the alcohol represented by the above formula []
R' is the same as the hydrocarbon group explained in the section of R of the phenylene bis(α-cyanobutadienecarboxylic acid) ester represented by the above formula []. Alcohol is used in an amount of 2 to 500 moles, preferably 2 to 200 moles, per mole of carboxylic acid. The catalyst used is a general esterification catalyst, such as inorganic acids such as sulfuric acid, phosphoric acid, and hydrogen chloride, and organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and benzenesulfonic acid. The reaction temperature is -30℃ to 200℃, preferably -
It is carried out at a temperature ranging from 10℃ to 150℃. If it is less than that, the reaction will not proceed sufficiently, which is not preferable, and if it is more than that, it will cause undesirable side reactions, which is not preferable. The reaction time is 10 minutes to 48 hours, preferably 30 minutes to 24 hours, although it depends on the reaction temperature.
If it is less than that, the reaction will not be completed sufficiently, and if it is more than that, there is no point in prolonging the reaction, so it is not preferable. In this case as well, the reaction does not necessarily proceed in a homogeneous system, but also in a heterogeneous system. Even in such a case, the raw materials gradually dissolve and react, and the product precipitates out again. The thus obtained phenylenebis(α-cyanobutadienecarboxylic acid) and its ester derivatives can be purified by methods such as recrystallization.
Further, its structure and purity can be confirmed by elemental analysis, nuclear magnetic resonance spectroscopy, infrared absorption spectroscopy, ultraviolet-visible absorption spectroscopy, chromatography, etc. Phenylene bis(α-
Cyanobutadienoic acid) and its derivatives are useful as raw materials for visible light-sensitive polyesters, and are widely used in the information electronics field, in the form of resist resins, laser-sensitive direct plate-making resins, etc.
It is used in fields such as printing. The present invention will be explained in detail with reference to Examples below. However, the present invention is not limited to this. In the examples, all parts are by weight. Example 1 3000 parts of water and 88 parts of caustic soda were placed in a three-necked flask, and 202 parts of methyl cyanoacetate was added thereto.
After heating to 50°C and stirring for 1 hour, the mixture became homogeneous. Next, 168 parts of p-phenylenediacrolein was added and stirred under heating at 70 to 80°C in a nitrogen atmosphere, and the reaction mixture became homogeneous in about 3 hours. When the mixture was allowed to cool and concentrated hydrochloric acid was added until it became acidic, a red solid precipitated out. This was filtered, thoroughly washed with water, and then dried to give 260 parts (yield: 84%) of p-phenylenebis(α-cyanobutadienecarboxylic acid) (-a). The melting point of this compound was over 300°C.
The infrared spectrum and elemental analysis values are shown in Table 2. Example 2 33.6 parts of p-phenylenebis(α-cyanobutadienecarboxylic acid) (-a) was mixed with 3000 parts of normal butanol.
When the mixture was heated and refluxed with 60 parts of concentrated sulfuric acid, the reaction mixture became homogeneous in 5 to 6 hours. When this was allowed to cool, reddish-orange needle-shaped crystals were precipitated. When the crystals were filtered and dried, 37.3 g of p-phenylene bis(n-butyl α-cyanobutadienecarboxylate) (-b) was obtained (yield: 86
%) obtained. The ¹ HNMR spectrum of this product showed the following values. ¹ HNMR (CDCl ₃ , δ) 0.76-2.40 (m) 14H 4.30 (t) 4H 6.9-8.2 (m) 7.68 (s) 10H Also, the ultraviolet rays of this product in acetonitrile -
In the visible spectrum, λmax was observed at 390 nm. When recrystallized from dioxane-isopropanol, the melting point was 186-187°C, and the infrared spectrum and elemental analysis are shown in Table 2. Example 3 33.6 parts of p-phenylenebis(α-cyanobutadienecarboxylic acid) was added to 500 parts of 2-ethylhexyl alcohol, and 50 parts of concentrated sulfuric acid was added thereto, followed by heating under reflux. The reaction mixture became homogeneous in about 4 hours, and when it was allowed to cool, orange needle-like crystals were precipitated. When filtered and dried, p-phenylene bis(α-cyanobutadienoic acid 2-ethylhexyl) (
-c) was obtained in 40 parts (yield 69%). When this compound is recrystallized from isopropanol, it reaches 145-146℃.
The infrared spectrum and elemental analysis are shown in Table 2. Example 4 18.6 parts of p-phenylenediacrolein and 20.4 parts of cyanoacetic acid were placed in 1000 parts of ethanol. While stirring at room temperature, 5 parts of piperidine as a catalyst was added. After stirring at room temperature for 12 hours, the reaction mixture turned red-orange. The produced solid was collected by filtration, washed twice with 50 parts of chilled ethanol, and dried to obtain 24 parts of p-phenylene bis(α-cyanobutadienecarboxylic acid (-a) (yield 71%)). The infrared spectrum and melting point of this compound were both consistent with those of Example 1. Examples 5 to 21 Examples 5 to 7 were similar to Example 4, with cyanoacetate (R=CH ₃ , C ₂ H ₅ , n -C ₄ H ₉ ).In Examples 8 to 12, methyl cyanoacetate was used to carry out the synthesis reaction by changing the solvent.
Furthermore, in Examples 13 to 21, synthesis reactions were carried out using methyl cyanoacetate, methanol solvent, and different catalysts. These results are shown in Tables 1 and 2. Examples 22 to 25 m-phenylenediacrolein and cyanoacetic acid (ester) were placed in an alcohol solvent, and a synthetic reaction was carried out using piperidine as a catalyst. These results are summarized in Tables 3 and 4.

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[Table] Items in the table have the same meaning as in the main text.

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[Table] Reference Example A reaction was carried out in the same manner as in Example 4. 9.3 parts of p-phenylenediacrolein and cyanoacetic acid ester

A reaction was carried out for 12 hours using 19.9 parts of [Formula], 500 parts of methanol as a solvent, and 5 parts of piperidine as a catalyst. As a product, 6.3 parts (yield 24.6%) were obtained.

Claims (1)

[Claims] 1. The following general formula [] [However, in the formula, R is the same or different, and is a group selected from the group consisting of a hydrogen atom and a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and Ar is a m-phenylene group or a p-phenylene group. represent. ] Phenylene bis(α-cyanobutadienecarboxylic acid) or its ester derivative represented by: 2 General formula below [] OCH-CH=CH-Ar-CH=CH-CHO
... [] [However, in the formula, Ar is m-phenylene group or p-
Represents a phenylene group. ] Phenylene bis-acrolein represented by and the following general formula [] [However, in the formula, R is a hydrogen atom and a carbon atom number of 1 to 10
A group selected from the group consisting of monovalent aliphatic hydrocarbon groups. ] The following general formula [] is characterized by dehydration condensation with α-dianoacetic acid or its ester derivative represented by [] [However, Ar and R are as defined above. ] A method for producing phenylene bis(α-cyanobutadienecarboxylic acid) or its ester derivative. 3 General formula below [] [However, in the formula, Ar represents m-phenylene or p-phenylene group. ] Phenylene bis (α-cyanobutadiene carboxylic acid) represented by the following general formula [] ROH ... [] [However, in the formula, R represents a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms. ] The following general formula [] is characterized by causing an esterification reaction with an alcohol represented by [However, in the formula, Ar and R are as defined above. ] A method for producing an ester derivative of phenylenebis(α-cyanobutadienecarboxylic acid) represented by: