DE2065418B2 - Process for the preparation of photosensitive polymeric esters - Google Patents

Description

triethylammonium iodide, added. When compared to that rushes commonly used inert organic solvent, with the exception of aprotic polar ones 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 chlorine in the polymer, 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, Toluene, chloroform, dimethylformamide, tetrahydrofuran and hexamethylphosphoramide, soluble.

If, in turn, as mentioned above, the cinnamic acid ester of polyvinyl alcohol, which is a known photosensitive polymer, is used as the photosensitive polymer, it has a poor film-forming ability, is very brittle in the form of films, but is soluble in solvents such as methyl ethyl ketone and cyclohexane its solubility in the important solvent acetone is low. In contrast, the polymeric ester obtained in this embodiment of the invention is used to advantage because of its film-forming ability, its flexibility in the form of films, and its acetone solubility. If the chemical equivalent of the carboxylic acid salt is less than that of the chlorine in the chloromethyl group of the polymer to be esterified, an ester with a low degree of esterification is obtained. Depending on the degree of esterification, a polymeric ester with the required physical properties is formed.

Other examples that illustrate this embodiment are the following:

Example elbowsl9

A carboxylic acid salt and, if necessary, methyltriethylammonium iodide as a catalyst become a polymer with a chloromethyl group in the aliphatic side chain, which is in an apro- "5 Table polar solvent is dissolved, and the mixture is left at a given Temperature for a certain number of hours. After the reaction, the reacted mixture is added added to water to precipitate the product. The precipitate is dissolved in methyl ethyl ketone and the solution was again added to water for reprecipitation and purification.

The obtained polymeric ester is confirmed by observations of the IR spectrum and the NMR spectrum ^a 5, and its degree of esterification is determined by the quantitative analysis of the unreacted chlorine remaining in the product. The methods of microanalysis are used for halogen.

The results of the analysis are shown in the following table:

example Polymer Mole Cai bonsate salt G 9.3 Mole solvent 70 Kataly
sator Reaction
condition Hours. product Vereste
foresight
Degree Abbrev
tongue 0.05 link 0.05 Abbreviation cm '
tongue G ⁰ C 10 G 0.98 1 PCEA 6.73 Potassium- 10.1 HMPA 70 1.0 100 11.0 0.05 cinnamat 0.05 10 0.93 2 PCEA 6.73 Ammo HMPA 1.0 100 10.5 niumcinn- 11.2 40 0.05 amat 0.06 10 0.96 3 PECH 4.63 Potassium- 41.0 HMPA 350 1.0 100 7.3 0.20 cinnamat 0.22 5 0.84 4th PECH 18.5 Potassium- 18.7 HMPA 150 4.0 100 34.0 0.10 cinnamat 0.11 8th 0.87 5 PECH 9.25 Sodium- 21.5 HMPA 150 2.0 100 17.8 0.10 cinnamat 0.11 5 0.81 6th PECH 9.25 Sodium- HMPA 2.0 60 18.3 a-cyano- 21.2 150 0.10 cinnamat 0.11 6th 0.88 7th PECH 9.25 Potassium- HMPA 2.0 80 20.5 cinnamili- 17.6 150 0.10 denacetate 0.10 8th 0.91 G PECH 9.25 Potassium- HMPA 2.0 70 18.1 furfuryl 20.1 150 0.10 acrylate 0.10 7th 0.74 9 PECH 9.25 Potassium- HMPA 2.0 50 13.8 p-azido- 10.25 50 0.05 benzoate 0.055 10 0.91 10 PCEVE 6.35 Potassium- HMPA 1.0 80 10.6 cinnamat

Example polymer

■: ... ■ Abbreviation

Mole

Carboxylic acid salt compound g mole

Solvent Catalyst Reaction Product 'sator condition

Abbreviation cm ^s g ⁰ C hrs. G Veresle-

tongue

• ■ - degree

PCEVE 5.35 0.05

PCEVE 5.35 0.05

PCEVE 5.35 0.05

PCEVE 5.35 0.05

PVCA 6.03 0.05

PVCA 6.03 0.05

PVCA 6.03 0.05

PVCA 6.03 0.05

PVCA 6.03 0.05

Compare - PECH 9.25 0.1
example

Sodium a-cyanocinnamate

Potassium-

cinnamili-

denacetate

Potassium furfuryl acrylate

Kallamp azidobenzoate

Potassium cinnamate

Sodium a-cyanocinnamate

Potassium-

cinnamili-

denacetate

Potassium furfuryl acrylate

Potassium-

p-azido

benzoate

Potassium cinnamate

10.75 11.2 9.7 11.1

10.25 10.75

11.2 9.7

11.1 20.5

0.055 0.055 0.655 0.055

0.055 0.055 0.055 0.11

HMPA 50 1.0 50 5 5.2 0.63

HMPA 50 1.0 80 10 11.2 0.90

HMPA 50 1.0 80 10 10.1 0.91

HMPA 50 1.0 70 8 10.3 0.75

HMPA 50 1.0 70 5 10.3 0.97

HMPA 50 0.5 50 5 10.1 0.96

HMPA 50 1.0 50 5 11.3 0.93

HMPA 50 1.0 50 5 9.8 0.96

HMPA 50

50 6 9.3 0.92

glyme 150 2.0 60 8 0 -

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 (2-chloroethyl vinyl ether), PVCA: poly-vinyl chloroacetate).

Abbreviations of the solvents:

HMPA ^ hexamethylphosphoramide, glyme: ethylene glycol dimethyl ether.

Example 20

65.1 g of potassium cinnamate and 2.0 g of methyltriethylammonium iodide were added to 75.5 g of epichlorohydrinethylene oxide mixed polymers with a ratio of epichlorohydrin to ethylene oxide = 50 mol percent: 50 mol percent dissolved in 500 ml of dimethylformamide, and the mixture was at 100 ^° C. for hours implemented. After the reaction, the reacted mixture was added to 10 liters of water to precipitate the product. The precipitate was dissolved in methyl ethyl ketone and the solution was again poured into water for precipitation. Then, this precipitate was redissolved in methyl ethyl ketone, and the solution was poured into 101% 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 added to 75.5 g of epichlorohydrin-ethylene oxide copolymers (the same as in Example 20), dissolved in 500 ml of dimethylformamide, and the mixture was ^{reacted at 100 °} C. for 10 hours. 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 of ammonium cinnamate were added to 75.5 g of epichlorohydrin-ethylene oxide copolymer (the same as in Example 20) dissolved in 500 ml of hexamethylphosphoramide, and the mixture was ^{reacted at 100 °} C. for 10 hours. 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 cinnamate ester of the polymers obtained in Example 1 and 0.24 g of 5-nitroacenaphthene 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 ones will be Areas of the photosensitive film dissolved and washed away with monochlorobenzene. As a result the images are traced on the pane of glass, from which those up to the 17th level can be distinguished are.

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 drying the coating created in this way at 50 ° C. for one hour, a film with a thickness of 12 μ is obtained 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

t5 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 against the tensile strength applied Shows sufficient resistance.

Attempt 3

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, a doctor blade being used for coating, the film thickness being 100 μ results. After one hour

Drying the coating thus obtained at 50 ⁰ C to erhall on the polyester film surface prior to a film 12 μ thickness.

The photosensitive film layer on the polyester surface is slightly heated using) Pressure rollers are stacked on the copper sheet 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)

1 2 0 or 1 mean with the proviso that for the case Claim: a = b = 1 R _{2 is} a phenyl radical and for the Case a = 1 and b = 0 R ₂ denotes the phenyl, nitrophenyl, Process for the production of light-sensitive chlorophenyl, hydroxyphenyl, acetoxyphenyl or borrowed polymeric esters by ester formation from 5 styrylphenyl radicals or 1-naphthyl, 2-naphthyl, chloromethyl groups in the side chain containing 2-furfuryl, 9- Anthryl, 2-thienyl-4-pyridyl, p-azidodic polymers with carboxylic acid salts of the following phenyl and p-sulfonazidophenyl groups and for the formula case a = 0 and ft = 0 R ₂ the p-azidophenyl or (p-sulfonazidophenyl group mean, cr-'unden, the I ^x \ ίο is characterized in that a polymer with I J chloromethyl groups in the aliphatic side chain C = CH / α - (CH = CH) s - R _{2 m} j _t (J _61n 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 15 In the case of polymers, the chlorine of the chloromethyl group is a phenyl radical in the case of a = b = 1 R ₂ in the aliphatic side chain, as, for example, indicates and in the case of a = 1 and b = 0 R ₂ the homopolymers or copolymers of epichlorophenyl, nitrophenyl, chlorophenyl, hydroxy hydrins, vinyl chloroacetate, of 2-chloroethylvinylphenyl, acetoxyphenyl or styrylphenyl radical ether and of 2-chloroethyiacrylate, less reactive or one 1-naphthyl, 2-naphthyl, 9-anvhryl, ao as the bromine of the bromomethyl groups and also ge-2-furfuryl, 2-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 O = O and ft = 0 R _2, the p-azidophenyl or has a high activity. For this reason mean p-sulfonazidophenyl group, which characterizes the chlorine in the chloromethyl groups of the aliphage, that a polymer with »5 tables side chain of polymers in general chloromethyl groups in the aliphatic side is almost chemically inert, which leads to unsatisfactory chain with the carboxylic acid salt in one A pro results when the chlorine is condensed by chloromethyltic polar solvents. 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 to condense chloromethyl polystyrene with 35 Examples of R _{2 of} the carboxylic acid salt of ante-cinnamic acid in the presence of potassium carbonate in the given formula are phenyl, nitrophenyl, chlorine entities 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 analogous of the above phenyl rings in ortho-, meta- or para-conversion with polymers which are in the aliphatic side 4 ° 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 p-sulfonazidophenyl groups. Examples of the car possible. bonic acids, which according to the invention used am- In addition, it is known to form maleic anhydride monium salts or alkali salts, p-azido-vinyl acetate copolymer with cinnamic acid chloride, benzoic acid, cinnamic acid, m-nitrocinnamic acid, p-chlorine, the latter being converted directly into polycinnamic acid, p-methoxycinnamic acid, κ -Cyanocinnamic acid, inner chain (not the side chain) enters the chemical cinnamilideneacetic acid, % - 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) - furister and acetic acid vinyl ester Ester exchange 5 ° furylacrylic acid, χ -cyano - /? - (2) -furfuryl acrylic acid, reaction of polyvinyl acetate and methyl cinnamic acid, β - (2) - thienyl acrylic acid, β - (4) - pyridyl acrylic acid is produced 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. tical 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, photosensitive polymeric esters through ester- carried out by adding the carboxylic acid salt to the formation of chloromethyl groups in the side chain ^6o in aprotic polar solvents, such as hexa-containing polymers with carboxylic acid salts methyl-phosphoramid, dimethylformamid, diethyl following formula formamid, dimethylacetamid, dimethylsulfoxyd and (R \ N-methylpyrrolidone, adding dissolved polymers. 'ι ¹ \ The condensation reaction takes place without one i _ _ru J _irv j _ "". ρ ⁶ 5 catalyst smooth, depending on the type of solvent, c - lh / ο - ^ h - LHji K _{2 but it} generally proceeds with high yield where M is ammonium or alkali metal, R ₁ and a high degree of esterification by adding a hydrogen atom or a nitrile group and α and b quaternary ammonium salt, for example methyl