DE2065418C3 - Process for the preparation of photosensitive polymeric esters - Google Patents

Description

triethylammonium iodide, added. When compared to that a commonly used inert organic solvent, with the exception of aprotic polar solvents If solvent is used, the ester formation does not take place at all, even if the solvent is used which dissolves polymers having a chloromethyl group.

A slight excess of the carboxylic acid salt is generally used in the reaction versus the chemical equivalent of the polymer's chlorine, but one also gets one for a photosensitive one Polymeric useful polymeric esters at a chemical equivalent of not less than 0.3. The polymeric ester obtained is in commonly used solvents such as acetone, benzene, ToluoJ, chloroform, dimethylformamide, tetrahydrofuran and hexamethylphosphoramide, soluble.

If, in turn, as mentioned above, the cinnamic acid ester of des as the photosensitive polymer If polyvinyl alcohol, which is a known photosensitive polymer, is used, it has a poor film-forming capacity, is very brittle in the form of films in solvents such as methyl ethyl ketone and cyclohexane, but its solubility in the important solvent is acetone small amount. In contrast, the one obtained by this embodiment of the invention becomes polymeric Ester because of its film-forming ability, its flexibility in the form of films and its acetone solubility, used with advantage.

Salt is less than that of the chlorine in the chloromethyl group of the polymer to be esterified, so an ester with a low degree of esterification is obtained. Depending on the degree of esterification, a polymeric ester is formed with the required physical Properties.

Other examples illustrating this embodiment are the following:

Example elbowsl9

A carboxylic acid salt and, if necessary, methyl triethylammonium iodide as a catalyst become a polymer with a chloromethyl group in the aliphatic side chain, which in an apro-

¹ table polar solvent is added, and the mixture is allowed to react at a given temperature for a certain number of hours. After the reaction, the reacted mixture is added to precipitate the product into water. The precipitate is dissolved in methyl ethyl ketone and the solution is again added to water for reprecipitation and purification.

The resulting polymeric ester is determined by observation of the I.R. spectrum and the N.M.R. spectrum

^a 5 is confirmed, and its degree of esterification is determined by the quantitative analysis of the unreacted chlorine which remains in the product. The methods of microanalysis are used for halogen.

The results of the analysis are in the following

When the chemical Aqur / alent in carboxylic acid G 9.3 Mole Table shown: cm ³ Kataly Reaction Hours. product Vereste example Polymer. Cai bonsate salt solvent sator condition foresight 10.1 G ⁰ C G Degree Abbrev Mole connection 0.05 Abbreviation 70 10 0.98 tongue tongue 11.2 0.05 70 1.0 100 10 11.0 0.93 1 PCEA 6.73 0.05 Potassium- HMPA cinnamat 41.0 1.0 100 10.5 2 PCEA 6.73 0.05 Ammo 0.06 HMPA 40 10 0.96 niumcinn- 18.7 amat 0.22 350 1.0 100 5 7.3 0.84 3 PECH 4.63 0.05 Potassium- 2L5 HMPA cinnamat 0.11 150 4.0 100 8th 34.0 0.87 4th PECH 18.5 0.20 Potassium- HMPA cinnamat 21.2 0.11 150 2.0 100 5 17.8 0.81 5 PECH 9.25 0.10 Sodium- HMPA cinnamat 2.0 60 18.3 6th PECH 9.25 0.10 Sodium- 17.6 0.11 HMPA 150 6th 0.88 Λ-cyano- cinnamat 2.0 80 20.5 7th PECH 9.25 0.10 Potassium- 20.1 0.10 HMPA 150 8th 0.91 cinnamili- denacetate 2.0 70 18.1 8th PECH 9.25 0.10 Potassium- 10.25 0.10 HMPA 150 7th 0.74 furfuryl acrylate 2.0 50 13.8 9 PECH 9.25 0.10 Potassium- 0.055 HMPA 50 10 0.91 p-azido- benzoate 1.0 80 10.6 10 PCEVE 6.35 0.05 Potassium- HMPA cinnamat

Polymer ; 5.35 5 20th G 65 418 cm* F. Kataly 6th Hours. product 5.2 0 Vereste sator foresight example Abbreviation ι Carbonic acid salt G G Degree tongue 5.35 Mole 10.75 50 Reaction 5 11.2 0.63 connection Mole solvent condition PCEVE 1.0 ⁰ C 5.35 0.05 11.2 Abbreviation 50 10 10.1 0.90 11th Sodium- 0.055 tongue PCEVE 5.35 «-Cyano- 1.0 50 10.3 0.05 cinnamat 9.7 HMPA 50 10 0.91 12th Potassium- 0.055 PCEVE 6.03 cinnamili- 11.1 50 1.0 80 8th 10.3 0.75 0.05 denacetate HMPA 13th PCEVE 6.03 Potassium-
furfuryl
acrylate 0.055 1.0 10.1 0.05 Potassium- 10.25 50 80 5 0.97 14th p-azido- 0.055 HMPA PVCA 6.03 benzoate 10.75 50 1.0 70 5 11.3 0.96 0.05 Potassium- HMPA 15th PVCA cinnamat 0.055 0.5 6.03 0.05 Sodium- 11.2 50 70 5 9.8 0.93 16 Λ-cyano- 0.055 HMPA PVCA cinnamat 1.0 50 6.03 0.05 Potassium- 9.7 HMPA 50 5 9.3 0.96 17th cinnamili- 0.055 PVCA denacetate 1.0 50 9.25 0.05 Potassium- 11.1 HMPA 50 6th 0.92 18th furfuryl 0.055 PVCA acrylate 50 0.05 Potassium- 20.5 HMPA 150 8th , 19th p-azido 0.055 BAD LUCK benzoate 2.0 50 0.1 Potassium- HMPA Comp.- cinnamat 0.11 example 60 glyme

Abbreviations of the polymers:

PCEA: poly (2-chloroethyl acrylate),
PECH: poly (epichlorohydrin)
(with the exception of the oligomer in Example 3, which was used in the form of a rubber-like material),
PCEVE: poly - ^ - chloroethylvinyläthsr),
PVCA: poly vinyl chloroacetate).

Abbreviations of the solvents:

HMPA iHexamethylphosphoramide,
glyme: ethylene glycol dimethyl ether.

Example 20

65.1 g of potassium cinnamate and 2.0 g of methyltriethylammonium iodide were 75.5 g Epichlorhydrinäthylenoxid-Mischpolymerem with a quantitative ratio from epichlorohydrin to ethylene oxide = 50 mol percent: 50 mol percent dissolved in 500 ml of dimethylformamide, and the mixture was reacted at 100 ° C for 10 hours. After the reaction it was the reacted mixture was added to 101 water to precipitate the product. The precipitation was in Dissolved methyl ethyl ketone, and the solution was again poured into water for precipitation. Then this became The precipitate was redissolved in methyl ethyl ketone, and the solution was added to 10 1 of methanol for precipitation.

93 g of polymeric ester were obtained in which 25% of the total amount of the monomer units was esterified was.

The relative photosensitivity of the polymeric ester obtained compared to a commercially available one photosensitive polyvinyl alcohol cinnamate had a value of 650 compared with the sensitivity of the commercial product = 100.

Example 21

153 g of potassium cinnamate and 2.0 g of methyltriethylammonium iodide were converted into 75.5 g of epichlorohydrin-ethylene oxide copolymers (the same as in Example 20) dissolved in 500 ml of dimethylformamide, and the mixture was kept at 100 ° C during 10 hours implemented. After the reaction, the reacted mixture was treated as in Example 20.

113 g of polymeric ester were obtained, in which 49.2% of the total amount of the monomer units were esterified.

The relative photosensitivity of the polymeric ester obtained showed a value of 1,500 as compared with the sensitivity of the commercial product of 100.

Example 22

83 g Ammoniumcinnamat were added to 75.5 g of epichlorohydrin-ethylene oxide-Mischpolymerem (the same as in Example 20) dissolved in 500 ml Hexamethylphospfaoramid, was added and the mixture was reacted at ⁰ C for 10 hours SOO. After the reaction, the reacted mixture was treated as in Example 20. A polymeric ester was obtained in which 35.3% of the total amount of the monomer units was esterified.

The following tests were carried out to demonstrate the advantageous properties.

Attempt 1

3.0 g of the ciramate ester of the polymers obtained in Example 1 and 0.24 g of 5-NHroacenaphthene as a sensitizer, both dissolved in 15 cm ^{3 of} cyclohexanone, are applied to the surface of a glass pane by means of a vortex application device. After drying, a film with a thickness of less than 1 μ is obtained on the surface of the glass pane.

A # 2 step wedge (from Kodak Company) with 21 stepped images is then placed on the photosensitive film formed on the glass surface and exposed to a for 4 minutes 40 watt low pressure mercury lamp at a distance of 10 cm. After exposure, the unexposed areas of the photosensitive film are dissolved and washed away with monochlorobenzene. As a result, the images are traced on the glass, from which those up to the 17th level are distinguishable.

Attempt 2

A copper sheet is coated with 3.0 g of the cinnamate ester of the polymer obtained in Example 1 and with 0.24 g of 5-nitroacenaphthene, both dissolved in 15 cm ^{3 of} cyclohexanone, using a doctor blade, a film having a thickness of 100 μ results. After one hour of drying the thus created coating at 5O ⁰ C to obtain a film having a thickness of 12 μ on the copper surface.
A negative is then placed on the photosensitive film obtained on the copper surface and it is exposed for 4 minutes with a 40 watt low-pressure mercury lamp at a distance of 10 cm. After exposure, the unexposed

ίο areas of the film dissolved and treated with monochlorobenzene washed away. The film is then treated with an aqueous ferric chloride solution for etching, wherein the insoluble areas of the film are sufficiently resistant to the etching solution, and one obtains

clear etched images on the copper.

It is found that by observing the strength of the 12 μ thick film on the copper surface using the Erichsen film tester, cracks appear on the copper sheet at D = 8.5 mm, while the film shows no cracks, but rather this compared to the tensile strength applied Shows sufficient resistance.

Attempt 3

As a polyester film is coated with 3.0 g of the cinnamate ester of the polymer obtained in Example 1 and with 0.24 g of 5-nitroacenaphthene as a sensitizer, both dissolved in 15 cm ^{3 of} cyclohexanone, using a doctor blade during the coating, whereby a film thickness of 100 μ results. After an hour

Drying the thus obtained coating at 50 ⁰ C is obtained on the polyester film surface of a film of 12 μ thickness.

The photosensitive film layer on the polyester surface is easily coated ^{on the copper sheet using heated pressure rollers at a temperature of 100 °} C., and the polyester film can be easily peeled off from the photosensitive film layer.

A polypropylene film used in place of the polyester also shows a successful result.

Claims (1)

0 or 1 mean with the proviso that for the case Claim: c = b = 1 R _{2 is} a phenyl radical and for the Case a = 1 and i = 0R ₂ the phenyl, nitrophenyl, Process for the preparation of photosensitive chlorophenyl, hydroxyphenyl, acetoxyphenyl or borrowed polymeric esters by ester formation from 5 styrylphenyl radical or a 1-naphthyl, 2-naphthyl, Chloromethyl groups in the side chain contain- 2-furfuryl-, 9-anthryl-, 2-thienyl-, 4-pyridyl-, the polymers with carboxylic acid salts following p-azidophenyl and p-sulfonazidophenyl groups and Formula for the case a - 0 and b = 0 R ₂ the p-azidophenyl ( _R. Or p-sulfonazidophenyl group mean, found ^{,, 1} ^ ίο which is characterized in that a polymer r ru , ru-cvi \ w with chloromethyl groups in the aliphatic side c - ch / ο - ten - cnj & - ^ _{2 chain} J ₁₁ J _{1 the} carboxylic acid salt in an aprotic where M ammonium or alkali metal, R ₁ a polar solvent is condensed.
Hydrogen atom or a nitrile group and α These esters are photosensitive,
and b are 0 or 1 with the proviso that is In polymers, the chlorine of the chloromethyl group for the case a = b = 1 R _{2 is} a phenyl radical in the aliphatic side chain, as, for example, and for the case a = 1 and b = 0 R ₂ the homopolymers or copolymers of epichlorophenyl, nitrophenyl, chlorophenyl, hydroxy hydrine, vinyl chloroacetate, 2-chloroethylvinylphenyl, acetoxyphenyl or styrylphenyl radical ether and 2-chloroethyl acrylate, less reactive or ( ine 1-naphthyl, 2-naphthyl, 9-anthryl, »o as the bromine of the bromomethyl groups and also ge-2-furfjryl,? .- thienyl, 4-pyridyl, p-azidophenyl rings reactive as the chlorine of the chloromethyl group of the and p-sulfonazidophenyl group and for the p-chloromethylstyrene polymer, which, in contrast to the case of O = O and A = OR ₂ , has a high activity for the p-azidophenyl or p-sulfonazidophenyl group mean, this characterizes the chlorine in the chloromethyl groups of the aliphage, that a polymer with 25 tables side chain of polymers in general chloromethyl groups in the aliphatic side chain is almost chemically inert, which leads to unsatisfactory chain with the carboxylic acid salt in a pro results when the chlorine is condensed by chloromethyl table polar solvent. groups as a functional group in the reaction is used with such substances.
30 It has now been found that in the case of the invention according to the method, the condensation reaction very much runs smoothly and polymer esters form when worked in an aprotic, polar solvent will. It is already known that chloromethylpolystyrene _{can be condensed with 35 Examples of R 2 of} the carboxylic acid salt of ante-cinnamic acid in the presence of potassium carbonate in the formula given are phenyl, nitrophenyl, chlorine in the absence of a solvent. This phenyl, hydroxyphenyl, acetoxyphenyl or styryl reaction is based on the high activity of chlorine phenyl groups, the substituted groups being the chloromethyl group (DT-PS 9 59 228). The analogy of the above phenyl rings in ortho, meta or para conversion with polymers which are in the aliphatic side 40 position, 1-naphthyl, 2-naphthyl, 9-anthryl, chain chloromethyl groups, is because of the 2-furfuryl -, 2-thienyl, 4-pyridyl, p-azidophenyl essentially less reactive chlorine and practically no p-sulfonazidophenyl groups. Examples of the car possible. In addition, it is known to form maleic anhydride monium salts or alkali salts, p-azido-vinyl acetate copolymers with cinnamic acid chloride, benzoic acid, cinnamic acid, m-nitrocinnamic acid, p-chlorine, the latter being converted directly into the poly- cinnamic acid, p-methoxycinnamic acid. ^ -Cyanocinnamic acid, merenkette (not the side chain) occurs (Chemical Cinnamilidenessigsäure, <x - Cyanocinnamilidenessig-Zentralblatt 1967 [12], 2930). In addition, it is also known to be acid, β - (1) - naphthylacrylic acid, β - (2) - naphthylic acid, copolymers of cinnamic acid vinyl acrylic acid, β - (9) - anthrylacrylic acid, β - (2) - furester and acetic acid vinyl ester through ester exchange 5 ° furylacrylic acid, α - cyano - β - (2) - f urfurylacrylic acid, reaction of polyvinyl acetate and methyl cinnamic acid β - (2) - thienyl acrylic acid, β - (4) - pyridyl acrylic acid ester in a tetrahydrofuran-dioxane mixture and p- Sulfonazidobenzoic acid. These acids will deliver. Depending on the amount of methyl cinnamate used in the condensation reaction, this reaction only leads to an equilibrium of ammonium salts, sodium salts or potassium salts; the work-up of the reaction mixture is applied. mixture is therefore relatively complex (chemical The condensation reaction of a polymer, which Zentralblatt 1966 [18], 2654.) ches the chloromethyl group in the aliphatic There has now been a process for making side chain containing, with the carboxylic acid salt, being photosensitive polymeric esters carried out by ester by adding the carboxylic acid salt to the formation from chloromethyl groups in the side chain ⁶ ° in aprotic polar solvents such as hexa- containing polymers with carboxylic acid salts methyl-phosphoramide, dimethylformamide, diethyl following formula formamide, dimethyl acetamide, dimethyl sulfoxide and ( _R ,. N-methylpyrrolidone, added to dissolved polymers. ι * \ The condensation reaction takes place without one r ru) (ru ru \ ρ ^6s catalyst smooth, depending on the type of solvent, C - CH / β - (CH = CH) ₆ R _{2 but ver externa} i f _{it t is} generally at a high yield where M is ammonium or alkali metal, R _{1 is} a and a high degree of esterification by being a Hydrogen atom or a nitrile group and α and b quaternary ammonium salt, for example methyl