DE1063803B - Process for the production of products which are soluble in organic solvents and which become insoluble when exposed to light - Google Patents

Description

The invention aims to produce compounds which are soluble in organic solvents by Cross-link and become insoluble when exposed to light.

It has been found that such compounds can be prepared surprisingly easily if cinnamic acid is used or cinnamic acid derivatives, which have at least one reactive hydrogen atom, with di- or Reacts polyfunctional isocyanates, the reactants are chosen so that the obtained Reaction products contain at least three groups of a cinnamic acid derivative.

Cinnamic acid derivatives include, for example, the esters, amides, hydrazides or nitriles of cinnamic acid understood when they contain groups with reactive hydrogen atom. You can, by the way to be appropriately substituted. These requirements correspond to z. B. Compounds of the following formula:

R ₃

R ₂ R2

Where X = CN, COOR ₁ , CON (Ri) ₂ , CONHN (R ₁ ).,; In _{addition to a hydrogen atom, R 1} can be an alkyl or aryl radical which optionally also carries groups with reactive hydrogen atoms. R ₂ denotes hydrogen atom, alkyl, aryl, alkoxy or halogen atom. In _{addition to hydrogen atoms, R 3} includes one or more alkyl, aryl or alkoxy groups that can still carry substituents with reactive hydrogen atoms, or also halogen atoms, nitro, hydroxyl, amino, mercapto, carboxyl, carbonamide and sulfonamide groups to understand. Overall, at least one of the substituents must have a group with a reactive hydrogen atom. The group or groups with reactive hydrogen atoms can accordingly be located both on the benzene nucleus and in its substituents as well as in the alcohol component of the ester or the amine component of the acid amide or hydrazide. The benzene nucleus can contain fused aromatic rings. These cinnamic acid derivatives can all be prepared by methods known per se. Suitable compounds are, for example: alkyl p-amino cinnamate, m-oxy-α-chlorocinnamic acid, monoglycol o-methylcinnamate, alkyl i ^ '-dioxy ~ a-phenylcinnamate, / S- (a-naphthyl) acrylic acid, ethyl p-aminocinnamic acid nitrile, p-dioxycinnamic acid nitrile.

The term of the cinnamic acid derivative to be used according to the invention also includes the cinnamic acid esters of polyhydric alcohols, provided the benzene nucleus has at least one substituent with reactive hydrogen atoms or polyhydric alcohols partially esterified with cinnamic acid, such as processes for production
of in organic solvents

soluble products,

those exposed to light

become insoluble

Applicant:

Paint factories Bayer Aktiengesellschaft,
Leverkusen-Bayerwerk

Dr. Wolf-Dietrich Schellenberg, Leverkusen,
Dr. Dr. hc Dr. eh Dr. hc Otto Bayer,

Leverkus en-B ayerwerk,
Dr. Heinrich Rinke and Dr. Werner Siefken,

Leverkusen,
have been named as inventors

z. B. the bis (p-aminocinnamic acid) glycol ester or the p-oxycinnamic acid ester of trimethylolpropane. Suitable Cinnamic acid derivatives are also the polyvalent acid amides, which are formed from cinnamic acid with polyvalent amines are accessible, e.g. B. the reaction product of 2 moles of p-Nitrözimtsäurechlorid and 1 mole of hexamethylenediamine, which is then reduced to diamine. Finally, suitable cinnamic acid derivatives are also those polyesters which contain cinnamic acid condensed in, for example a polyester made from phthalic acid, adipic acid, maleic acid in Combination with cinnamic acid or p-dioxäthylaminocinnamic acid on the one hand and trimethylolpropane, pentaerythritol bis-cinnamic acid ester and glycol on the other hand.

Suitable di- or polyfunctional isocyanates are, for. B. p-phenylene diisocyanate, hexamethylene diisocyanate, Tolylene diisocyanate, diphenylmethane diisocyanate, m- and p-xylylene diisocyanate and triphenylethane-4,4 ', 4 "-triisocyanate. The higher molecular weight isocyanates mentioned below can also be used for the inventive Process are used.

It is not necessary for the process of the present invention to have compounds with free isocyanate groups be used; it is also possible to use derivatives with blocked isocyanate groups (so-called Isocyanate releasers) (Angew. Chem., A 59, 265 [1947]).

909 608/439

3 4

Requirement for the production of in organic The speed of the by irradiation of light

Solvent-soluble compounds that can undergo light-induced crosslinking by adding

become insoluble from the effects of the aforementioned sensitizers. As such, can

Reaction partners is now that the reaction partners so with particular advantage compounds from the class of

selected and under such reaction conditions 5 cyanines, the triphenylmethane dyes, the benzane

be implemented that premature crosslinking, ins- thrones, the quinones or anthraquinones use

in particular find premature insolubility avoided. These dyes make the named

will. Furthermore, care must be taken that the re-reaction products are particularly vis-à-vis visible ones

Action product sensitized at least three residues of a cinnamic acid light. The degree of networking depends

contains derivatives. io according to the strength of the exposure and the amount of

This can e.g. B. can be achieved in that two cinnamic acid derivatives in the polymer. So he lets himself

low molecular weight reactants with one another easily vary. Networking will make the

be set, in particular the implementation of a body insoluble, harder and less sensitive to

polyvalent with a monovalent or else the transacids and alkali and against solvents. The after

Settlement of two divalent low molecular weight compounds produced by the process according to the invention

oindings comes into question. A well usable light exposure crosslinkable substances can, for. B.

Reaction product provides z. B. the implementation of 1 mole for coatings, foils and the like. Use.

Eiexamethylene diisocyanate or toluene diisocyanate with The production of moldings is also possible,

see e.g. 1 mol of pentaerythritol bis-cinnamic acid ester or p-diox- whose surface is damaged by subsequent exposure

ethylaminocinnamic acid ethyl ester. The reaction is obtained which can be improved. With particular advantage can

products with already film-forming properties, the compounds according to the invention as auxiliaries in

but they are still soluble in organic solvents. use the reproduction technique, as the light

They only become insoluble after exposure. Instead of exposure to the high molecular weight layers on the from

/ to start from relatively low molecular weight components, cross-link areas hit by light, while those not

According to another embodiment of ^{FIG. 2,} 5 points struck by the light can remain unchanged. at

present invention reactive hydrogen after treatment with a suitable solvent

Cinnamic acid derivatives containing cinnamic acid, even with already higher levels, can then be removed from the unexposed areas

implement molecular polyisocyanates. so that imagewise graded layers with very

Higher molecular weight compounds with isocyanate groups with sharp contours can be obtained.

lind z. B. the reaction products of 1 moltrimethylol-30 While it z. B. it was not possible to

> ropan with 3 moles of a diisocyanate. Among these borrowed, suitable for photomechanical reproduction

3egriff also include the conversion products of higher - products according to the state of the art, such as chrome

Molecular polyhydroxy compounds with an over-gelatin, on copper or on plastic as a base

I need diisocyanates. These include, for example, the use of isocyanate, the applicability of the process

Modified polyesters, polyester amides, polyethers or 35 products according to the present invention on copper

Polythioethers with terminal NCO groups, also noteworthy and important. Also their shelf life

let reacted with an excess of diisocyanates without decreasing the photosensitivity or the

Hydrogenation products of a mixture of carbon monoxide and ethylene - the ability of the copying layer to develop is important

) polymerizates. Also polymerization products with free interpretation. The previously common light-sensitive products

'Socyanatgruppen are useful, such as the polymer 4 ° are not mechanically strong enough to, for example

made acrylic acid ethyl ester isocyanate or mixed polymer offset process to be used. You break a lot-

: ate the same with other monomers. As a result, it is more in terms of pressure than in terms of process products

possibly, the chemical and thus the physical according to the present invention is not the case. Latter

Properties of the photosensitive film are also largely chemically more resistant, which z. B. theirs

; u vary. As a suitable mixed polymeriza- 45 use in reproduction technology with trimetal plates

ients have made styrene, vinyl acetate and acrylic acid appear advantageous.

: cyclohexyl ester and methyl acrylate especially _. -I ₁

) lasts. The two reactants to be converted Example

are advantageously used in approximately equivalent amounts of 20 parts of trimethylolpropane monocinnamate

Conditions applied. Also a use of a 50 mixed with 13 parts of hexamethylene diisocyanate. the

Excess of the cinnamic acid derivative is possible. The mixture is heated at 8O ⁰ C for so long until

Reaction will expediently no longer detect any isocyanate groups in the case of space or something analytically

Leave the temperature in an organic solvent. The mass solidifies when it cools. Out of the solution

performed. Films can be made from the resulting clear solution of this product in cyclohexanone

With the evaporation of the solvent, films can be drawn which become insoluble under the action of light,
any threads or threads are pulled. As a solvent

Formamide, dimethylformamide, Beismel 2 are particularly suitable
Cyclohexanone, acetone, butyl acetate or hydrocarbon

substances, very generally those solvents that are associated with the 10 parts of a reaction product of 1 mol of tri

Socyanatgruppen containing starting material does not contain 60 methylolpropane and 3 mol of toluene diisocyanate

respond. 15.4% free isocyanate groups are with 26 parts

When the reaction obtained according to the invention cyclohexanone is diluted. One gives at room temperature

> rproducts are exposed to actinic light, a solution of 7.3 parts of m-amino cinnamon

Change your chemical acid ethyl ester more or less quickly in 26 parts of cyclohexanone and 1 part

ind thus physical properties through polymeric 65 hexahydrodimethylaniline. Then you heat up ation or dimerization of the double bonds of cinnamon at 85 ° C. After about 1 hour, no analytical results can be found acid derivatives. Depending on the structure of the photosensitive isocyanate groups, detect more. From the received

The various clear solutions can be drawn from a high-polymer body, films can be drawn under light bulbs Light sources are used. Cure under particular exposure and develop in the reproductive

Light with high levels of UV rays is ideal. 70 Proven technology well.

Example 3 Example 6

100 parts by weight of a copolymer of 50% To a solution of 40.0 g of 1,4-phenylene-bis (acrylic-

jS-Isocyanatoäthylmethacrylat and 50% vinyl acetate in säureoxäthylester) (0.13 mol) in 200 cc of dry di-100 parts by weight of cyclohexanone with addition of one chlorobenzene dropwise with stirring at 115 to 120 ⁰ C of 1 part by weight of Hexahydrodimethylanilin below 5 a solution of 21 4 g of 1,3-phenylene diisocyanate (0.133 stirring, ^{heated to 80 °} C. In the viscous mol obtained). The dropping time should be about 30 minutes. The solution is slowly stirred into a solution of 53% by weight. Then I ³ Z are heated to the boil for _{2 hours.} divide ethyl p-oxycinnamate into 300 parts by weight. The reaction is carried out in a nitrogen atmosphere by cyclohexanone. The reaction is completed after 3 hours. The polycondensation product separates out when it has ended at 80.degree. The resulting solution of the photosensitive resin is removed. After cooling, the dichlorous plastic is decanted, then benzene is diluted to a solid content and the resin is dissolved in 250 ecm of dimethylformamide, diluted by 4%. This solution can be applied to the offset. For precipitation, the solution is added dropwise to 2.5 l of methanol. Use the sector with great success. One covers z. B. photosensitive polyester urethane falls in the form of a thick granular zinc plate with a layer of this solution threads and cakes. It can be easily vacuumed and and dried into a film. If one exposes the 15 to be dried. The polyester urethane melts under a light-sensitive layer behind a line, grid decomposition at 200 to 210 ^° C. Yield 57.2 g = 94% or half-tone negative about 4 minutes with 30,000 lux and theory.

subsequently developed with cyclohexanone or methyl- The relative viscosity of a 1% solution in m-cresol

glycol acetate, a copy is obtained which is divided into r \ _Tel = 1.68; this corresponds to a K value of 50. particularly high mechanical strength. After 20 For the production of photomechanical images, the offset process can be used to produce prints with a dimethylformamide or cyclohexanone solution in very high print runs. cast films through anodized aluminum sheets

. Λ λ gridded negatives or positives with a carbon arc

Example 4 lamp irradiated. The exposure time is 2 to

100 parts by weight of a copolymer of 70% 25 less than 1 minute. The picture comes with the said p-Isocyanatoäthylmethacrylat and 35% styrene and 5% solvents developed. The networked parts of the film Maleic anhydride in 100 parts by weight of cyclohexanone absorb fat color.

are with the addition of 1 part by weight of hexahydro- The said 1,4-phenylene-bis- (acrylic acid-oxäthyl-

dimethylaniline heated with stirring at 8O ⁰ C. In the ester) is represented as follows:

The viscous solution obtained is slowly stirred into a solution 30 into a solution of 600 g (9.7 mol) of anhydrous from 76 parts by weight of ethyl m-amino cinnamate in ethylene glycol in 160 ecm of dry pyridine and 250 ecm of 300 parts by weight of cyclohexanone. The reaction is absolute dioxane to wear under cooling complete after about 3 hours at 8O ⁰ C for. The solution 10 ⁰ C resulting in portions 115 gl, 4-phenylene-bis- (acrylic acid-diwird then diluted to a solids content of 4%. Chloride) (0.45 mol) of a. After adding the acid chloride, a copper foil is coated with this solution, which is stirred for 30 minutes at room temperature and, in turn, laminated onto a plastic, the reaction mixture is finally heated for 1 hour. After drying exposing the 100 ⁰ C. Subsequently, are distilled off after the dash negative of pyridine and dioxane glycol, excess photosensitive layer; Glycol useful in the electrical circuit diagram, then developed with an oil pump vacuum. The residue is poured into 1.5 liters of ice water while it is still about cyclohexanone and etches the 40 exposed. After short copper spots with a ferric chloride solution. The crude 1,4-phenylene-bis- (acrylic acid thus receives a copper image of the circuit diagram on the oxethyl ester) is crystallized over a period of time. freed from acidic components, washed neutral and off

400 ecm of 50% alcohol recrystallized. yield

TjAieniel ς «86.5 g = 64% of theory (1st fraction). Mp = 136 ° C,

^P molecular weight 306, C ₁₆ H ₁₈ O ₆ .

50 parts by weight of poly-isocyanatoethyhnethacrylate in.

50 parts by weight of cyclohexanone are added. Example

0.5 parts by weight Hexahydrodimethylanilin under 2.80 g cinnamon-p-carboxylic acid bis- (oxyäthylester) (1 x 10 ~ ²

Stirring to 8O ⁰ C warmed. In the resulting viscous 50 mol) and 1.63 gl, 3-phenylene diisocyanate (1.02 · 10 ^-2 mol) solution is stirred slowly added a solution of 59 by weight are dissolved in 20 cc of dry chlorobenzene I ¹ Z ₂ hours in divide cinnamic acid oxyethyl ester in 300 parts by weight of a nitrogen atmosphere with good stirring to give cyclohexanone. The reaction is heated to boiling after 3 hours. The chlorobenzene is terminated after cooling of 8O ⁰ C. For further processing, the precipitated resinous polyester urethane is diluted and the solution obtained is diluted with cyclohexanone on a solid. The resin is dissolved in 50 ecm dimethylformamide content of 4%. This copy preparation can be z. B. to and falls by dropping in 0.51 of methanol. Yield: production or processing of bi- or tri-metal 4.2 g = 95.5% of theory. Melting point = 175 to 180 ^° C., use plates with good success. So you can z. B. r \ _rel = 1.48, K = 42.6.

coat a degreased copper plate with the solution. Analogously to example 6, the product can be made from solution,

After an exposure behind a line, grid or 60 z. B. from dimethylformamide, cyclohexanone, to photo halftone original and the usual development, sensitive films can be cast. The light sensitivity now bathe the plate in a silver cyanad solution and allow 4 to 6 minutes.

create a silver picture on a copper background. The said cinnamon-p-carboxylic acid bis (oxyethyl ester)

You can use them instead but also after the development is shown as follows:

Cover with other metals, so they z. B. after the 65 to a solution of 400 g of ethylene glycol (6.5 mol) chrome in the usual process. On the other hand, you can start from 100 ecm dry pyridine and 100 ecm absolute but also from finished bimetal plates, which are dripped in dioxane with cooling at 10 ⁰ C a solution is coated in the usual way, exposed and developed from 70 g of cinnamon-p-carboxylic acid dichloride ( 0.305 mol) in, after which the chromium in the usual way and 400 ecm of absolute dioxane for 30 minutes. An-way is galvanically or chemically etched away. The reaction mixture is then heated for 1 hour

to simmer. The work-up is carried out as in Example 6. The crude yield is 79 g = 92% of theory.

The cinnamon-p-carboxylic acid bis (oxyethyl ester) is recrystallized from 100 ecm of methanol; the 1st fraction yields 40.8 g with a melting point of 93 to 94.degree. Molecular weight 280; C ₁₄ H ₁₆ O ₆ .

Example 8

33.60 g of cinnamon-p-carboxylic acid bis (oxyethyl ester) (0.12 mol) and 9.18 g of 4-phenylene bis (acrylic acid oxyethyl ester) (0.03 mol) are added with 24.48 g 1,3-phenylene diisocyanate (0.153 mol) in 300 ecm dry chlorobenzene ^{heated to boiling for 1 x} / ₂ hours with thorough stirring in a nitrogen atmosphere. The work-up is carried out as in Example 6. The polyester / ethane mixed condensate is dissolved in 250 ml of dimethylformamide and precipitated in 2.5 l of methanol. Yield: 32.0 g = 92.5% of theory. M.p. = 175 to 180 ^° C; _lrel = 1.56; K = 45.8.

The mixed condensate can be cast from solutions as in Examples 6 and 7 to form photosensitive films will. The sensitivity is 1 to 2 minutes. The exposed film can, among other things, be treated with glycolnonomethyl ether acetate to be developed. The film adheres firmly to copper, aluminum, etc.

The physical mixture of 20% polyester urethane according to Example 6 and 80% polyester urethane according to Example 7 behaves like the fish condensate described above.

Example 9

3.06 g of 1,4-phenylene bis (acrylic acid oxyethyl ester) 0.01 mol), 2.54 g of terephthalic acid - bis (oxyethyl ester) 0.01 mol) and 3.26 g of 1,3-phenylene diisocyanate are η 60 ecm dry chlorobenzene with thorough stirring η a nitrogen atmosphere 1 ^x / ₂ hours to boil. After decanting the chlorobenzene after aging, the polyester-urethane mixed condensate is dissolved in 1 cm of dimethylformamide and α 0.5 l of methanol is precipitated by dropping it. Yield: 5.7 g = 64% of the theory; η _Τί1 = 1.50; K = 43.4.

The mixed condensate can be made from dimethylformamide

solution to be cast into photosensitive films. The sensitivity is 2 to 5 minutes when used a charcoal arc lamp. Films on a glass substrate show good resistance to dilute nitric acid.

Example 10

2.49 g ⁽³ 7,5-10- MoI) l, 4-phenylene-bis- (acrylsäureoxpropylamid) (known to be obtained by aminolysis of l, 4-phenylene-bis- (acrylic acid-dimethyl ester) with propanol-amine 1 , 3 at 160 to 170 ⁰ C, mp. Dioldiamids of 269 ° C) and 1.22 g of 1,3-phenylene diisocyanate (7.65 · 10- ^s mol) are dissolved in 30 cc of dry dimethylformamide in Na-atmosphere IV Heated to 100 ^° C. for _{2 hours.} To isolate the polyamide urethane, the dimethylformamide solution is added dropwise to 300 ecm of methanol. Yield: 2.6 g = 70% of theory. M.p. = 245 to 248 ^° C; η _τα = 1.36; K = 37.

Claims (3)

Patent claims: 1. Process for the preparation of products which are soluble in organic solvents and which are exposed to light become insoluble, characterized in that cinnamic acid or cinnamic acid derivatives, the at least contain a reactive hydrogen atom, with di- or polyfunctional isocyanates converts, the reactants are chosen so that the products at least three times the Grouping of a cinnamic acid derivative included. 2. The method according to claim 1, characterized in that the polyfunctional isocyanates isocyanate-modified polyoxy compounds with terminal N C O groups are used. 3. The method according to claim 1, characterized in that the polyfunctional isocyanates Isocyanate group-containing polymers are used. Considered publications:
U.S. Patent Nos. 2,728,745, 2,282,827.