JPS5869208A - Light-insolubilizable polyvinyl alcohol derivative and its production - Google Patents

Abstract

PURPOSE:The titled photopolymer which is highly sensitive in spite of its low content of photosensitive functional groups and is suitably used as a photoresist, a photosensitive vehicle or the like, prepared by introducing particular photosensitive functional groups into polyvinyl alcohol. CONSTITUTION:A photopolymer (light-insolubilizable polyvinyl alcohol derivative) prepared by replacing part of repeating units of a polyvinyl acetate (partial) saponificate with about 0.1-20mol of a unit represented by formulaI, wherein R1 is H, cyano, carboxyl, alkoxycarbonyl, R2 is carboxyl, alkoxycarbonyl, cyano or carbonyl and n is 0 or 1. The above photopolymer is formed by reacting a polyvinyl acetate (partial) saponificate (preferably, one having an average polymerization degree of about 200-3,000, and an acetyl group content of below about 30mol%) with an aldehyde of formula II (or its acetal derivative), e.g., p-formylcinnamic acid, in the presence of a catalyst (e.g., phosphoric acid, sulfuric acid).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides #111 and polyvinyl alcohol derivatives that are insolubilized by light and a method for producing the same. , 7 relates to a novel photo-insolubilizable polyvinyl alcohol derivative that can be used as an otoresist, a photosensitive vehicle, a substrate for enzyme immobilization, etc., and a method for producing the same.

In recent years, photosensitive resin has been used as 7t Tregis F, an image resist for plate making such as lithography, letterpress, and gravure.
It is widely used as a photo-V cyst for O corrosion processing of wiring (integrated circuits, shadow masks, etc.), or as an adhesive for photosensitive paints, varnishes, and glass. It is used as a vehicle, a base material for a matrix of photosensitive resin letterpress plates and resin plates, and a base material for immobilizing enzymes.

Conventionally, 1 photosensitive resin and 1 azide group and 1 cinnamoy group,
Those having a photosensitive functional group such as an acryloyl group are known. However, since these photosensitive functional groups have low sensitivity, it is necessary to introduce them into the resin in large quantities, and they must usually be introduced at a rate of ~100 mol per repeating unit of the polymer. , therefore, it has the disadvantage of high cost and is not always satisfactory.

The present inventors have developed a highly photoinsolubilizing compound that overcomes the drawbacks of conventional photosensitive W resins. By introducing a sexual functional group, the purpose t
Based on this knowledge, the present invention was completed.

That is, in the heathering #1, some of the tapered units of the completely saponified or partially saponified polyvinyl #1 are groups or alkoxycarbonyl groups, and 1. is a carboxyl group, an alkoxycarbonyl group, a cyano group, or a carbamoyl group, and 1 is 0 or 1. Saponified polyvinyl acetate (by reacting an aldehyde represented by the general formula (R1, 11! in the formula, having the same meaning as nFif II) or its acetal derivative, completely saponified or partially saponified vinyl acetate) 1111v return unit -sK is expressed by the general formula (D
The present invention provides a method for producing a photo-insolubilizable privinyl alcohol derivative having a structure substituted with the unit shown below.

The novel polyvinyl alcohol derivative represented by such a general formula exhibits a very high degree of m even in the ultra-low range of 01 to 20 moles per repeating unit.

The novel polyvinyl alcohol derivative of the present invention has the general formula (
It can be easily produced by reacting the aldehyde represented by 1) or its acetal derivative.

An example of an aldehyde represented by the general formula (1) is #i%yp-y #A/Z Luna 4 antiacid, ? −
7 ormylated cinnamic acid ester, P-7 ormylated cinnamic acid ary, '-cyano P-7 ormylated cinnamylic acid ester
fF acid, --cyano-P-7 ormylicinna 19f-acetic acid ester, P-7 ormylicinnamylidene acetic acid, P-
7 milcinnatide acetate, -monoethoxycarbonylate! -7 lucinna turbid ethyl acetate, -1 cyanide P-7 lumyl cinnamylidene acetamide, -1 cyanide! -7 olumyl cinnamylidene acetanilide and the like can be mentioned. Examples of acetal derivatives include dimethyl acetal and diethyl acetal of these aldehydes.

These aldehyde or acetal derivatives are produced by, for example, reacting tele-7talaldehyde or its mono-7tal with a compound having an active methylene group such as malonic acid to convert the F-71 lumyl cinnamon # derivative into a mono- or P-7 ormylkinyl derivative. By the reaction between envy dehyde and a compound containing an active methylene group! -7# Lumil cinnamylidene vinegar i! #Derivatives are easily synthesized. On the other hand, saponified polyvinyl acetate used as a raw material is completely saponified, as well as Sl! Although it is possible to use iIS-separated K, in order to increase water solubility, K is preferably 40, which contains some unsaponified acetyl groups.
It is desirable to use a compound having an acetyl group content of less than 30 moles for +1111. Furthermore, this completely saponified or partially saponified polyvinyl acetate has an average degree of polymerization of 20.
A degree of polymerization in the range of 0 to 3000 is suitable, but especially from the viewpoint of handling the obtained compound, the degree of polymerization is 500! 000
Preferably.

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

That is, the photocrosslinkable 5-rivinyl alcohol derivative of the present invention represented by the general formula (D) is produced by reacting completely or partially saponified polyvinyl acetate with an aldehyde or its acetal derivative represented by the general formula (2). This reaction is advantageously carried out in water or a water-containing organic solvent in the presence of an acid catalyst.
There are no particular restrictions on the acid used as a catalyst, and it may be either an anhydrous acid or an organic acid, but phosphoric acid and sulfuric acid are preferred in terms of solubility in water and ease of handling. , aldehyde or its acetal derivative strain, is preferably used in a ratio of αl to 30 mol≦ per vinyl alcohol unit in completely saponified or #'i partially saponified polyvinyl acetate; The concentration of partially saponified polyvinyl acetate is preferably in the range of 1 to 10 parts by weight.

In addition, the reaction temperature is suitably in the range of room temperature to LOO℃, and the reaction time is about 2 to 40 hours.The reaction solution after the zero reaction has been completed can be used as it is as a highly sensitive photosensitive solution, and it can also be used for the main purpose. If it is necessary to separate KFi as a solid product, the reaction solution should be sterilized in a poor solvent such as acetone or methanol, the resulting precipitate separated, washed with alcohol, etc., and then dried under reduced pressure. Bye.

The photoinsolubilizable vinyl alcohol derivative of the present invention has a content of 41 photosensitive functional groups & α1-30 per repeating unit.
Even in the low range of 1 mole, 1 itself has 1 laf%, which is sufficient for ultraviolet light, but by adding an appropriate sensitizer, the sensitive range can be further expanded to the visible region. I can do it. Is this sensitizer a photosensitive functional group? -7th group is a cinnamic acid group, for example, 74-2) a-1-su7thylamine, L2-benzanthraquinone, biclamide, 5-nitroacenaphthene, 3- Methyl-1-siade L9-benzanthrone 1 Michler's ketone, etc., and when the photosensitive functional group is a P-7 milcinnatridenide group, tc
tt, such as erythrosin, rosebenjfh, and the like. These sensitizers may be added after reaction path T to a solution IvK in which a purified photo-insolubilizable polyvinyl alcohol derivative is dissolved in an appropriate solvent. The amount added can be appropriately selected depending on the required sensitivity, but it is preferably in the range of 0 to 60,000 liters relative to the photosensitive functional group.

The photoinsolubilizable polyvinyl alcohol derivative of the present invention to which a sensitizer has been added has a photosensitivity equivalent to or higher than that of polyvinyl cinnamate sensitized with 5-nitroacenaphthene! @
Show degree. In other words, the photoinsolubilizable polyvinyl and alcohol derivatives of the present invention have a lower introduction rate of photosensitive functional groups and a smaller amount of sensitizer than conventional products;
It exhibits sufficiently high sensitivity and is economically extremely valuable. Therefore, it is not only useful as a photoresist or photosensitive vehicle, but also has a crosslinking reaction that proceeds specifically as a photodimerization reaction. Therefore, it is extremely useful as a fixing material for biofunctional materials such as enzymes, biological cells, fragments, and microorganisms.In addition, the adhesive properties of polyvinyl alcohol can be used as adhesives and binders whose properties improve when exposed to light. O can also be used as a paint base material etc. Next, the present invention will be explained in more detail with reference to Examples.

Reference Example 1 Production of g-cyano-P-phtyl cinnamylidene methyl acetate: From derephthalaldehyde diethyl monoa heptatal and acetaldehyde! -Die)xymethylcinnamaldehyde was synthesized, and this compound was synthesized from Fogq and methyl cyanoacetate 2.
97"f was dissolved in 1 odLIc of methanol, 1 drop of piperidine was added, and the mixture was stirred at room temperature for about S hours. The precipitated crystals were collected by filtration and recrystallized from methanol-heirasan to give 11 cyano!-sheds. Dimethylcinnamylidene methyl acetate was obtained at 390 mp.
It was 5-8&5°C.

Separately, 2 drops of hydrochloric acid were added to the filtrate, and the mixture was heated and stirred at about 50°C for 5 hours, and the resulting crystals were recrystallized from methanol to obtain 260q of g-cyano-F-71lumylcinnamylidene methyl acetate. It was done.

This substance has dark yellow needle-like crystals, mp gl~22
0°C λ11&X B44nm, #=number aaoo (methanol).

Example 11j - Preparation of ethyl acetate containing monoethoxycarbonyl-P-7 oromyl cinnamaldehyde: Dissolve 234 kg of P-jethoxymethyl cinnamaldehyde and 160 kg of diethyl malonate in 5 sj of methanol, and add 1 drop of piperidine. , and stirred at room temperature for 3 hours. After concentrating methanol to about half, 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 diluted with methanol.
When recrystallized from water, α-ethoxylic 15AI-F-7 oromylcinnamylidene acetate ethyl 108wII was obtained as yellow scale crystals. This item costs 90-
*z”c, λl1ax ii!95mm, am-50
250 (methanol).

Reference Example 3 F-7 Olumyl Cinnamaldehyde Methyl Acetate P-9 468 g of ethoxymethyl cinnamaldehyde and 218 g of malonic acid were dissolved in 4-pyridine, 1 drop of piperidine was added, and the mixture was heated and poured for about 1 day.

After pyridine was distilled off under reduced pressure, methanol and one drop of concentrated sulfur were added, and the mixture was heated under reflux for about 6 hours. After distilling off the methanol, water was added and extracted using a four-mouth rum.The extract was dried.
After I7, chloroform was distilled off, and the obtained 751m was recrystallized from hequinane to obtain P-7* #milcinnamylidene methyl acetate 137x as amber needle crystals. This one is Otori plOα1-1OL5℃, λ
mm! ff195mmμm31% fiQO (methanol) 〇What reference number --cyano-? -7t kt Production of lucinnamylidene acetanilide: Diethoxymethylcinnamaldehyde 234 cape and -cyanoacetanilide 160a were dissolved in methanol 5-, and after adding 1 drop of piperidine to 111rw at room temperature.
I am careful to stir it.

When the precipitated crystals are filtered and recrystallized from methanol, u
p a-Cyano-P-jethoxymethylcinnamylidene acetanilide 121''F was obtained as yellow phosphorus gavage crystals at 165-167°C.

250 pounds of this stuff, 5 tons of methanol, 1 g of water
After adding 1 drop of concentrated hydrochloric acid to the solution, the mixture was stirred in a room for 8 hours. Methanol was distilled off, water was added, and the mixture was extracted with methylene chloride. After dry bombing, methylene chloride was distilled off, and the residue was recrystallized from methanol to form yellow needle-shaped crystals of α-cyano-P-7 ormylcinnamylidene acetanilide 1B? '
W was obtained. This one is +mp 175.5-17
1>5℃, λwrhX 346n+m, #=29236
(methanol).

Example 1 Saponification Bo')iIam vinyl (average degree of polymerization 1?
To a 6 weight aqueous solution &41 of OO), 2 g Lt of acetic acid and α3f of phosphoric acid were added, and to this was added dropwise a 2S1 solution of P-7* methyl lumyl cinnamate α8q in acetic acid to give a solution of about 50 to 6
The mixture was heated and stirred at 0°C for 15 hours.

To the thus obtained reaction solution was added 0.5 equivalents of 7-cetyl 1-nitro-1-7 tylamine as a sensitizer per 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 and vinegar-1-ocymethyl-74-lumamide, resulting in an hA pattern on the aluminum plate. was gotten.

To a photosensitive resin solution synthesized in the same manner as in Example 1, picramide was added as a sensitizer in an amount α5 equivalent to the photosensitive group.

By performing the same operations as in Example 1, a clear image was obtained on the aluminum plate.

Example 3 85 saponified vinyl acetate* (average polymerization 1[1'FOo
) 5 weight water attack solution 2. lII/C dimethylacetacede l- and phosphoric acid αtl were added.
7 Olumyl cinnamylidene methyl acetate 5JL 4'f 25-solution of dimethyl acetamide was added dropwise to about 50-60
The mixture was heated and stirred at ℃ for 27 hours. The reaction solution thus obtained was incubated in acetone, and the precipitate was washed and dried under reduced pressure. Photosensitive book resin 40w9 purified in this way
was dissolved in 1 liter of water and 1 g Lt of methyl cellosolve, applied to an aluminum plate, exposed to a xenon lamp through a negative film, and then developed with water to obtain a bright image on the aluminum plate. It was done.

Example 1 Dimethylformamide α5- and phosphoric acid α2f were added to 85% saponified polyvinyl acetate (average degree of polymerization 1700) avli+f 1% aqueous solution L6I, and to this was added dimethyzate/7
The luminamide α5-solution was added dropwise, and the mixture was heated and stirred at about 50°C for 24 hours. The reaction solution obtained in this way was applied to an all-aluminum plate, exposed to light using a 1,700 liter lamp through a negative film, and then developed in a mixed solvent of water and acetic acid to form a bright image on the aluminum plate. fiI was obtained.

Although this material was not sensitized, it exhibited a photosensitivity approximately 25 times higher than that of polyvinyl cinnamate sensitized with 5-nidoR acenaphthene.

Example 5 Sag saponified polyvinyl acetate (average degree of polymerization x?OO
) 6 weight aqueous solution 2. lIK dimethylacetamide 1m
and 02 ft of phosphoric acid, and to this was added dropwise 12 kg of dimethylacetamide and phosphoric acid containing 1-cyano P-7 ormylicinna, and 24 ft of dimethyl acetate at about 60-60°C.
The mixture was heated and stirred for hours. The reaction solution obtained in this way was washed with acetic acid, and the precipitate was washed and dried under reduced pressure. Photosensitivity obtained by purification in this way! 40q of alkaline fat to l- of water
The solution was dissolved in methyl cellosolve l- and applied to an aluminum plate, exposed to a xenon lamp through a negative film, and then developed with water to obtain an aluminum plate with a bright image. .

Claims (1)

[Claims] l Completely saponified or partially saponified polyacetic acid (in the formula 0
11 is a hydrogen atom, a cyano group, :48g xyl group or an alkoxycarnyl group, ml is a carboxyl group,
A photo-insolubilizable polyvinyl alkyl derivative having ** substituted with a unit represented by an alkoxydicarbonyl group, a cyano group, or a carbamoyl group, where the number is O or l. 8 Completely saponified or partially saponified polyvinyl acetate is added to the general formula (R1 in the formula is a hydrogen atom, a cyano group, a carboxyl group, or an alkoxycarbonyl group, and R is a carboxyl group, an alkoxycarbonyl group, a cyano group, or a carbamoyl group). The polyvinyl group is prepared by reacting an aldehyde or its acetal conductor (in which "I + R
1 has the same meaning as above).