JPS5867702A - Light insolubilizing polyvinyl alcohol derivative and its preparation - Google Patents

Abstract

PURPOSE:The titled derivative, prepared by reacting polyvinyl acetate with a specific aldehyde derivative, capable of exhibiting a high sensitivity even with a low content of photosensitive functional groups, and suitable for photoresists, etc. CONSTITUTION:A light insolubilizing polyvinyl alcohol derivative, expressed by formula III[R1 is H or acetyl; (k) and (l) are natural numbers]or formula IV [(m) is a natural number], and prepared by reacting (A) a completely or partially saponified polyvinyl acetate having 200-3,000 average polymerization degree with (B) 0.1-30mol%, based on one vinyl alcoholic unit in the component (A), aldehyde, obtained by reacting cinnamoyl chloride with aminoacetaldehyde dimethyl acetal, etc., and expressed by formulaI[R is alkylene or phenylene; X is O or imino; (n) is 1 or 2], e.g. 2,2-dimethoxyethyl cinnamide, or an acetal derivative thereof, in the presence of an acidic catalyst, e.g. phosphoric acid, to give the repeating units of the component (A) partially substituted by the units expressed by formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel polyvinyl alcohol derivative that is insolubilized by light and a method for producing the same.More specifically, the present invention relates to a novel polyvinyl alcohol derivative that is insolubilized by light and a method for producing the same. This invention relates to a novel photo-insolubilizable polyvinyl alcohol derivative that can be used as a photosensitive vehicle, a substrate for enzyme immobilization, etc., and a method for producing the same.

In recent years, photosensitive resins have been used as photoresists, such as image resists for plate making such as planography, curved plates, and gravure, resists for corrosion processing such as printed wiring, integrated circuits, and shadow masks, and adhesives for photosensitive paint faces and glass. It is widely used as a photosensitive vehicle for paints and printing inks, for photoresists, as a matrix base material for photosensitive resin curved plates and resin plates, and as a base material for enzyme immobilization. There is.

Conventionally, photosensitive resins include azide F group, cinnamoyl group,
Products with photosensitive functional groups such as acryloyl groups are known. However, since these photosensitive functional groups have low sensitivity, it is necessary to introduce large amounts into the resin, and they are usually used in polymers. It has to be introduced at a ratio of 50 to 100 moles per repeating unit, which has the drawback of increasing costs and is not necessarily satisfactory.

The present inventors have developed a novel photoinsolubilizable compound that overcomes the drawbacks of conventional photosensitive resins.
The present invention has been made based on this knowledge to have found a way to achieve the object, and to have completed the present invention based on this knowledge. (In the formula, R is an alkylene group or a phenylene group, X is an oxygen atom or an imino group, and n is an integer of 1 or 2) Saponified or partially saponified polyvinyl acetate is completely saponified or partially saponified by reacting an aldehyde represented by the general formula (R, X and n in the formula have the same meanings as above) or an acetal derivative thereof. A method for producing a photo-insolubilizable polyvinyl alcohol derivative having a structure in which some of the repeating units of polyvinyl acetate are substituted with units represented by the general formula (+), and completely saponified or partially saponified polyvinyl acetate Some of the repeating units are units represented by the general formula (1) and the general formula (M in the formula is a hydrogen atom or an alkali metal atom, and the phenyl group may have an inert nuclear substituent in some cases) Photoinsoluble (14
A polyvinyl alcohol derivative and a completely saponified or partially saponified polyvinyl acetate are combined with an aldehyde represented by the general formula (n) or an acetal derivative thereof, and the general formula (M in the formula has the same meaning as above, phenyl The group may optionally have an inert nuclear substituent) by reacting with benzaldehyde or its acetal derivative represented by the general formula ( The present invention provides a method for producing a photo-insolubilizable polyvinyl alcohol derivative having a structure substituted with the unit represented by 1) and the unit represented by the general formula (sha).

The saponified polyvinyl acetate used as a raw material in the present invention may be completely saponified or partially saponified, but it may contain some unsaponified acetyl groups to increase water solubility. is preferable, and it is particularly desirable to use one having an acetyl group content of less than 30 molar percentages. Therefore, the photo-insolubilizable polyvinyl alcohol derivative of the present invention has the general formula (in which R, X and n are as defined above). have the same meaning, R1 is a hydrogen atom or an acetyl group, or both, k and 1 are natural numbers) or the general formula (in which R, Ri, and X%, l and n have the same meanings as above, m is a natural number, and the phenyl group having a sulfonic acid group may optionally have an active nuclear substituent.

Further, the fully saponified or partially saponified polyvinyl acetate used in the present invention is suitably one with an average degree of polymerization in the range of 200 to 3000, and in particular, from the viewpoint of handling the target compound, the average degree of polymerization is 500. A range of 2,000 to 2,000 is preferred.

Examples of the compound represented by the general formula (It) used to introduce a photosensitive functional group in the present invention include the following compounds.

(1) N-(formylmethyl)cinnamide (2) N-
(Formylmethyl)cinnamylideneacetamide (3) (Formylmethyl)cinnamate (4)
4-formylbutyl cinnamate (5) Formylmethyl cinnamylidene acetate (6) 2-methoxy-4-formyl cinnamylidene acetate (7) p-formylphenyl cinnamylidene acetate (s) ( p-formylphenyl) cinnamate The phenyl group present in these compounds can optionally be substituted with substituents,
For example, it may be substituted with an alkyl group, a methoxy group, a cyan group, a nitro group, etc.Acetal derivatives of the above compounds can also be used as components for introducing photosensitive functional groups.As the acetal derivatives, for example, these aldehyde Examples include dimethyl acetal and diethyl acetal.

These aldehyde and acetal derivatives can be easily produced from cinnamic acid or cinnamic acid chloride and, for example, 2,2-diethoxyethyl bromide or aminoacetaltehyde dimethyl acetal.

Furthermore, in order to increase the water solubility of the target photoinsolubilizable polyvinyl alcohol derivative, in addition to introducing a photosensitive functional group into completely saponified or partially saponified polyvinyl acetate, ) Introducing a sulfonic acid group using benzaldehyde or its acetal derivative is also included. As a compound represented by this general formula (yield), for example, sodium-2-methoxy-4
-Formylbenzenesulfonate and the like are used.

Next, the manufacturing method of the present invention will be explained.

That is, the photo-insolubilizable polyvinyl alcohol derivative of the present invention represented by the above general formula (V) is produced by reacting completely saponified or partially saponified polyvinyl acetate with an aldehyde represented by the general formula (n) or its acetal derivative. It can be obtained by This reaction is advantageously carried out in water or a water-containing organic solvent in the presence of an acid catalyst.

The acid 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, the aldehyde or its acetal derivative is preferably used in a proportion of 0.1 to 30 moles per vinyl alcohol unit in completely saponified or partially saponified polyvinyl acetate, and Or partially saponified polyvinyl acetate concentration is 1 to 10
A weight range is preferred.

Regarding the reaction temperature and reaction time, it is necessary to select conditions such that ester bonds and amide bonds are not hydrolyzed, and these conditions vary depending on the type of aldehyde used, but generally the reaction temperature is between room temperature and iodine. The range of temperature is suitable, and the reaction time is about 2 to 30 hours.

The resulting reaction solution can be used as it is as a highly sensitive photosensitive solution, or the desired product can be separated as a solid. If necessary, the reaction can be completed in a poor solvent such as acetone or methanol. After adding the liquid and separating the resulting precipitate, it may be washed with alcohol or the like (or dried under reduced pressure).

Furthermore, the photo-insolubilizable polyvinyl alcohol derivative of the present invention represented by the above general formula (Vl) is prepared by adding an aldehyde or its acetal derivative represented by the general formula (n) to completely saponified or partially saponified polyvinyl acetate. Formula (1
It can be obtained by reacting benzaldehyde represented by v) with its acetal derivative in the same manner as above. In this case, benzaldehyde or its acetal derivative represented by the general formula (Y) is preferably used in a proportion of 1 to 10 mol per vinyl alcohol unit in completely saponified or partially saponified polyvinyl acetate. The product thus obtained is a highly water-soluble, photoinsolubilizable polyvinyl alcohol derivative.

The photo-insolubilizable polyvinyl alcohol of the present invention has sufficient sensitivity to ultraviolet light even when the content of photosensitive functional groups is as low as 0.1 to 30 moles per repeating unit. However, by adding an appropriate sensitizer, the sensitive region can be further expanded to the visible region.

As this sensitizer, when the photosensitive functional group is a cinnamoyl group, for example, N-acetyl-4-nitro-1-
Naphthylamine, ■,2-penzanthraquinone, picramide, 5-nitroacenaphthene, 3-methyl-l-diaza-1,9-benzanthrone-Michael's ketone, etc., and the g-photosensitive functional group is a cinnamic IJ dene group. Examples include evaerythrosine and rose bengal. These sensitizers may be added to the reaction-completed solution or to a solution prepared by dissolving a purified photo-insolubilizable polyvinyl alcohol derivative in an appropriate solvent. The amount added can be appropriately selected depending on the required sensitivity, but if it is too small, the sensitivity will be low, and if it is too large, no further sensitivity can be expected and it is wasteful. The preferred range is 60 to 60 molar ratios.

The photoinsolubilizable polyvinyl alcohol derivative of the present invention to which a sensitizer has been added exhibits a photosensitivity rate that is equivalent to or several times 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, and despite the small amount of sensitizer added, it exhibits sufficiently high sensitivity and is economical. It is of extremely high value.

Therefore, this product is not only useful as a photoresist or a photosensitive vehicle, but also because the crosslinking reaction is a photodimerization reaction and proceeds specifically, it can be used for biological bases such as enzymes, biological cell fragments, and microorganisms. It can also be used as adhesives, binders, and paints whose properties improve when exposed to light.

Next, the present invention will be explained in more detail with reference to Examples.

Reference Example 1 Preparation of 2,2-dimetho-;'-ethylunnabenzumido 50 ug of cinnamic acid chloride was dissolved in 5 me of chloroform, and while stirring under ice cooling, 630 ug of aminoacetaldehyde dimethyl acetal was added. ~ with chloroform 5
Add solution dissolved in ml dropwise. 1 at room temperature after completion of the dropwise addition.
After stirring for a while, add about 1 ornl of water and extract. After drying the organic layer over magnesium sulfate, chloroform was distilled off and the resulting residue was recrystallized from hexane to obtain colorless needle-like crystals of 2,2-dimethoxyethylcinnamamide 649.

This one has mp 70.5-71.5℃, λmax
(methanol): 272 nm, ε=1952
It was 0.

Reference Example 2 Production of 4,4-dimethoxybutylcinnamate Potassium cinnamate 9,3 t and 0:4-ri, rho 1
, 1-diftquinbutane6. Add to lfi dimethylpolamide 30- and heat on an oil bath at about 120°C for 14 hours with stirring. After cooling, excess potassium cinnamate and generated potassium chloride are filtered off, and the filtrate is poured into water and extracted with ethyl acetate.

After drying the organic layer, ethyl acetate was distilled off and the resulting residue was distilled under reduced pressure to give 4,4-dimethoxybutyl/nname.
) 5.3f was obtained.

This one has bp 110-114℃/1 mm H
g, λmax (methanol): 275nmx
It was ε-24000.

Reference Example a Production of 2-methoxy-4-formylphenyl cinnamate.

1.97 ml of the potassium salt of vanillin is poured into Kloporum 10, and a solution of 1.66 F of cinnamic acid chloride dissolved in 10 me of chloroform is added dropwise to this while stirring while cooling with water. After completion of the dropwise addition, at room temperature: (After stirring for an hour, extract by adding 20% of a 10% aqueous sodium carbonate solution. After drying the organic layer, chloroform is distilled off and the resulting residue is recrystallized from hexane. As a result, 2-methoxy-4-formylphenyl cinnamate 2.382 in the form of colorless scale crystals was obtained.

This product had a mp of 92 to 93°C, λmax (methanol): 281 nm, and ε-39000.

Reference Example 42. Preparation of 2-dimethoxyethyl 7-namilitene acetamide Cinnamilitane acetyl chloride 481~ was dissolved in 10 ml of methylene chloride, and the solution was stirred while cooling on ice.
A solution of 525 ml of aminoacetaldehyde dimethyl acetal in 10 ml of methylene chloride is added dropwise.

After stirring at room temperature for 3 hours after the addition, the main fishing 20-
Add and extract. After drying the organic layer, methylene chloride was distilled off, and the resulting residue was recrystallized from hexane to give 2,2-
547 ml of dimethoxyethyl cinnamylidene acetamide was obtained.

This product had a temperature of m9105 to 106°C, λmax (methanol): 304 nm% ε-22360.

Example 1 85 saponified polyvinyl acetate (average degree of polymerization 1700)
1ζ Rei 5 weight aqueous solution 2.1 t, acetic acid 0.5 ml, dimethylacetamide 0.5 m/and phosphoric acid 0.22
and 70.5 mg of 2,2-dimethoxyethylcinnamamide obtained in Reference Example 1 and 0.5-mg of acetic acid.
and 0.5 ml of dimethyl acetamide solution was added dropwise to about 8
The mixture was stirred at 0 to 90°C for 27 hours.

To the reaction solution thus obtained, 1.4 equivalents of N-acetyl-4-nitro-1-naphthylamine as a sensitizer was added to the photosensitive functional group. This solution was applied to an aluminum plate, exposed through a negative film to a xenon lamp, and then developed in a mixed solvent of methyl cellosolve, water, and dimethylacetamide, resulting in a clear image on the aluminum plate. .

This product was about three times more sensitive than polyvinyl cinnamate sensitized with 5-nitroacenaphthene.

Example 2 5% by weight aqueous solution of 85% saponified polyvinyl acetate (average degree of polymerization +700)2. N7 with 0.5 ml of acetic acid, 5 ml of dimethylacetamide Q and 0.2.9 ml of phosphoric acid
2,2-dimethoxyethylcinnamilitenacetamide + 0.41n9 obtained in Reference Example 4 and 5.8 m9 of sodium 2-methoxy-4-formylbenzenesulfonate were added to this with 0.5 ml of acetic acid and dimethyl acetate. Add a solution of 0.5 ml of cetamide in a mixed solvent, and add about 80~
The mixture was stirred at 90°C for 25 hours.

The reaction solution obtained in this way was treated with I as a sensitizer.
35.2 m9 of J% rosin was added and applied to an aluminum plate, which was then exposed to a xenon lamp through a negative film. When this was then developed with hot water, an aluminum plate with a clear image of 7 was obtained.

Its relative sensitivity to polyvinylcinnamate sensitized with 5-nitroacenaphthene was hook-and-loop.

Example 3 To a 5% by weight aqueous solution 2.1.9% of 85% saponified polyvinyl acetate (average degree of polymerization 1700) was added 0.5ml of acetic acid, 0.5ml of dimethylacetamide, and 0.2% of phosphoric acid. ! i' and this di 2,2-jethoxyethylcinnamate 5
2.8 to 5 mt of acetic acid and 0.5 mt of dimethylacetamide.
5 ml solution was added and mixed for 25 hours at about 80-90''CM.

After adding 0.4 equivalents of N-acetyl-4-nitro-1-naphthylamine as a sensitizer to the reaction solution obtained in this way with respect to the photosensitive functional group, it was applied to an aluminum plate and a negative film was prepared. exposed to a xenon lamp through Next, this was developed in a mixed solvent of water, dimethylacetamide, and acetic acid to obtain an aluminum plate with a clear image.

The relative sensitivity of this to polyvinyl cinnamate sensitized with 5-nitroacenaphthene was about 1.5 times.

Further, the content of photosensitive functional groups was examined by ultraviolet absorption spectroscopy and was found to be approximately 1.7 mol%.

Example 4 1.6 g of a 6.7% by weight aqueous solution of 99% saponified polyvinyl acetate (average degree of polymerization 2000) and 0.5 ml of acetic acid! , 0.5 ml of dimethyl acetamide and 20.29 ml of phosphorus were added, and to this was added 4,4-dimethoxybutylic acid obtained in Reference Example 2.
Namet 52. 0.5 ml of acetic acid and dimethylacetamide] solution of SMY was added and stirred at about 50 to 60°C for 6 hours.

After adding 0.4 equivalent of N-acetyl-4-nitro-1-naphthylamine as a sensitizer to the reaction solution obtained in this way, based on the photosensitive functional group, the mixture was coated on an aluminum plate, and a negative film was formed. exposed to a xenon lamp through Then, when developed in a mixed solvent of water, methyl cellosolve, and dimethyl acetamide, an aluminum plate with a clear image was obtained.

The relative sensitivity of this to polyvinyl cinnamate sensitized with 5-nitroacenaphthene was about 6 times higher. Further, the content of photosensitive functional groups was examined by ultraviolet absorption spectroscopy and was found to be approximately 5 mol %.

Patent applicant Makoto Ishiita, Director of the Agency of Industrial Science and Technology

Claims (1)

[Claims] ■ Some of the repeating units of completely saponified or partially saponified polyvinyl acetate are formed by the general formula (in the formula, R is an alkylene group or a phenylene group, X is an oxygen atom or an imino group, and n is l or an integer of 2) A photo-insolubilizable polyvinyl alcohol derivative having a structure substituted with a unit represented by: 2 Fully saponified or partially saponified polyvinyl acetate, an aldehyde represented by the general formula (in the formula, R is an alkylene group or a phenylene group, X is an oxygen atom or an imino group, and n is an integer of 1 or 2) or A part of the repeating units of completely saponified or partially saponified polyvinyl acetate, which is characterized by reacting its acetal derivative, has the general formula (R, X and n have the same meanings as above). ) A method for producing a photo-insolubilizable polyvinyl alcohol derivative having a structure substituted with a unit represented by: 3. Some of the repeating units of fully saponified or partially saponified polyvinyl acetate have the general formula (in the formula, R is an alkylene group or a phenylene group, X is an oxygen atom or an imino group, and n is an integer of 1 or 2. ) and (wherein M is a hydrogen atom or ゛ is an alkali metal atom,
A photo-insolubilizable polyvinyl alcohol derivative having a structure substituted with the degree shown in (the phenyl group may have an inert nuclear substituent in some cases). 4 Fully saponified or partially saponified polyvinyl acetate, aldehyde represented by the general formula (in the formula, R is an alkylene group or a phenylene group, X is an oxygen atom or an imino group, and n is an integer of 1 or 2) or The acetal derivative is reacted with benzaldehyde or its acetal derivative represented by the general formula (M in the formula is a hydrogen atom or an alkali metal atom, and the phenyl group may have an inert nuclear substituent depending on the case). A part of the repeating units of completely saponified or partially saponified polyvinyl acetate/L, which is characterized by Production of a photo-insolubilizable polyvinyl alcohol derivative having a structure substituted with a unit represented by the general formula (M in the formula has the same meaning as above, and the phenyl group may have an inert nuclear substituent in some cases) Method.