JPS6220210B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing reactive polymers having alkenyloxy units.

Conventionally, a polymer compound containing a phenyl group having a functional group as a constituent unit is obtained by reacting polyhalomethylstyrene having an active halogen atom with a functional group that reacts with the halomethyl group. It can also be obtained by introducing a reactive functional group into polystyrene having a hydroxyl group in its aromatic ring by esterification, etherification, or the like. Examples of these include poly(4-vinylphenyl cinnameral)
), poly(4-vinylphenyl allyl ether), poly(4-vinylphenyl glycidyl ether), poly(4-vinylphenyl propagyl ether), or a resin in which a cinnamoyl group is introduced into a novolac resin (especially Publication number 50-15026)
It is represented by However, when these resins are used as constituent components of paint film-forming compositions or as polymer compounds that constitute photosensitive resin compositions, there are drawbacks such as insufficient reactivity. have.

The present inventors have conducted extensive research in order to improve the drawbacks of conventional reactive polymers, and as a result have accomplished the present invention.

That is, the present invention has the following general formula: 2-halogenoethyl vinyl ether is reacted with a phenolic novolak resin having a structural unit represented by the formula in an inert solvent in the presence of an alkali catalyst. The structural unit shown by and the formula It has a structure in which the structural units represented by are bonded in series, and the content of formula () is at least 2 mol%
The present invention provides a method for producing a reactive polymer. Phenolic novolak resins composed of circulating units represented by the general formula () above are known as phenolic resins, and are condensation products of phenol and formaldehyde, which can be produced by either dry or wet methods. It may be something you have.

The structural unit represented by formula () can be obtained by reacting 2-halogenoethyl vinyl ether with the hydroxyl group in the structural unit represented by formula (). In the reaction, a suitable condensing agent, such as an alkali metal compound such as anhydrous sodium carbonate, potassium carbonate, sodium hydride, metallic sodium,
sodium methylate, sodium ethylate,
The reaction can also be accelerated by adding an alkali metal alcoholate such as sodium butyrate, a quaternary ammonium salt compound such as triethylbenzylammonium chloride, tetraethylammonium chloride, tributylbenzylammonium chloride, etc. The reaction can be carried out in an inert solvent such as ethyl cellosolve, dimethyl sulfoxide, ethyllene glycol monomethyl ether, dimethyl acetamide. In addition, there is no particular restriction on the reaction temperature, but from room temperature to
A range of 100℃ is desirable. The reaction solution obtained in this way is concentrated or the solid is collected by an appropriate means such as drying, the part soluble in a solvent such as dichlorotane or diethyl ether is collected, and the obtained solution is mixed with a large amount of hexane. The desired reactive polymer can be obtained by adding it to.

The reactive polymer obtained by this reactive polymer production method is a white powder with an infrared absorption spectrum of 1602 cm ^-1 based on olefin.
975cm ^-1 , and 1240cm ^-1 based on ether bonds
It shows the characteristic absorption of. It is also soluble in organic solvents such as acetone, dimethylacetamide, dimethylformamide, ethylene glycol monoether, diethyl ether, and dioxane.
However, it is insoluble in n-hexane.

The polymer obtained by producing the reactive polymer of the present invention has an alkenyloxy group in its constitutional unit that is highly reactive to acidic substances such as Lewis acids, protonic acids, and cations.

Such a reactive polymer is dissolved in a suitable organic solvent, the above-mentioned active substance is added thereto, applied to a support, and cured by drying. In addition, a generator of a substance that becomes active on the reactive polymer when irradiated with light is added to the reactive polymer and solvent, and this solution is applied to a support such as an aluminum plate, copper plate, zinc plate, or copper-clad laminate. It can be applied onto a surface by means such as casting, spraying, or coating, and then dried to form a film. The coating film thus obtained is irradiated with light through a negative film, and the unexposed areas are removed with a solvent to form a negative image. This photoreaction is due to the polymerization reaction of alkenyloxy groups, and the reaction is completed in an extremely short time.
It has the advantage that it surpasses the performance of conventional dimerized photosensitive resins and is not affected by oxygen at all.

As mentioned above, the reactive polymer obtained by the present invention can be used not only for photosensitive resins and curable paints, but also for chemical milling resins for printed circuits, photocurable printing inks, etc. .

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

Example 1 A reaction vessel introduced with nitrogen was washed with hexane.
4.8 g of 50% sodium hydride and dried N・N−
Pour 25ml of dimethylacetamide and add a novolak type phenolic resin with a number average molecular weight of 900 to this solution.
10.6g dried N/N dimethylacetamide 70
ml of the solution was added and stirring was continued for about 2 hours. Next, 30 g of 2-chloroethyl vinyl ether, 1.5 g of anhydrous sodium carbonate, and 0.05 g of triethylbenzylammonium chloride were added to this solution, and the mixture was reacted at 80° C. for 24 hours. Most of the N·N-dimethylacetamide and unreacted 2-chloroethyl vinyl ether were removed by distilling the reaction solution at 90°C under reduced pressure. Add diethyl ether to the residue to make a homogeneous solution. The resulting homogeneous solution is washed three times with saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate, and then the desiccant is removed by filtration. A solid residue is obtained by distilling the obtained solution under reduced pressure. This residue was dissolved in diethyl ether containing a small amount of methylene chloride, this solution was poured into a large amount of vigorously stirred hexane, and the formed precipitate was filtered off and dried under reduced pressure. The obtained product weighed 13.5 g, and its infrared absorption spectrum showed absorption by vinyl groups at 1602 cm ^-1 and 975 cm ^-1 ,
Absorption based on ether bonds was observed at 1220 cm ^-1 . The substitution rate determined by elemental analysis was 95%.

Example 2 85% potassium hydroxide in a reaction vessel introduced with nitrogen
Add 6.6 g of dried methyl carbitol and 70 ml of dried methyl carbitol, add 13 g of novolac type phenolic resin with a number average molecular weight of 850 to this solution, and add 13 g of dried methyl carbitol.
A solution dissolved in 80 ml was added and stirring was continued for about 3 hours. Next, 31 g of 2-chloroethyl vinyl ether and 1.8 g of potassium carbonate were added to this solution, and the mixture was heated at 90°C.
The reaction was allowed to proceed for 28 hours. Most of the methyl carbitol was removed by distilling the reaction solution at 90°C under reduced pressure.
Remove unreacted 2-chloroethyl vinyl ether.
Add diethyl ether to the residue to make a homogeneous solution. The resulting homogeneous solution is washed three times with saturated sodium bicarbonate solution and dried over anhydrous sodium sulfate, and then the desiccant is removed by filtration. A solid residue is obtained by distilling the obtained solution under reduced pressure. This residue was dissolved in diethyl ether containing a small amount of methylene chloride, this solution was poured into a large amount of vigorously stirred hexane, and the formed precipitate was filtered off and dried under reduced pressure. The product obtained was 16.4g
So, from its infrared absorption spectrum, it is 1600 cm ^-1 .
Absorption due to vinyl groups was observed at 980 cm ^-1 and absorption due to ether bonds was observed at 1230 cm ^-1 . The substitution rate determined by elemental analysis was 90%.

Example 3 A reaction vessel introduced with nitrogen was washed with hexane.
Add 4.5 g of 50% sodium hydride and 30 ml of dried dimethyl sulfoxide, and add 11.5 g of novolac type phenolic resin with a number average molecular weight of 980 to this solution.
A solution prepared by dissolving the above in 80 ml of dry dimethyl oxide was added, and stirring was continued for about 1 hour. Next, 35 g of 2-chloroethyl vinyl ether, 2.5 g of anhydrous sodium carbonate, and 2.5 g of tetrabutylammonium bromide were added to this solution, and the mixture was reacted at 90°C for 32 hours. Most of the dimethyl sulfoxide and unreacted 2 were removed by distilling the reaction solution at 95°C under reduced pressure.
-Excluding chloroethyl vinyl ether. Add diethyl ether to the residue to make a homogeneous solution. The resulting homogeneous solution is washed three times with saturated sodium bicarbonate solution and dried over anhydrous sodium sulfate, and then the desiccant is removed by filtration. A solid residue is obtained by distilling the obtained solution under reduced pressure. This residue was dissolved in diethyl ether containing a small amount of methylene chloride, this solution was poured into a large amount of vigorously stirred hexane, and the formed precipitate was filtered off and dried under reduced pressure. The obtained product weighed 14.5 g, and its infrared absorption spectrum showed absorption due to vinyl groups at 1600 cm ^-1 and 975 ^-1 and absorption based on ether bond at 1220 cm ^-1 . Replacement rate determined from elemental analysis is 96%
It was hot.

Example 4 Metallic sodium 2.3 was added to a reaction vessel into which nitrogen was introduced.
Prepare g and 70ml of dried methyl carbitol,
Add 12.2g of novolak type phenolic resin with a number average molecular weight of 1200 to this solution and dry methyl carbitol.
A solution dissolved in 80 ml was added and stirring was continued for about 2 hours. Next, 30 g of 2-chloroethyl vinyl ether and 1.5 g of sodium carbonate were added to this solution, and the mixture was heated at 70°C.
The mixture was allowed to react for 28 hours. Most of the methyl carbitol and unreacted 2-chloroethyl vinyl ether are removed by distilling the reaction solution at 80°C under reduced pressure. Add diethyl ether to the residue to make a homogeneous solution. The resulting homogeneous solution is washed three times with saturated sodium bicarbonate solution and dried over anhydrous sodium sulfate, and then the desiccant is removed by filtration. A solid residue is obtained by distilling the obtained solution under reduced pressure.

This residue was dissolved in diethyl ether containing a small amount of methylene chloride, this solution was poured into a large amount of vigorously stirred hexane, and the formed precipitate was filtered off and dried under reduced pressure. The obtained product weighed 15.3 g, and its infrared absorption spectrum showed absorption due to vinyl groups at 1600 cm ^-1 and 975 cm ^-1 and absorption based on ether bond at 1220 cm ^-1 . The substitution rate determined by elemental analysis was 97%.

Claims (1)

[Claims] 1. General formula 2-halogenoethyl vinyl ether is reacted with a phenolic novolak resin having a structural unit represented by the formula in an inert solvent in the presence of an alkali catalyst. The structural unit shown by and the formula It has a structure in which the structural units represented by are bonded in series, and the content of formula () is at least 2 mol%
A method for producing a reactive polymer.