JPS5928571B2 - Photoinsoluble polymer materials and their manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water-soluble photo-insoluble polymeric material that exhibits high sensitivity with an extremely small introduction rate of photosensitive groups, and a method for producing the same.

Photosensitive resins have been used as printing plate manufacturing materials, photoresists for photoetching and photomilling, and as photosensitive vehicles for paints and printing inks, but recently research has begun to explore their use in immobilizing enzymes. ing.

By the way, photosensitive resins with photosensitive residues such as azide groups, cinnamoyl groups, and acryloyl groups have been known so far, but due to the influence of these resins on enzymes and problems with water solubility, etc. However, conventional photosensitive resins could not be said to be fully satisfactory.

As a photosensitive polymer suitable for such new applications,
A resin having a stilbazolium group produced by the reaction of a polymer of 2-chloroethyl vinyl ether and stilbazole (
Japanese Patent Application No. 53-022512) and resins into which stilbazolium groups or related groups are introduced by polyvinyl alcohol hair acetalization reaction (Japanese Patent Application No. 53-96803 and Japanese Patent Application No. 53-136536) have been proposed.

In particular, the latter one should be noted as having extremely high sensitivity and offering excellent film properties.
On the other hand, when these photosensitive resins are used for the above-mentioned purposes, a large film thickness is often required.

In order to sufficiently photoinsolubilize a thick film, light must penetrate sufficiently into the film. For this purpose, the extinction coefficient of the photosensitive group plays an important role.
If a photosensitive group has an excessively large extinction coefficient, the irradiated light will be sufficiently absorbed at the film surface, making it unsuitable for sufficiently photo-insolubilizing a thick film. The extinction coefficient of a stilbazolium group or its analogous group is on the order of tens of thousands, which is relatively large. For this reason, when polymers with photosensitive groups of this type are photo-insolubilized with a film thickness of several microns or more, light does not penetrate sufficiently to the bottom, which prevents sufficient resolution during image formation. I can't do it. As a result of extensive research aimed at improving this point, the present inventors discovered that the objective could be achieved by introducing a chalcone-type photosensitive group with a further reduced absorption coefficient into polyvinyl alcohol, and based on this knowledge, As a result, the present invention has been completed.

That is, in the present invention, in polyvinyl acetate saponified with 70 mol% or more, 0.5 to 1
0 mol% of vinyl alcohol units are represented by the general formula (1) (m in the formula is an integer from 1 to 6, n represents 1 or 2, A
The present invention provides a photo-insoluble polymer material which is substituted with a photosensitive structural unit represented by a phenyl group, a substituted phenyl group, a pyridyl group, or a pyridinium group, and a method for producing the same.

In the photo-insoluble polymer material of the present invention, the ratio of the above-mentioned structural units to other structural units, such as simple vinyl alcohol units or vinyl acetate units, is 0.
．． A l range of 5:99.5 to 10:90 is preferred.

The photosensitive structural units of the present invention cannot be said to be completely water-soluble, so if an excessive amount of the structural units is introduced outside of this range, the water solubility will be significantly reduced and the product will become insoluble in water. . However, if a polar solvent such as hydrous alcohol, dimethylformamide, or formamide, or a mixed solvent thereof with water is used as the solvent, the rate of introduction of the photosensitive structural unit can be further increased. The photoinsoluble polymer material of the present invention is a new photocrosslinkable substance that is soluble in water, and has approximately 40%
It is sensitive to light up to around 60 nm and becomes insoluble. This product is made by adding a phenyl group such as the general formula (), a substituted phenyl group, a pyridyl group such as , or a pyridinium group with high water solubility to polyvinyl acetate that has been saponified by 70 mol% or more. I can do it.

These compounds can be easily obtained by a dehydration reaction between an acetophenone derivative represented by the corresponding general formula (2) (R.m in the formula has the same meaning as above) and an aromatic aldehyde.

On the other hand, the degree of polymerization of polyvinyl acetate saponified at 70 mol% or more is preferably about 300 to 3,000. In this case, if the degree of polymerization is too low, the irradiation time required for insolubilization will be significantly long, and if it is too high, the viscosity will increase, which may impede practical use. The reaction between the acetal compound represented by the above general formula () and polyvinyl alcohol or polyvinyl acetate, that is, the polymer acetalization reaction, is carried out by an acid-catalyzed reaction in water or in an aqueous solution containing a water-soluble organic solvent. I can do it.

In this case, the acetal compound represented by () is preferably used in an amount of 0.5 to 20 mol % per vinyl alcohol unit. Any inorganic or organic acid can be used as the catalytic acid, and examples thereof include hydrochloric acid, sulfuric acid, phosphoric acid, p-toluenesulfonic acid, citric acid, and glycolic acid. The larger the amount added, the shorter the reaction time, so it is preferable, but it is sufficient that the pH of the aqueous solution or aqueous solution containing the organic solvent is about 2 or less. The reaction time is about 5 hours to 3 days, and the reaction is carried out at room temperature to 100°C. Further, in this reaction, the optimum concentration of saponified polyvinyl acetate is in the range of 2 to 20 wt%. The progress of this polymer acetalization reaction can be easily tracked by forming a film from the reaction solution itself and measuring its photosensitivity.

The reaction solution after the reaction has completed itself has practical sensitivity and can be used as a photosensitive solution. Alternatively, in order to remove the acid used as a catalyst, it may be neutralized with ammonia or an alkali hydroxide, or a basic ion exchange resin may be used. In addition, in order to further purify the resin, after the reaction is complete, the reaction mixture is poured into a large amount of a non-solvent such as acetone or dioxane to precipitate the desired photoinsoluble polymer material, which is then separated and added to the alcohol. wash with Although the photoinsoluble polymeric material of the present invention is soluble in water and has a low photosensitive group introduction rate, it exhibits practical sensitivity equivalent to or higher than, for example, polyvinyl alcohol containing dichromate. . Moreover, since the extinction coefficient of the photosensitive group at long wavelengths is about several thousand, even a thick resin film can be sufficiently photo-insoluble. Therefore, a photo-insolubilized film that adheres sufficiently to the substrate can be obtained. The photoinsoluble polymeric material of the present invention is useful not only as a photoresist or printing machine, but also as a water-based paint base, a vehicle for printing ink, and the like.

Furthermore, since the crosslinking site is achieved by dimerization of the double bonds of unsaturated ketones, the crosslinking reaction proceeds specifically, making it extremely useful as an immobilization carrier for biofunctional materials such as enzymes, living cell fragments, and microorganisms. Useful. On the other hand, if the adhesive strength of polyvinyl alcohol is considered, it can also be used as an adhesive or binder whose properties can be improved by light irradiation. Next, the present invention will be explained in more detail based on Examples and Reference Examples. Reference Example 14. Sodium hydroxide in 77 was dissolved in methanol in 150, p-acetylphenol in 507 was dissolved, and the solvent was distilled off under reduced pressure to obtain p-acetylphenol.

It was dried overnight at 50° C., then added to 100 CTII of dimethylformamide, and refluxed with 55 V of chloroacetaldehyde dimethyl acetal for 10 hours.

The precipitate was filtered off, water was added to the liquid, the oil layer was extracted twice with benzene, and the benzene layer was washed with alkali. After confirming the disappearance of acetylphenol by thin layer chromatography, the mixture was further washed with water twice and dried over anhydrous potassium carbonate. By distilling the residual oil after benzene distillation under reduced pressure, Bpll48
27.37 of p-(2,2-dimethoxyethoxy)acetophenone at ˜149° C. was obtained. Thus obtained p-(2・
5? 0.19y of 2-dimethoxyethoxy)acetophenone and 0.52g of 2-formylpyrimidine? of ethanol, and in this as little water as possible.
107 of sodium hydroxide was added and stirred at room temperature. 7
If water is added after a period of time, crystals will precipitate out, which are collected by filtration and washed with water to produce 1-(2-pyridyl)-2-(4-dimethoxyethoxybenzoyl)ethylene with a yield of 82%. Obtained.

Compounds shown in Table I were obtained in a similar manner. however,
The compounds in this table, V1 is 11, were each obtained by treating with dimethyl sulfate.

Example 1 Compound M97η in Table 1 obtained in Reference Example was converted to 5.00y of 7
．． After dissolving in an aqueous solution of 7% by weight completely saponified polyvinyl alcohol (degree of polymerization 1800),
% phosphoric acid was added and heated at 90° C. for 24 hours.

A small amount of ethanol is added to the reaction solution to make a clear solution, which is reprecipitated in a large amount of ethanol to separate the resinous material.
A -4.50y photosensitive resin was obtained by neutralizing with ammonia-containing ethanol, washing with ethanol, and vacuum drying. This resin was hot-dissolved in water containing a small amount of methoxyethanol, applied to an aluminum plate, exposed through a step tablet, and developed with warm water to obtain an image. This resin exhibited a sensitivity that was approximately the same as that of a polyvinyl cinnamate photosensitive resin (TPR manufactured by Tokyo Ohka Co., Ltd.). Furthermore, the sensitivity of a resin produced under the same conditions with an increased amount of Compound M to 194 Wa was approximately three times that of TPR. Example 2 To 4,00y of a 10% by weight solution of partially saponified polyvinyl alcohol (degree of polymerization 1700) was added 1.007y of acetic acid,
To this was added 18.6m of the compound in Table 1 dissolved in a small amount of acetic acid, and further 0.50y of 85% phosphoric acid was added and heated at 85°C for 20 hours.

The reaction product was reprecipitated in ethanol, neutralized with ammonia-containing ethanol, washed with ethanol, and then vacuum-dried. The sensitivity of this resin was almost the same as that of its younger sister, KTPR. Examples 3 to 12 In the same manner as in Examples 1 and 2, the other compounds shown in Table 1 were reacted with polyvinyl alcohol or partially saponified polyvinyl alcohol to obtain resins as shown in the table.

Claims (1)

[Claims] 1. 70 mol% with a degree of polymerization in the range of 300 to 3000
In the above saponified polyvinyl acetate, 0.5 to 10 mol% of vinyl alcohol units contained in the vinyl constituent units can be expressed by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (m in the formula is 1 to 6 , n is 1 or 2, and A is a phenyl group, a substituted phenyl group, a pyridyl group, or a pyridinium group. material. 2 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. , R represents a lower alkyl group or an alkyl group);
In polyvinyl acetate saponified at 70 mol% or more, which is characterized by reacting with polyvinyl acetate saponified at 70 mol% or more, 0.5 to
10 mol% of vinyl alcohol units are expressed by the general formula ▲mathematical formula,
There are chemical formulas, tables, etc. ▼ A method for producing a photo-insoluble polymer material substituted with a photosensitive structural unit represented by (m, n, A in the formula have the same meanings as above).