JPH0356246B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel reactive polymer compound having a vinyloxy group.

Polymer compounds with reactive functional groups pendant on the linear backbone molecular chain are used in various fields of polymer industry by utilizing their properties such as reactivity with various modifiers and insolubilization through photocrosslinking and chemical crosslinking. Widely used.

Conventionally, polymer compounds with such reactive functional groups have been produced by reacting polyhalomethylstyrene with active halogen atoms with a compound having the desired functional group and capable of reacting with halomethyl groups, or by using novolak resin. It was produced by reacting a polymeric compound having a polyhydric phenol group such as with a compound having a desired functional group and a group capable of reacting with a hydroxyl group.

However, products made from polyhalomethylstyrene have unreacted halogen atoms in the molecule, which limits their applications, and products made from novolak resin have a clearly defined chemical structure. It has the disadvantage that it cannot be used for applications that require precision because it is difficult to specify.

In recent years, as it has become possible to industrially produce polyvinylphenols, it has been proposed to use them as a raw material and introduce allyl groups, propargyl groups, glycidyl groups, etc. through etherification. Its reactivity is insufficient for use as a component of a photosensitive resin composition.

The present inventors aim to improve the drawbacks of conventional polymer compounds with reactive functional groups and develop a new reactive polymer compound that can be used stably in any field of application. for,
As a result of extensive research, the inventors discovered that the objective could be achieved using a polymer compound obtained by reacting poly(hydroxystyrene) with haloethyl vinyl ether, and based on this knowledge, they came up with the present invention. .

That is, the present invention provides the formula Constituent unit and formula represented by It has a molecular structure in which the structural units represented by are bonded in series, and has a molecular weight of 2,000 to 200,000 when converted to a homopolymer consisting only of the structural units (), and the content of the structural units () is at least 5 mol%. The present invention provides a polystyrene-based polymer compound.

The polymer compound of the present invention has a molecular weight of 2000 to
It can be produced by reacting poly(hydroxystyrene) of 200,000 with haloethyl vinyl ether represented by the general formula: X-CH ₂ CH ₂ OCH=CH ₂ . Examples of the haloethyl vinyl ether of the general formula () include 2-chloroethyl vinyl ether, 2-chloroethyl vinyl ether,
-Bromoethyl vinyl ether is preferably used. These compounds need to be used in an amount of at least 5 mol % based on the hydroxyl groups in the raw materials. If the amount is less than this, the reactivity of the resulting polymer compound will be insufficient.

The reaction between poly(hydroxystyrene) and haloethyl vinyl ether is performed using dimethylformamide,
This can be carried out by bringing the two into contact in a solvent such as dimethyl sulfoxide, ethyl cellosolve, or ethylene glycol monomethyl ether, if necessary in the presence of an alkali metal compound. There is no particular restriction on the reaction temperature, but a range from room temperature to 100°C is desirable.

The novel polymer compound of the present invention thus obtained is a white powder and exhibits characteristic absorptions of 1602 cm ^-1 and 975 cm ^-1 due to olefins and 1240 cm ^-1 due to ether bonds in its infrared absorption spectrum. This compound is soluble in organic solvents such as acetone, dimethylacetamide, ethylene glycol monoethyl ether, diethyl ether, and dioxane, but is insoluble in n-hexane.

The novel polymer compound of the present invention has a vinyloxy group in its side chain that has high reactivity toward Lewis acids, protoic acids, and cations, so it can be reacted with various modifiers to further improve polymerization. It can be used as an intermediate for producing a molecular compound or as a component of a photosensitive resin composition using a photocrosslinking agent.

For example, the polymer compound of the present invention is dissolved in a suitable organic solvent, the above active substance is added,
It is applied to a support and hardens upon drying. In addition, a generator of a substance that becomes active in a new polymer compound when irradiated with light is added to the polymer compound solution.
This solution can be applied onto the surface of a support such as an aluminum plate, copper plate, zinc plate, etc. by means such as casting, spraying, coating, etc., and dried to form a film. The coating film thus obtained is irradiated with light through a negative film, and the poorly exposed areas are removed with a solvent to form a negative image. This photoreaction is due to the polymerization reaction of vinyloxy groups, and the reaction is completed in an extremely short time, surpassing the performance of conventional dimerized photosensitive resins.
Moreover, it has the advantage of not being affected by oxygen at all.

As mentioned above, the polymer compound of the present invention can be used not only for photosensitive resins and curable paints, but also for
It can also be used in 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 50% of nitrogen-introduced reaction vessel was washed with hexane.
% sodium hydride and 25 ml of dry N,N-dimethylacetamide were added, and to this solution was added 12 g of poly-4-vinylphenol with a number average molecular weight of 21,000 to 70 ml of dry N,N-dimethylamide. Add the dissolved solution while stirring,
Stirring 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, and the mixture was reacted at 80°C for 6 hours. The reaction mixture was distilled under reduced pressure at 80°C to remove most of the N,N-dimethylacetamide and unreacted 2-chloroethyl vinyl ether were removed. Next, diethyl ether was added to the residue to dissolve it, this solution was washed three times with saturated sodium bicarbonate solution, dried over anhydrous sodium sulfate, and the filtered solution was distilled under reduced pressure until the residue became solid. components were removed. The residue was again dissolved in diethyl ether containing a small amount of methylene chloride, and this solution was poured into a large amount of hexane with vigorous stirring, and the formed precipitate was filtered off and dried under reduced pressure. 13.6 g of solid product were thus obtained. As a result of the infrared absorption spectrum, absorption due to vinyl groups was observed at 1602 cm ^-1 and 975 cm ^-1 , and absorption due to ether bond was observed at 1240 cm ^-1 , indicating that the hydrogen groups of vinylphenol were converted to vinyloxyethyl ether. Ivy. Furthermore, the conversion rate determined by elemental analysis was 71%.

Example 2 50% of nitrogen-introduced reaction vessel was washed with hexane
% Sodium hydride 4.8 g (0.1 mol), dry N,
Pour 20 ml of N-dimethylacetamide, add to this solution with stirring a solution of 12 g of poly-4-vinylphenol with a number average molecular weight of 38,000 dissolved in 70 ml of dry N,N-dimethylacetamide, and continue stirring for about 2 hours. continued. Next, 2-chloroethyl vinyl ether 30
g, 1.5 g of anhydrous sodium carbonate, and 0.05 g of triethylbenzylammonium chloride were added, and the mixture was reacted at 80° C. for 10 hours.

The reaction product was separated and purified in the same manner as in Example 1.
15.8 g of solid product were thus obtained. As a result of infrared absorption spectrum analysis, 1602cm ^-1 and 975cm
Absorption due to vinyl groups at ^-1 and absorption based on ether bonds at 1240 cm ^-1 were observed, and absorption due to phenolic hydroxyl groups almost disappeared. Furthermore, the conversion rate determined by elemental analysis was 93%.

Example 3 A 50°C solution was washed with hexane in a reaction vessel into which nitrogen was introduced.
% Sodium hydride 4.8 g (0.1 mol), dry N,
Pour 20 ml of N-dimethylacetamide, add to this solution with stirring a solution of 12 g of poly-4-vinylphenol with a number average molecular weight of 38,000 dissolved in 70 ml of dry N,N-dimethylacetamide, and continue stirring for about 2 hours. Ta. Then,
To this were added 30 g of 2-chloroethyl vinyl ether, 1.5 g of anhydrous sodium carbonate, and 0.05 g of triethylbenzylammonium chloride, and the mixture was reacted at 80°C for 24 hours. The reaction product was separated and purified in the same manner as in Example 1. 16.2 g of solid product were thus obtained. Results of infrared absorption spectrum analysis, 1602
absorption by vinyl groups at cm ^-1 and 975 cm ^-1 , and 1220
Absorption due to ether bonds was observed at cm ^-1 , and the magnitude of absorption due to phenolic hydroxyl groups was not different from that of the product of Example 2. Furthermore, the conversion rate determined by elemental analysis was 99%.

Example 4 4.8% sodium hydride was added to a reaction vessel into which nitrogen was introduced.
(0.1 mol) and 20 ml of dry dioxane, and to this solution, poly-4-
60ml of dioxane with 12g of vinylphenol dried
After adding the solution with stirring, stirring was continued for about 2 hours. Then add 2 to this
- 30 g of chloroethyl vinyl ether, 1.5 g of anhydrous sodium carbonate, and 0.05 g of tetrabutylammonium chloride were added, and the mixture was reacted under reflux for 10 hours.
The reaction product was separated and purified in the same manner as in Example 1. 15.4 g of solid product were thus obtained. For this product, the infrared absorption spectrum of Example 2 was observed, and the magnitude of absorption due to phenolic hydroxyl groups was not different from that of the product of Example 2.
Furthermore, the conversion rate determined by elemental analysis was 98%.

Example 5 Methyl carbitol 70 was added to a reaction vessel into which nitrogen was introduced.
ml, add 12 g of poly-4-vinylphenol and dissolve. Then 85% potassium hydroxide
After adding 6.6 g and confirming complete dissolution, the mixture was stirred for 1 hour. Add 30 g of 2-chloroethyl vinyl ether and 1.5 g of potassium carbonate to this solution, and
After reacting for 24 hours, the mixture was separated and purified in the same manner as in Example 1. 15.5 g of solid product were thus obtained. The infrared absorption spectrum of Example 2 was observed for this product, and the magnitude of absorption attributable to phenolic hydroxyl groups was almost the same as that of the product of Example 2.

Example 6 70 ml of dried methyl carbitol was placed in a reaction vessel into which nitrogen was introduced, and 12 g of poly-4-vinylphenol was added and dissolved. Then metallic sodium
After adding 2.3 g and confirming the reaction, the mixture was stirred for 2 hours. Add 30 g of 2-chloroethyl vinyl ether and 1.5 g of sodium carbonate to this solution, and heat at 80℃ for 24 hours.
The mixture was allowed to react for a certain period of time, and then separated and purified in the same manner as in Example 1. 15.1 g of solid product were thus obtained. The infrared absorption spectrum of Example 2 was observed for this product, and the magnitude of absorption attributable to phenolic hydroxyl groups was almost the same as that of the product of Example 2.

Example 7 50% of nitrogen was introduced into the reaction vessel and washed with hexane.
% Sodium hydride 4.8 g (0.1 mol), dry N,
20 ml of N-dimethylacetamide was charged, and a solution of 14 g of poly-4-vinylphenol dissolved in 20 ml of dry N,N-dimethylacetamide was added to this dispersion, followed by stirring for an additional 2 hours. Next, 30 g of 2-chloroethyl vinyl ether and 1.5 g of anhydrous sodium carbonate were added to this solution.
The reaction was carried out at 80°C for 24 hours. The reaction mixture was prepared in Example 1.
By separating and purifying the solid product in the same manner as
15.4g was obtained. As a result of infrared absorption spectrum analysis, absorption by vinyl groups was detected at 1602 cm ^-1 and 975 cm ^-1 .
In addition, absorption based on ether bonds was observed at 1220 cm ^-1 . Absorption of phenolic hydroxyl groups almost disappeared.

Claims (1)

[Claims] 1 formula Constituent unit and formula represented by It has a molecular structure in which the structural units represented by are bonded in series, and has a molecular weight of 2,000 to 200,000 when converted to a homopolymer consisting only of the structural units (), and the content of the structural units () is at least 5 mol%. A polystyrene-based polymer compound.