JPS6071604A - Novel high polymer - Google Patents

Abstract

PURPOSE:A novel high polymer, obtained by reacting a high polymer having phenolic hydroxyl groups in the backbone molecular chain with a haloalkyl vinyl ether, useful for photosensitive resins, curable coating materials, etc., and containing alkenyloxy units. CONSTITUTION:A novel high polymer, containing one or more units of formula III(R1 is phenylene; R2 is bifunctional organic group), and obtained by reacting a high polymer containing one or more constituent unis of formula I (R1 is as described above) in the backbone molecular chain, e.g. poly-4-vinylphenol, with a haloalkyl vinyl ether of formula II (X is halogen; R2 is as described above), e.g. 2-chloroethyl vinyl ether, in a solvent if necessary in the presence of an alkali metal compound.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel polymeric compound having alkenyloxy units.

Conventionally, polymer compounds containing a phenyl group having a functional group as a constituent unit are obtained by reacting polyhalomethylstyrene having an active halogen atom with a functional group that reacts with a halomethy/I/ It can also be obtained by reacting a reactive functional group with a polymer compound having a polyhydric phenol group, such as a resin. In recent years, polyvinylphenol has come to be produced on an industrial scale, and this polymer compound has been used to produce polymer compounds having a phenyl group having a functional group as a constituent unit.

Their production method is based on etherification to polyvinylphenol, and is typified by the production method of polyvinyl allyl ether, polyvinyl propargyl ether, and polyvinyl glycidyl ether compounds. These polymer compounds have drawbacks such as insufficient reactivity when used for special purposes, for example, as polymer compounds constituting photosensitive resin compositions.

The present inventors have completed the present invention as a result of intensive research aimed at improving the drawbacks of conventional polyvinylphenol polymer compounds.

That is, the present invention is directed to a polymer compound containing a small number of units of the general formula % (in which R1 represents a phenylene group) in the basic molecular chain. Provided is a novel polymeric compound having a small number (both 1 unit) of the general formula % (R1 and R2 have the same meanings as above), which is obtained by reacting a haloalkyl anyl ether represented by the formula %. It is something to do.

At least one used as a basic component in the present invention
The polymer compound having units of the general formula (II) may be of any type as long as it has a phenolic hydroxyl group. Examples include 2.3- or 4-hydroxystyrene, 4-hydroxy-3- Homopolymers of nitrostyrene and copolymers of this monomer with linear polymerizable monomers such as acrylonitrile, styrene, σ-methylstyrene, vinyl acetate, alkyl acrylates, alkyl methacrylates, and maleic anhydride. The molecular weight of these hydroxyl group-containing polymer compounds is preferably about 2,000 to 200,000.

Examples of the haloalkyl alkenyl ether represented by the general formula (n) include 2-chloroethyl vinyl ether and 4-chloromethylphenyl vinyl ether. The compound represented by the general formula in+ is determined based on the hydroxyl equivalent of the raw material polymer compound (it is preferable to use a chemically calculated amount, but the amount may be more than that. Usually, the alkenyloxyalkyloxy group to be formed is Contains b tm Acid unit (B) and structural unit (A) are 100:0
It is used in a ratio ranging from 5:95 to 5:95.

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

The novel polymeric compound of the present invention obtained in this way is a white powder with an infrared absorption spectrum of <1602 CrrL-' and 975 cm,-' based on the olefin and <1240 (1n-' of It exhibits Y-type absorption. It is also soluble in organic solvents such as acetone, dimethylamide, ethylene glycol monoethyl ether, diethyl ether, and dioxane. However, it is insoluble in n-hexane.

The novel polymer compound of the present invention has a Lewis acid in its side chain,
Butronic acid has an alkenyloxy group that is highly reactive towards cations.

Such a novel polymeric compound 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 in a new polymer compound when irradiated with light is added to the polymer compound solution, and this solution is applied to aluminum plates, copper plates, etc.
It can be applied onto the surface of a support such as a zinc plate by means of 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 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, surpassing the performance of conventional dink type photosensitive resins, and also has the advantage of being completely unaffected by oxygen. be.

As mentioned above, the novel polymer compound of 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.

Add 12 g of poly-4-vinylphenol with a number average molecular weight of 21,000 to a solution of 7°me of N,N-dimethylamide.
was added with stirring, 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,
After reacting at 80°C for 6 hours, the reaction mixture was heated to 80°C.
Most of the N,N-dimethylacetamide and unreacted 2-chloroethyl vinyl ether were also removed by vacuum distillation at °C, and diethyl ether was added to dissolve the residue. This solution is washed three times with saturated sodium bicarbonate solution and dried over anhydrous sodium sulfate, and the filtered solution is distilled under reduced pressure to remove liquid components until the residue is solidified. 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 vigorously stirred hexane, and the formed precipitate was filtered off and dried under reduced pressure. The obtained product weighed 13.6 g, and its infrared absorption spectrum showed absorption due to vinyl groups at 1602 cwL-' and 975 tx-', and absorption due to ether bond at 1240 crrr-'', indicating that the hydroxyl group of vinylphenol was present. It was converted into vinyloxyethyl ether.

The conversion rate determined by elemental analysis was 7196.

Example 2 4.8 g (0.1 mol) of 50% sodium hydride washed with hexane and dry N were added to a reaction vessel into which nitrogen was introduced.

20 ml of N-dimethylacetamide was charged, and a solution of 12 g of poly-4-vinylphenol with a number average molecular weight of 38,000 dissolved in 70 rnl of dry N,N-dimethylacetamide was added to this solution with stirring, and stirring was continued for about 2 hours. Ta. Next, 30 g of 2-chloroethyl vinyl ether, 1.5 g of anhydrous sodium carbonate, and 0.05 g of ethylbenzylammonium chloride were added thereto, 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 product was obtained, with an infrared absorption spectrum conversion of 93%.

Example 3 4.8 g (0.1 mol) of 50% sodium hydride washed with hexane and dry N were added to a reaction vessel into which nitrogen was introduced.

20 ml of N-dimethylacetamide was charged, and to this solution was added a solution of 12 g of poly-4-vinylphenol with a number average molecular weight of 38,000 dissolved in 70 Inl of dry N,N-dimethylacetamide with stirring.
Stirring was continued for an hour. Next, 30 g of 2-chloroethyl vinyl ether and 1.5 g of anhydrous sodium carbonate were added to this.
,)'J Ethylbenzylammonium chloride 0.0
5 g was added and reacted at 80°C for 24 hours.

The reaction product was separated and purified in the same manner as in Example 1. Product 1
6.2g was obtained, and its infrared absorption spectrum showed that 16
02 crtt-'' and 975 Y-' were absorbed by the vinyl group. The conversion rate determined by elemental analysis was 99%.

Example 4 4.8 g of sodium hydride (0
, 1 mol) and 20 WIl of dry dioxane,
Add 53 ml of dioxane containing 12 sho of poly-4-vinylphenol with a number average molecular weight of 8300 to this solution.
was added with stirring, 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 tetrabutylammonium chloride were added to this, and 1
The reaction was allowed to proceed for 0 hours. The conversion rate from the reaction product is 989
It was 6.

Example 5 70 ml of methylcarpitol was charged into a reaction vessel into which nitrogen was introduced, and 12 g of poly-4-vinylphenol was added and dissolved. Next, 6.6 g of 85% potassium hydroxide was added, and complete dissolution was confirmed, followed by stirring for 1 hour. 30 g of 2-chloroethyl vinyl ether and 1.5 g of potassium carbonate were added to this solution, and the temperature was almost the same as at 80°C.

Example 6 Methylcarpitol 7 dried in a reaction vessel introduced with nitrogen
0? nl and 12g of poly-4-vinylphenol.
was added and dissolved. Next, 2.3 g of sodium metal was added and reaction was confirmed, followed by stirring for 2 hours. Add 2 to this solution
-30 g of chloroethyl vinyl ether and 1.5 g of sodium carbonate were added, and the mixture was reacted at 80°C for 24 hours, and then fractionated and purified in the same manner as in Example 1. The product obtained was 15.1 g. Practical Example 7 4.8 g (0.1 mol) of 50% sodium hydride washed with hexanoate and dry N were added to a reaction vessel to which nitrogen was introduced.

Claims (1)

[Claims] (1) A haloalkyl compound represented by the general formula % (in which R1 represents a phenylene group) is added to a polymer compound containing at least one structural unit represented by the general formula % (in the formula % phenylene group) in the basic molecular chain. A novel polymer compound obtained by reacting vinyl ether and having at least one unit represented by the general formula % (in which R1 and R2 have the same meanings as above).