JPS5911601B2 - Method for producing photo-insolubilizable polyvinyl alcohol derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a novel polyvinyl alcohol derivative that is insolubilized by light, and more specifically, shows high sensitivity even with a low content of photosensitive functional groups,
The present invention relates to a method for producing a novel photo-insolubilizable polyvinyl alcohol derivative that can be used as a photoresist, a photosensitive vehicle, a substrate for enzyme immobilization, etc.

In recent years, photosensitive resins have been used as photoresists, for example, image resists for plate making such as planography, letterpress, and gravure, photoresists for corrosion processing such as printed wiring, integrated circuits, and shadow masks, and photoresists for photosensitive paints, varnishes, and glass. It is widely used as an adhesive, etc., and is not limited to photoresists, but also as a photosensitive vehicle for paints and printing inks, a base material for photosensitive resin 30 letterpress and resin plates, a base material for enzyme immobilization, etc. It is used.

Conventionally, photosensitive resins include azide groups, cinnamoyl groups,
Those having a photosensitive functional group such as an acryloyl group are known.

However, these five photosensitive functional groups have low sensitivity, so it is necessary to introduce a large amount into the resin, and usually they must be introduced at a ratio of 50 to 100 mol% per repeating unit of the polymer. Therefore, it has the disadvantage of high cost, and is not necessarily satisfactory. The present inventors have conducted intensive research to develop a new photoinsolubilizing compound that overcomes the drawbacks of conventional photosensitive resins, and as a result, we have developed a method that incorporates a special photosensitive functional group into polyvinyl alcohol. The inventors have discovered that the objective can be achieved by introducing the above, and have completed the present invention based on this knowledge. That is, the present invention provides completely saponified or partially saponified polyvinyl acetate with the general formula (wherein R1 is a hydrogen atom, a cyano group, a carboxyl group, or an alkoxycarbonyl group, and R2 is a carboxyl group, an alkoxycarbonyl group, or a cyano group). or a carbamoyl group, and n is 0 or 1) or its acetal derivative, some of the repeating units of polyvinyl acetate that have been completely saponified or partially saponified are converted into

The present invention provides a method for producing a photo-insolubilizable polyvinyl alcohol derivative having a structure substituted with a unit represented by ((in the formula, R1, R2, and n have the same meanings as above).

The novel polyvinyl alcohol derivative represented by such a general formula exhibits extremely high sensitivity even when the content of photosensitive functional groups is as low as 0.1 to 20 moles per repeating unit.

The novel polyvinyl alcohol derivative of the present invention has the general formula 0 for completely saponified or partially saponified polyvinyl acetate.
) or its acetal derivative. Examples of such aldehydes represented by the general formula 0) include P-formylcinnamic acid, P-formylcinnamic acid ester,
P-formylcinnamic acid amide, α-cyano-P-formylcinnamylidene acetic acid, α-cyano-P-formylcinnamylidene acetate, P-formylcinnamylidene acetic acid, P-formylcinnamylidene acetic acid Examples include acetate ester, α-ethoxycarbonyl-P-formylcinnamylidene ethyl acetate, α-cyano-P-formylcinnamylidene acetamide, α-cyano-P-formylcinnamylidene acetanilide, etc. can.

Examples of acetal derivatives include dimethyl acetal and diethyl acetal of these aldehydes. These aldehyde or acetal derivatives can be prepared, for example, by the reaction of terephthalaldehyde or its monoacetal with a compound having an active methylene group such as malonic acid, or P-formylcinnamic acid derivatives or
P-formylcinnamylidene acetic acid derivatives are easily synthesized by reacting -formylcinnamaldehyde with a compound having an active methylene group.

On the other hand, saponified polyvinyl acetate used as a raw material can be completely saponified or partially saponified, but in order to increase water solubility, it is necessary to use partially saponified polyvinyl acetate containing acetyl groups. is preferable, and it is particularly desirable to use one having an acetyl group content of less than 30 mol%.

Furthermore, it is appropriate for this fully saponified or partially saponified polyvinyl acetate to have an average degree of polymerization in the range of 200 to 3,000, but from the viewpoint of handling the obtained compound, it is preferable to have a degree of polymerization of 500 to 2,000. suitable. Next, the manufacturing method of the present invention will be explained.

That is, the photocrosslinkable polyvinyl alcohol derivative of the present invention represented by the above general formula 0) can be obtained by reacting completely saponified or partially saponified polyvinyl acetate with an aldehyde or its acetal derivative represented by general formula H). obtained by.

This reaction is advantageously carried out in water or a water-containing organic solvent in the presence of an acid catalyst. In this case, the acid used as a catalyst is not particularly limited and may be either an inorganic acid or an organic acid, but phosphoric acid and sulfuric acid are preferred from the viewpoint of solubility in water and ease of handling. In this reaction, aldehyde or its acetal derivative is added at 0% per vinyl alcohol unit in completely saponified or partially saponified polyvinyl acetate.
．． It is preferable to use the polyvinyl acetate in a proportion of 1 to 30 mol%, and the concentration of completely saponified or partially saponified polyvinyl acetate in the reaction solvent is preferably in the range of 1 to 10% by weight. In addition, the reaction temperature is suitably in the range of room temperature to 100°C,
The reaction time is about 2 to 40 hours.

The reaction solution after the reaction is completed can be used as it is as a highly sensitive photosensitive solution, or if it is necessary to separate the desired product as a solid, it can be reacted in a poor solvent such as acetone or methanol. After adding the finishing liquid and separating the resulting precipitate, it may be washed with alcohol or the like and then dried under reduced pressure. The photoinsolubilizable polyvinyl alcohol derivative of the present invention has a photosensitive functional group content of 0.1 per repeating unit.
Even in the low range of ~30 mol%, it has sufficient sensitivity to ultraviolet light by itself, but by adding an appropriate sensitizer, the sensitive region can be further expanded to the visible region. .

When the photosensitive functional group is a P-formylcinnamic acid group, examples of the sensitizer include N-acetyl-4-nitro-1-naphthylamine, 1,2-benzanthraquinone, picramide, 5-nitro acenaphthene, 3-methyl-1-diaza-1,9-benzanthrone, Michler's ketone, etc., and when the photosensitive functional group is a P-formylcinnamylidene group, for example, erythrosine,
Examples include rose bengal. These sensitizers may be added after the completion of the reaction or to a solution of a purified photo-insolubilizable polyvinyl alcohol derivative dissolved in an appropriate solvent.
The amount added can be appropriately selected depending on the required sensitivity, but is preferably in the range of 20 to 60 mol % based on the photosensitive functional group. The photoinsolubilizable polyvinyl alcohol derivative of the present invention to which a sensitizer has been added exhibits a photosensitivity comparable to or higher than that of polyvinyl cinnamate sensitized with 5-nitroacenaphthene.

In other words, the photoinsolubilizable polyvinyl alcohol derivative of the present invention has a lower introduction rate of photosensitive functional groups than conventional products;
In addition, despite the small amount of sensitizer added, it exhibits sufficiently high sensitivity and is economically extremely valuable.

Therefore, this product is not only useful as a photoresist or a photosensitive vehicle, but because the crosslinking reaction is a photodimerization reaction and proceeds specifically, it can be used as a material for biofunctional materials such as enzymes, biological cell fragments, and microorganisms. It is also extremely useful as a fixing material. Furthermore, based on the adhesive properties of polyvinyl alcohol, it can also be used as adhesives, binders, paint base materials, etc. whose properties improve upon irradiation with light. Next, the present invention will be explained in more detail with reference to Examples.

Reference Example 1 Production of α-cyano-P-formylcinnamylidene methyl acetate: P-diethoxymethylcinnamaldehyde was synthesized from terephthalaldehyde diethyl monoacetal and acetaldehyde, and this product contained 702η and methyl cyanoacetate 297r! 9 was dissolved in 10 d of methanol, 1 drop of piperidine was added, and the mixture was stirred at room temperature for about 3 hours.

The precipitated crystals were collected by filtration and recrystallized from methanol-hexane to obtain α-cyano-P-diethoxymethylcinnamylidene methyl acetate at 390°C. This one is mp
The temperature was 82.5-83.5°C. On the other hand, two drops of hydrochloric acid were added to the filtrate, and the mixture was heated and stirred at about 50°C for 1 hour, and the resulting crystals were recrystallized from methanol to produce α-cyano-P.
-260 mg of methyl cinnamylidene acetate was obtained.

This substance is dark yellow needle-like crystals, mp217-220℃
λma)c344nm, ε=48.300 (methanol). Reference Example 2 Production of α-1ethoxycarbonyl-P-formylcinnamylidene ethyl acetate: Dissolve 234η of P-diethoxymethylcinnamaldehyde and 160Wlf of diethyl malonate in 5d of methanol, add 1 drop of piperidine, and cool to room temperature. The mixture was stirred for 3 hours.

After concentrating the methanol to about half, 5 liters of water and 1 drop of concentrated hydrochloric acid were added, and the mixture was stirred at room temperature overnight. The precipitated crystals were collected by filtration and recrystallized from methanol and water to obtain α-1ethoxycarbonyl-P-formylcinnamylidene ethyl acetate 108 as yellow flaky crystals. This thing is
Mp9O-92°C, λMax295nm, ε=50.
250 (methanol 71/). Reference Example 3 Production of P-formyl cinnamylidene methyl acetate: P-
468η of diethoxymethylcinnamaldehyde and 218η of malonic acid were dissolved in pyridine 4a, one drop of piperidine was added thereto, and the mixture was heated under reflux for about one day.

After pyridine was distilled off under reduced pressure, 4 ml of methanol and 1 ml of concentrated sulfuric acid were added.
Add dropwise and heat to reflux for about 6 hours. After distilling off methanol, 5 d of water was added and extracted with chloroform. After drying the extract, chloroform was distilled off, and the resulting residue was recrystallized from hexane to obtain P-formylcinnamylidene methyl acetate 137T19 as pale, colored needle-like crystals. This one is MplOO, 5-101.5℃, λM
ax 295 nm, ε-35.500 (methanol). Reference Example 4 Production of α-cyano-P-formyl cinnamylidene acetanilide: P-diethoxymethyl cinnamaldehyde 234η and α-cyanoacetanilide 1
60η was dissolved in 5d of methanol, 1 drop of piperidine was added, and the mixture was stirred at room temperature for 1 hour.

When the precipitated crystals are filtered and recrystallized from methanol, M
α-Cyano-P-diethoxymethylcinnamylidene acetanilide 3 as yellow scaly crystals with a pl of 65-167°C
21r! 9 was obtained.

J this thing 250rf1f methanol 5ml
and 1 WLI of water, and after adding 1 drop of concentrated hydrochloric acid, the mixture was stirred at room temperature for 8 hours. After distilling off methanol, 5 d of water was added and extracted with methylene chloride. After drying, methylene chloride was distilled off, and the residue was recrystallized from methanol to obtain 187 mf of α-cyano-P-formylcinnamylidene acetanilide as pentamorphic yellow needles. This one is Mpl75
．． 5-176.5℃, λMax346nm, ε=292
36 (it was methanol paste.Example 2d of acetic acid and 0.3f of phosphoric acid were added to 8.4t of a 5% by weight aqueous solution of 1485% saponified polyvinyl acetate (average degree of polymerization 1700), and methyl P-formylcinnamate was added to this. 60.8 rv of acetic acid 2d solution was added dropwise to approx.
The mixture was heated and stirred at 60°C for 15 hours.

To the reaction solution thus obtained was added 0.5 equivalents of N-acetyl-4-nitro-1-naphthylamine as a sensitizer based on the photosensitive group. This solution was applied to an aluminum plate, exposed to light using a xenon lamp through a negative film, and then developed in a mixed solvent of water, acetic acid, and dimethylformamide to obtain a bright image on the aluminum plate. Example 2 To a photosensitive resin solution synthesized in the same manner as in Example 1, 0.5 equivalent of picramide was added as a sensitizer based on the photosensitive group.

By performing the same operations as in Example 1, a clear image was obtained on the aluminum plate. Example 3 Dimethylacetamide 1a and 0.2f of phosphoric acid were added to 2.1r of a 5% by weight aqueous solution of 85% saponified polyvinyl acetate (average degree of polymerization 1700), and a-cyano-P-formylcinnamylidene was added to this. Methyl acetate 38.4W9 dimethylacetamide 2.51! Add Ll solution dropwise, about 50-6
The mixture was heated and stirred at 0°C for 27 hours.

The reaction solution obtained in this way was poured into acetone,
The precipitate was washed and dried under reduced pressure. The photosensitive resin 40r11f thus purified was dissolved in 1 d of water and 1 d of methyl cellosolve, applied to an aluminum plate, exposed to light with a xenon lamp through a negative film, and then developed with water. A clear image was obtained on the aluminum plate. Example 4 To 1.6 t of a 6.7 wt% aqueous solution of 85% saponified polyvinyl acetate (average degree of polymerization 1700) was added 0.5 d of dimethylformamide and 0.2 f7 of phosphoric acid, and to this was added P-formyl cinnamylidene. A solution of 1.3η of methyl acetate in 0.5a of dimethyl formamide was added dropwise, and the mixture was heated and stirred at about 50 to 60°C for 24 hours.

The reaction solution thus obtained was applied to an aluminum plate, exposed to light using a xenon lamp through a negative film, and then developed in a mixed solvent of water and acetic acid to obtain a bright image on the aluminum plate. Although this material was not sensitized, it exhibited a photosensitivity rate approximately 2.5 times that of polyvinyl cinnamate sensitized with 5-nitroacenaphthene. Example 5 To 2.1 t of a 5 wt% aqueous solution of 85% saponified polyvinyl acetate (average degree of polymerization 1700), 1 ml of dimethylacetamide and 0.2 t of phosphoric acid were added, and to this was added α-cyano-P-formylcinnamylidene. A solution of acetanilide 12η in dimethylacetamide 1d was added dropwise, and the mixture was heated and stirred at about 50 to 60°C for 24 hours.

The reaction solution obtained in this way was poured into acetone,
The precipitate was washed and dried under reduced pressure.

Claims (1)

[Claims] 1 Completely saponified or partially saponified polyvinyl acetate has a general formula ▲ mathematical formula, chemical formula, table, etc. ▼ (R_1 in the formula is a hydrogen atom, a cyano group, a carboxyl group, or an alkoxycarbonyl group) One of the repeating units of polyvinyl alcohol characterized by reacting with an aldehyde or its acetal derivative represented by the following formula: R_2 is a carboxyl group, an alkoxycarbonyl group, a cyano group, or a carbamoyl group, and n is 0 or 1. A method for producing a photo-insolubilizable polyvinyl alcohol derivative having a structure in which the part is substituted with a unit represented by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (R_1 and R_2 in the formula have the same meanings as above) .