DE2123623A1 - Radiation sensitive polymers and processes for their preparation - Google Patents

Description

Freedom of knowledge poijmera uni / experienced too your creation

The invention relates to novel _strahlur:; >-erpii; idliche P-Oi. ^ "mere and espondera sfcstrahlungsft '" peach .. »ILcl'ö Ρί L; /. T: ere with both dye and AÄidosuLfjnjioyr ^ anLlyialkOÄ ^ carDonyleinheicen in their chain, also it> t Ais invention m the establishment of permanent connections zwLvjhs :. Saosfcraten ur.d aen GZZLderten polishing or * r -.iriesrischer ". Anchoring of the polymers concerned on substrates.

As far as is known, is that the polymers according to de: * λγfindung including new and zn polymers known not analog Sqostanzen. As a result, the use of these olyrers for the concentration of colorants on subscribers is new and in the pertinent.

The subject matter of the invention is thus s: ". Riir: L,» nj33mpfLnciliüne nait AfLecierkehröriden ülnlieiten of the form-iL a.)

CtI

CH

I γ

BATH

where 1 * 2 eii.en short-chain alkoxy radical or a phenyl :? 8st represents and one of X and Ϊ represents a residue of the formula -CCOR, in which R is in each case a residue of formula

(SO, N _S ) _V

H // sac

• A

is where mean:

A is an alkylene radical with a total of 2 to 10 carbon atoms, where Z is up to 6 carbon atoms. Valence bonds can lie;

R ^{v is} a short-chain alkyl radical or a halogen atom; χ * 1 or- 2y

y »an integer from 0 to 2, where giLfc that χ + y is not greater than 3 »

and in which the SO _P left substituent of the phenyl radical hangs in one of the 3-1 ^ - or 5-positions of the phenyl radical and at least one of these 3 "i ^ - or 5-3ths of a length is unsubstituted;

and the other of the radicals K and Y represents a nest of the formula -COR-i, in which R ^ in each case a by removing the y / asssrstoffafcoms from the primary Kyeirο : <y L group of a radical containing such a group, from the prir amino group of a dye containing such a group or from the amino group of an azo coupler is formed or a combination b.) on (in the polymer chain) recurring units of the formulas:

BATH ORIGINAL

109343 / 1S83

CH

Xi

CH I

H ₈ -CH

CHj

• ahead

the meaning given: possesses unc. eir.er der

Remnants X ,, una Z _x , for a remainder of the rcrael -JOOH una eggs: .. naere for a nest -CLOR, in which R a! e has the meaning given, stands, and

CH

Xs

CH

I Z ₈

CH ■

CH ₂

: τΐ

the indicated meaning is given by one of the

ν. or in

i \ este

others for a remainder GOR ^, in v / elchem H ₁ . has the meaning entered, stands.

una Zp for a Hest of the formula - * XCH and the

Erf indun _o s _L -en.äfi can also v / eraen an iarosücii 'chemically anchored on a substrate, ir.uerc. :. Strfchiun ^ s can polymers on the substrate is effected.

Under the ^ usaruck "alkylene radical irit ins ~ esar.t 2 οίε 1G Carboni tor.en, where 2 to 6 carbon; .. tcr.e zv. Ischen the Vaienzbinaungen can lie "standu for a zv.eiv.ervj ej3n aliphatic carbon residue; with aen. an ^ egebanen Content of carbon atoms on the one hand in the ressT'jon -te st ... and on the other hand in the two valence binaries. connecting

BATH ORIGINAL

10984 9/16 & 8

-Zf-

Chain. Examples of such ^ lkylenreste are ethylene, 1,2-propylene, 1,3-Prooj leri-, 1,4-butylene-, 1,2-pentylene-, 1,3-eexylene-, 2,2-dimethyl-i, 3-propylene-, 2-aethyl-1,4-butylene-, 3-i>; ethyl-1,2-pentylene, '2-ethyl-1,2-octylene radicals and the like · ·

The expression "short-chain alkyl radical" is to be understood as meaning a radical with 1 to 6 carbon atoms inclusive, for example an ethyl, ethyl, propyl, butyl, pentyl or iiex ^ lrect or an isomer thereof. The term " ^M short-chain alkoxy radical" is understood to mean an alkoxy radical with 1 to 6 carbon atoms, including, for example, a ethoxy, ethoxy, propoxy, 3utoxy, pentoxy or kexoxy radical, or a radical of these, see below The term "Htlogenatom" stands in the usual.

In the present case, the expression "sensitive" means that the polymers according to the invention: o upon exposure to a thermal and / or actinic i-ltri: - ': luny ; .M1-fourth and. a molecular itodification; lead.

Else aminophenols to understand with which a Diczoniumvüroindung to form a Ftrbstoffs kunpelt (v -;; eoiet üolic _'; .r,.':; L: By "iizokupplern" are in the tuf j "" rDstofi £ "... see W Encyclopedia of Chemical Technology "Ec. Kirk-.1 thrr.er", 2.; .usrobe, 1963, Volume 2, page 870 ff). Examples of such azo couplers are p- ^ minophenol, 2-iimino-1- n £ iphthol, 4-amino-'l-ru.p -.- thol, 5-arnino-1-n & phthol and the like.

The radiation sensitive polymers according to the invention are derived from polymers with recurring hydride units the formula:

R ₈
I.

_CH CH CH ₈ iv

I BATH

CO
^ o ^ - 5

109849/1688

wherein R- has the meaning given, where two or more of these imhydride units with the formation of recurring Modified units of the i'ormeIn I, II or III are. If the radiation-sensitive polymers according to the invention contain two or more units of the formula I, they don't necessarily have to be recurring Contains units of the I-formulas II and III. she can, however, have such recurring units. However, if the radiation sensitive polymers according to the '' Invention have no recurring units of the formula I, they must contain a combination of recurring units of the formulas II and III. Me distribution of this recurring units of the x'Ormulas I, II and III and of unchangeable units of the formula IV in the polymer chain of the polymers according to the invention is completely arbitrary, as can be seen from the various, later Production method explained in more detail results.

as in the preparation of strahlunb'se: ⁿ pf indlichen terialien polymers according to the invention as Ausgengsm & Poly used ereη with the recurring ü / nit IV consist ems known mixing polymers of maleic anhydride and styrene or a suitable short-chain vinyl ether Alky!. a In the preparation of the radiation-sensitive polymers according to the invention, which contain a combination of recurring units of the formulas II and III in their polymer chain, the starting polymer is preferably mixed with a mixture of a suitable alcohol H-OH in which R has the meaning given , and a suitable amino- or hydroxyl-containing dye or an azo coupler R ,, H _f in which R * has the meaning given. The reaction takes place in the presence of a tertiary base and, advantageously, in the presence of an inert, organic solvent. Examples of usable tertiary bases used in the

BAE60B1G1NAL 109849/1688

ueaktionsgemisch accordingly in the ßegel in a lunge at least 10 wt -. / j of the Ausgangsmischpoly kidney included are pyridine, K, Hi) imethylanilin, triethylamine, UT-morpholine, N-Methylpiperid'in and the like .. Preferably, sls tertiäte Base Pyridine used. The pyridine can optionally be used in such a way that it can serve both as a solvent and as a catalyst for the reaction. According to the invention, the reaction is preferably carried out in such a way that the two reactants are allowed to react dissolved in the pyridine.

Instead of the excess pyridine serving as solvent, however, it is also possible to use an inert organic solvent, ie an organic solvent which neither enters into a lieakfeion with the reactants nor otherwise interferes with the desired reaction process. Examples of suitable inert organic solvents are Benaol, toluene, xylene ₈ tetrahydrofuran, dioxane and the like. "

The reaction of the Äusgangsmischpolymeren with the mixture of the alcohol HOH and the amino- or hydroxyl-containing dye or Izokuppler H ^ H is advantageously V / else at elevated temperatures, ie at temperatures of about 50 ° to about 150 ⁰ C, to suitable reaction rates to achieve". The reaction can of course be followed in the usual way, for example by continuously monitoring the IR spectrum of an aliquot part of the reaction mixture.

The radiation-sensitive polymers obtained in this way can isolate themselves from the reaction mixture according to customary known processes. Thus the desired end product is in the reaction mixture usually in the form of his salses, which comes from the tertiary Alfine catalyst and those formed during the reaction

1038 * 9/1688

- "7 -

free CarboxyIreεten has arisen before. So let yourself the two reactions that take place in different places in the molecule of the iiUSß & iigsmischOOlyraeren expire, by folrende Express equations:

a b f. f

• tertiary _nu L _{- P} "_

-CH CH-CH-CH- + R-OH _A. ~ ^CH CH - CH CH ₈

II ^amine j | ■

₀ ^ co · cooR ^

(IV)

_a b ^ ⁸ tertiary i

TJ

- CH- CH-CH-CHa- ^{+ R} * ^H £ ** £ * -CH-CH-CH-CH ₂ -

_c0 COR ₁ CCO ⁶

* -0 "* (tertiary

(IV) (VI) amine) ©

In the equations given, the remainder of H ₁ R ^ and R2 have the meaning given.

For reasons of simplicity, the ring opening in the inhydride part of the junction copolymer is shown in the two equations in such a way that the carbon core a has the remainder of the formula -COOR or -CQR, d & s carbons ton; b carries the Cerbonsäuresalzrest. For the expert, however, it should be self-evident that? the anhydride part in the starting polymer can also open in the opposite way, so that in the end product the residues of the formulas -JOOR and / or -CCR ,, on the carbon base. b and the carboxylic acid salt residue at Kohlenstoifatom a hanging KÖRA he _t .. For the R & chmenn it should also be understood dai: in the produced according to the method described more polar a far ^ ehena arbitrary distribution of oeiaeij possible structural units is given. The radiation-insensitive polymers according to the invention should include all such polymers with the most varied of properties. Kcrbintitlonen on structural units aes colored. Type belong.

109849/1688 BAD ORlGlHAL

The straiilunrserrpfinulichen polymers geraä ^r? The invention is therefore aun your jrfeaktionsgerrn by acidification and - in the case, there !? no inert solution -Ltte 1 was used - isolated by filtering off, centrifuging off and the like (of the precipitated polar). If an inert solvent was used in the reaction, the desired polymer can be isolated from the solution by precipitation with a solvent, such as, for example, carbon tetrachloride, in which the polymer is not soluble, or by evaporation of the solvent in question.

For those skilled in the art, it should be self-evident that the number of Anhyuria units in the iiUBgcr ^ .pmischpoi ^ meren, those in the described ','. 'also implemented veraer :, of the total amount and the relative lengths of iv. iFchpolyr.eren and oerj two monomeric reaction components used in the reaction depends. In advantageous V / eiε-e the relative Lies in alcohol ROH and dye or Acokuor ^ ler R ^ H in the described iieaktion per LoI R ^ H about 0.2 to about 5 i. oils · ROH make up, with then dar. struMun -.- sernofinaliche Polymers per recurring unit of ionr.cl II about Contains 0.2 to 5 recurring units of egg ror :: el Il £. The i, .engexiant parts of RCH and R ^ H are preferably used in the described implementation chosen so that on, jec.es i.ol des the former about 1 loI of the latter is used. Read Radiation-sensitive polymers have in this i'alle pro recurring unit of iormel II a recurring unit the iormel III on.

Furthermore, the relative LoI ratio is advantageously from home mischoolj'rerem to xieaktioj participants ROH and R ,, H selected such that about 20 to about 100; ν of the i.nh ^ third units contained in the base copolymer converted into units of formulas II or III;:.

BAD - 9 109849/1888

Preferably v / ground the Reaktioiiste ilne ^ mer in such reli.-tive! ". Olverhültnissen an _o replaces them that about 8C £? the anhydride units contained in the starting material are converted into units of the formulas I'I or III.

Sin andores method of making the radiation sensitive Polymers according to the invention with a combination of repeating units of the formulas II and III in the polymer chain consists in the fact that one has the described • Conversion between the starting copolymer and the active participants HOH and R ^ H instead of stepwise at the same time se carries out. So is under the described reaction conditions first reacted the starting copolymer with one of the reactants & 0H and R ^ H, whereupon this formed "intermediate product" with the other participant further implemented. The order in which the two respondents are used is not critical.

Regardless of the manufacturing process used the radiation-sensitive polymers of the above The type is obviously the distribution of the various units of the formula II and III in the polymer chain v / ei arbitrary and not controllable during testing. !

The radiation-sensitive polymers according to the invention with recurring units of the formula I can be produced by treatment and extension of the two-stage process described. Thus, under the reaction conditions described, the starting copolymer is reacted with one of the other reactants ROH or R ^ H , with, depending on the relative ratio of the reactants, one or more anhydride unit (s) of the starting copolymer into the tertiary imine salt of the corresponding half-ester or

SAD ORiGiMAL 109849/1688 - 10 -

-ainids der'Formula V or VI is transferred (verden). The "free" carboxylic acid is then set free from the amine salt obtained, whereupon this, depending on which reactant HOH or R ^ H was not used in the first stage, is esterified or amidated. This esterification or arcidation reaction can be carried out by customary known methods. For example, in the case of esterification of the alcohol and the acid at elevated temperatures, ie at temperatures of about 50 ° to about 150 ⁰ C, in the presence of traces of a mineral acid such as beispieIsweise sulfuric acid, hydrochloric acid and the like., As well as advantageously in combined presence of an inert organic solvent of the described Typi together · Preferably used mau as the inert organic Jiösun & s- 'medium, such, for example, "benzene _s that with a water it azeotropic mixture forms and consequently to remove the cleaved off during the esterification reaction, water and an acceleration able to contribute to the esterification reaction. In the case of amination, the free carboxylic acid units in the intermediate polymer are converted into the corresponding acid chloride by reaction with thionyl chloride and the like, whereupon this is reacted with a suitable amino dye or aminophenol under the reaction conditions usually used in the preparation of amides.

However, if the desired repeating unit of the formula I should contain an amide group, this group is preferably introduced in the first of the two reaction stages, by cutting through the anhydride ring of the Ausgarigsmischpolyeeren Reaction with a suitable amino pigment or aminophenol opens. The second reaction stage is then always an esterification.

As in the case of the radiation-sensitive polymers according to

- 11 109849/1688

BATH

the invention having the repeating units of the I · or me in II and III can also be a str "hlur £ sen: pf inoliehe" polymer of the invention having the recurring Einli3it I regard the latter in zvfei Various; 's otrul?...: turfor: .. en exist. This depends a lot on how the anhydride ring, the unit IV of the starting mixture, has opened. The product obtained in the process described has a polymer chain in which some repeating units have one structure and other repeating units have the other structure. For reasons of simplification, however, this situation is subsumed under the single formula I for the relevant repeating units of radiation-sensitive polymers according to the invention.

For the person skilled in the art, it should be self-evident that the percentage of the The described seduction of anhydride units converted into units of the formula I in the initial mixed polyxerene by using the correct oil ratios of the participants is also possible. It is also possible to use radiation-sensitive polymers according to the invention with a unit composed of recurring units of the formula I and the formula II or of the formula III or a mixture of all three recurring units by using in the last process stage one of those ',' close to esterifying or amidating agents which under the group to convert all free Ct-rboxy! / ^ v ischenoolj "nieren he forcier lent η stoichiometric" length lies. AjLe Surahlung- sensitive polymers according to the invention with a combination of all three recurring units of the formulas I, II and III in the polymer chain can be amidated or esterified some, but not all ^? free carboxyl units in the in the ge -

f.

described ¥; also produced radiation-sensitive polymers with recurring units of the formulas II and III in your chain.

BAD ORlGiNAL

109849/1688 - 12 -

In den'durch, the formula R ^ H, where R ^ the specified Has meaning, reproduced airino color can be used it is in the: Simultaneously from The Society of Dyers and Colourists, Bradford, Yorkshire, England and The American Association of Textile Chemists and Colors, Lowell, "Color Index" published in Massachusetts, 2nd edition, Bend 1, pages 1617-1653 »1965 described dyes act. These dyes form an amino residue in the molecule, but no other radical, such as a Hydroxy1- or amino radical, the one with the anhydride unit of the starting mixed polymer could react. Typical such dyes are crystal violet, methylene blue, malachite green, Auranin 0, basic fuchsin, aniline yellow, Disperse Orange 3 » Disperse Black 7 »Disperse Red 13» Disperse Red 9 »Vat Red 33» Stain Violet 6, Phenylene Blue, Disperse Orange 11, Katur Orange 6, Latur Brown 7 and i.atur Yellow 12.

In the case of the dyes containing a primary hydroxyl group of the formula R ^ H, in which R ^ has the meaning given, it can be such customary known dyes, which has a single primary hydroxyl group, but no other active group, e.g. a hydroxyl or amino group, those in reaction with an anhydride unit in the starting mixed polymer might occur.

Examples of such dyes with primary hydroxyl groups are natural orange 6 (2-hydroxy-1,4-naphthoquinone), natural brown 7 (8-hydroxy-1,4-nephthoquinone), natural yellow 1,2 [2- (p-hydroxyphenyl ) -1,4-naphthoquinone, the 2-hydroxyethyl ethers of these compounds (which are obtained by reacting the hydroxy dyes, for example the listed hydroxy dyes, with 1 mol part of ethylene oxide), Disperse Red 13 (Palacet Scarlet B) H2-chloro-4-nitro -4 '- (K-äthyl-Ii-hydroxyäthylamino) azobenzol.J and similar compounds, which by reacting basic color

- 13 -

109849/1688

BATH

substances with a secondary amino group (see "Color Index") with 1 VI part ethylene oxide were obtained.

Those radiation-sensitive polymers according to the invention with recurring units of the formulas I and / or III in which the remainder Ry. for one reads an aminophenol azo coupler, can be converted into a herbal unit with a jjiazoniur; salt with conversion of the radical R ^. The reaction can be carried out either before or after the anchoring of the radiation-sensitive polymer on a substrate, which is explained in more detail below.

The implementation of the Aüokomplexeinheit with the I / i can be according to the process and with the ui & zonium salts, v; ie she in "Encyclopedia of Chemical Technology", Kirk-Othner edition, 2nd edition, $ 196, volume 2, page 87C ff. During the diazotization, all can be im Azodiazo compounds listed in "Color Index", Volume 2, pages 2571-2612 uses v / earth.

The maleic anhydride copolymers used as starting materials when carrying out the process according to the invention with recurring units of the ϊ-formula IV are known and are found, for example, in the "Encyclopedia w of Chemical Technology ", Volume 8, pages 685 ff and Volume 11, Page 652 and in U.S. Patents 2,424,814 and. 2,047,398. These copolymers stand with the different molecular weights, e.g. with molecular weights from around 100CG0 to around 125C000 are available.

For the person skilled in the art, it should be understood that. the chain length of the r.'aleiric anhydride starting.-.- ischpolyreren when converting into the respective ester and amide polymer

- 14 109849/1688 _bA D

with recurring units I ₉ II or III remains unaffected. However, the overall definition of the polymer changes according to the anhydride units of the starting copolymer converted into ester and amide units.

As a rule, the ^ molecular weight of the photosensitive Polymers according to the invention between about 100,000 and about 2,000,000. These polymers are for the most part to resinous solids in polar solvents such as acetone, methyl ethyl ketone., Tetrahydrofuran, dioxane and the like. are soluble. Solutions of the polymers in question in the above As will be explained in more detail later, solvents can be cast into films «.

The radiation-sensitive polymers according to the invention with the recurring units of the formulas II and III due to the free carboxylic acid groups it contains (such) in the form of salts, e.g. as alkali metal - such as sodium -, Potassium or lithium salts, as alkaline earth metal, such as calcium, Strontium or barium salts or as aincioniusi salts or salts organic amines exist. These salts usually have a considerable solubility in water; this property enables them for special usability in certain areas of application. The free carboxylic acid units in the polymers according to of the invention with the repeating units of the formulas II and III can be converted into the transfer corresponding salt units; for example, the polymer can be in the form of a solution in a polar solvent be reacted with an aqueous solution of the base in question. The base used can be added in such a long amount be that only one or more or all of the carboxylic acid groups in the Po Iy tr.e renket te are neutralized.

BATH 109849/1688

- 15 -

The in the manufacture of the radiation-sensitive Polymers according to the invention; used as starting materials Alcohols R-01, in which R has the meaning given, can be obtained by reacting a suitable diol ΗΟ-λ-CK, where A has the meaning given owns, with buckets of suitable isoc; y & natobenzenesulfonyl chloride the formula:

(SO ₈ Cl) _x

// yk ^

OCN

(VII)

where H ^, χ and y have the narrow meaning, produce. This gives the corresponding intermediate sulfonyl chloride product of the formula:

Il

HO A-0 -C -NH ^

^^^ R (VIII)

whereupon this with conversion of aes sulfonyl chloride residue into a sulfonazide residue (i.e. into the desired alcohol) is reacted with liatric azide.

In the preparation of the base alcohol RCH, the diol O-A-OH and the isocyanatobenzenesulfonyl chloride of the formula VII are combined with one another under conditions known to those skilled in the art for the reaction of alcohols with isocyanates. The reactants are advantageously brought together at room temperature, ie at temperatures of the order of 20 ° to 25 ° C., in the presence of an inert, organic solvent of the type described. Kech to combining the Reektionsteilnehirer the reaction mixture obtained is gehal- at a temperature below 5O ⁰ C

BAD ORiGlNAt 109849/1688

th, to lead to the formation of undesirable by-products, reaction of the hydroxy radicals of the diol with the sulfonyl halide units Avoid isocyanatosulfonyl chloride.

If appropriate, the reaction between the diol and the isocyanatobenzenesulfonyl chloride of the formula VII can be carried out in the presence of a catalyst. Suitable catalysts are, for example, those which are customarily used to promote a reaction between hydrochloric radicals and isocyanate radicals, for example triethylamine, triethylenediamine, K ₁ IT ₁ R ¹ , N ¹ -Te trame thy! Ethylenediamine, K, Ii, K ¹ , N '-Tetraethylethylenediamine, Ui ^ ethylmorpho-' lin, K-ethylmorpholine, 1,1 ^ »I- ^ etramethylguanidine, j \, K, E ¹ , N ¹ -tetramethyl-1,3-butenediamine, tin (II) octoate, Dibutyltin dilaurate and the like.

The hydroxyalkyl carbamate intermediate formed in the Formula VIII can optionally be obtained from the reaction mixtures for example by evaporating the solvent, isolated and, for example by recrystallization, purified, before it is converted into the desired alcohol ROH. However, it is usually not necessary to make the connection of formula VIII prior to their conversion into the desired alcohol. Indeed, when implementing the ' Diol formed with the isocyan ^ tosulfonyl chloride of I'crmel VII Reaction product can be converted directly into the ultimately desired alcohol without further treatment. So can For example, the procedure you have described, the compound of formula VIII in an inert, organic Solvent-containing reaction mixture without any purification with a suitable amount of sodium azide, i.e. one Liol E & trium azide on each in the compound

109849/1688

of the formula VIII contained SOpCl radical, reacted v / ground. Since the reaction is exothermic, it is controlled by cooling, if necessary, to between the reaction temperature to hold around 25 ° and around 80 ° C. The atrium chloride formed during the reaction precipitates from the reaction mixture, with the amount of sodium chloride precipitated as a guide can serve for the progress of the implementation. The desired alcohol .ROH can be obtained from the heaktionge. separate mixed according to the usual methods. For example, the precipitated sodium chloride can be filtered off and that The filtrate is evaporated to dryness. The alcohol isolated in this way can be used in the synthesis of the polymers according to the invention by recrystallization and the like. Purified.

Most of the isocyanatobenzene sulfonyl chlorides of the formula VII used in the preparation of the alcohols ROH are known and can be obtained by phosgenation of the corresponding, known aminobenzenesulfonic acids according to customary known processes, for example according to that of Alberino and coworkers in the journal "J, Polymer Science ¹¹ , volume 5 »pages 3212-13« 1967 »described method.

As already stated, the novel radiation-sensitive Use polymers according to the invention in a wide variety of fields of application. So can this Polymers, for example, as chemical anchoring agents for dyes on the surfaces of a wide variety of substrates, such as paper, cotton and similar cellulose materials, metal, glass and the like, as well as on polymeric substrates such as polyolefins, polyurethanes, polyamides, Polyesters, polyacetals and the like, which are normally not absorbent for such x-dyes sir.i, used

109849/1 683

will. In this special field of application of polymers according to the invention, a coating of the latter is applied to part or all of the surface of the surface to be treated Substrate applied ». The application of the coating is carried out in an advantageous manner by spreading a Solution of the radiation-sensitive polymer according to the invention in a polar solvent of the type described with the help of suitable applicators on the Substrate

The coated substrate then becomes one for activation of the polymer according to the invention required thermal or actinic radiation. Here can use the most varied sources of radiation for thermal and / or uses akijin radiation; v / earth. Such sources of radiation are for example Kohlsnbogen, mercury vapor lamps, FluoreszenslampQXii argon incandescent lamps, photographic Floodlights and «Volfrsmlair« pen · Preferably one Radiation source uses j dig UV light of one wavelength emits between about 250 im and about 390 he.

If necessary, the coated substrate can be irradiated or exposed in an "imagewise" manner. This means' that a negative of the imaged on the surface of the substrate image between the coated substrate and dis radiation source is inserted, "Uas strab.lungsempfindiichs polymer is in the parts of the bsschieht © ^t: receive the radiation 8n substrate _0, activated and dsr substrate top? laugh "chemically anchored, or vie .. chemical anchoring the binding of strahlungseiapfindlichen polymers to aas substrate is probably due to a decomposition of the oulfonaziarestes BZV /. of the sulfonaside radicals in the units of the polymer in question with the formation of a nitrogen radical (I.itrene are compounds of the type UUg = SH-CH ₂ ) "which occurs with the -GH bonds in the substrate in the Aechnelv-irkuiig, this suspect

109849/168 © - 19 -

BATH ORIGINAL

However, rieakticnsmechariisciUB only serves as a drama the invention.

If that in the described manner is used as a coating Polymers of an azo coupler applied to the substrate are applied, i.e. if the repeating units of the formulas I or III are the remainder of an aminophsnol-uzokupplers contain, the coated substrate can then be treated with a diazonium salt solution to remove the azo complex residue to 'transfer to a dye unit. i> as üppli- ' decorating the diazonium salt on the azo complex can be carried out in a conventional manner, for example by immersion of the coated substrate in a diazonium salt solution or by applying the latter to the substrate by means of a A roller, a sponge and the like.

For the person skilled in the art, it should be understood that the process described for the chemical anchoring of basic dyes to polymers, usually for such . Dyes non-absorbent substrates can be transferred to a wide variety of dyeing and / or printing processes * So For example, the printing of polymeric films with advertisements and the like can be carried out continuously without difficulty carry out by running a continuous strip of film one after the other through different zones, in which first the Film with a radiation-sensitive polymer according to FIG Invention coated, thereupon the coated film by means of a suitable radiation source an activating image in accordance with the image Exposed to radiation and finally the polymer layer on the non-irradiated areas by washing with a solvent is removed * The latter measure can, for example, by washing the irradiated film with the one when it was applied the original layer or the original coating

- 20 109849/1688

Solvent used or a similar polar solvent be accomplished. If, on the other hand, the photosensitive polymer has free carboxyl radicals, can use the unmodified, photosensitive polymer of the substrate with an aqueous solution of a base such as sodium carbonate, sodium hydroxide, ammonium hydroxide and the like. to be washed off. In the event that the polymer forming the coating has a Zokupplerrest instead of a dye residue on top of that, the exposed or irradiated coating can then be post-treated with a diazonium salt solution will"

In a further form of application, the new radiation-sensitive ones are grounded Polymers according to the invention with the repeating units of the formula I as components of a Photoresist system used. So the polymers according to of the invention, for example, in the field of photo reproduction and photo printing for the production of printing stencils be used. Here, the polymer with the repeating units of the formula I in an oolar organic Solvents of the type described are dissolved and in the form of the solution as a film on a suitable substrate, e.g. Paper, metal or other film carriers customary in the field of reproduction technology, poured on. Then will between the in the described V / ice applied film on a base and a radiation source, which is a Activation of the radiation-sensitive polymer required Emits radiation, a negative of the image to be reproduced, e.g. a line, grid or grid vegetative, or a slide inserted. During the irradiation, the " Polymers at the points exposed to the radiation of the film on the base on the substrate anchored. In the non-irradiated areas of the film the polymer can be washed out with an oolar

- 21 -

T09849 / T688

BADORiGiNAL

! solvents or, in! 'all that polymers rr.it free Carboxy residues were used by washing them out with a remove aqueous solution of a 3ase of the type described. In this case, the irradiated polymer remains on the substrate in the form of a cone that is used in the irradiation corresponding positive or a negative corresponding to the positive used during irradiation. This image is highly resistant to solvents and mechanical Resistant to stress and can advantageously be used as a template for reproducing copies of the original uses v / earth.

In a corresponding manner, polymers according to the invention can be produced using the radiation sensitive Photoresist systems in other areas of photoresist, for example in the manufacture of printed circuits or on related, engaged in the production of images: areas of application in the form of one on a metallic substrate, such as for example eir: he copper foil or a copper sheet, anchored polymers can be used, whereby in the end a part of the or the entire niCiit-covered metal (s) is etched away. The last form of application is used for the production of the polymer image on the substrates concerned almost the same iV. measures as they were in connection with the production of printing stencils.

In the following, first the production of a starting verb indüng- sensitive to radiation during manufacture en-polymers' according to the invention used sulfonylcarbanilate described.

50.4 g (0.8% .ol) of ethylene glycol in 500 ml of acetonitrile were with a solution of 43.2 g (0.2 ilol) of after derr. from

- 22 -

^109849/1688 BADOB.G.NAJ.

4-isocyanatobenzenesulfonyl chloride described by L. Alberino and co-workers. The addition was carried out with stirring and cooling to a temperature of about 2 ° to 8 ⁰ C within 10 minutes. The reaction mixture was then left to stand at room temperature until (after about 30 minutes) the ITCO band observed in the IH spectrum of an aliquot of the reaction mixture disappeared. The resulting reaction mixture was admixed with 13 g (0.2 mol) of sodium azide, and the resulting mixture was stirred for 1 hour at room temperature, and the precipitated sodium chloride was filtered off, and about 80% of the solvent was evaporated from the filtrate under vacuum. The remaining filtrate was mixed with water to precipitate the water-insoluble product. The precipitate formed was filtered off, washed with water and dried under vacuum at room temperature. In this case were 52 .g (91% of theoretical yield) of white of a crystalline powder-4-azidosulfonylcarbanilat 2-hydroxyethyl due to its IR and NMR spectrum as having a melting point of 115 ° to 118 ⁰ C identified v / urde obtained . Recrystallization from acetonitrile white crystals precipitated with a melting point of 120 ° to 122 ⁰ C (determined by the Fisher-Johns Kethode) or 124 ⁰ C (determined by the DSC ^ ethod) were obtained.

Analysis of CqH ^ qN ^ OcS: Calculated: C = 37 »76; H = 3 * 46

found: C = 37.60; H = 3.73

In the manner described, but with replacement of the ethylene glycol by 1,3-propylene glycol, 1,4-butanediol, 1,3-pentanediol, 2,3-hexanediol, 1,5-iIeptanediol, 2,2-dietethyl-1,6-hexanediol and 2,5-diethyl-1,6-hexanediol

3-hydroxypropyl-4-azidosulfonylcarbanilate,

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109849/1688

BATH

^ -Hydroxybutyl - ^ - azidosulfor ^ ylcarbanilot,

3-hydroxy-2-metli ^ lperitj 1-4-azidosulfonylcarbanilat, Jp-Hydroxyheptyl - ^ - azidosulfonylcarbanilate, 6-hydroxy-2,2-di-tiethylhexyl-4-azidosulforiylcarbanilate and 6-hydroxy-2,5-diethylhexyl-4-azidosulfon; ylcarbanilate

manufactured. *

The following examples are intended to illustrate the preparation and use of the radiation-sensitive polymers according to the invention explain in more detail.

example 1

A mixture of 1.7% of a ftlaleic anhydride / methyl vinyl ether copolymer with an average molecular weight of 25CX) OO, 1.57 g of Palacet Scarlet B and 1.43 g of 2-hydroxyethyl-4-azidosulfonyl caΓbanilate were dissolved in 30 ml of anhydrous pyridine , whereupon the solution obtained was ^{heated to a temperature of 80 °} C. for 12 hours. The reaction mixture was then evaporated to dryness and the residue was dissolved in a mixture of equal parts of acetone and water. The resulting solution was acidified by adding 100 ml of 5N hydrochloric acid. The precipitate which separated out was filtered off, dried and dissolved in 50 ml of a mixture of acetone and methanol. This gave a solution of a photosensitized potassium anhydride / methyl vinyl ether mixed polymerisation, in which one of 2 units recurring in the chain is composed of a unit of the formula:

Supreme Court ₃

cn CH CH ₃

I I

COOP COOQ

- 24 T09849 / 1688

wherein one of the niests P and Q stands for a hydrogen atom and the other for a remainder of the formula:

O
CH ₂ CH ₃ - O - C - NH - <'V - SO ₈ N ₃

and one of two units recurring in the chain from a unit of the formula:

CH ₈

-. _CH OCH ₃ I. I. CH COOB CH- I. COOA

in which one of the radicals η and B for a hydrogen atom and the other for a radical of the formula:

CH ₉ -CH ₈ -N- ^ y- N = N- ^ y- NO ₃

C ₃ H ₈

stands, existed.

Li ith the help of a V.irDler was by spraying a small Amount of the polymer solution obtained on a polyethylene film cast a film. Then the received radiation; ε-sensitive Material for 5 minutes with one under the trade name "Hanovia Type SH sold- ^ mercury arc lamp exposed. After the end of the exposure, it was found that the film was anchored to the polyethylene substrate, through ~ the various abrasive forces could not be removed and not brought into solution in acetone and other polar solvents could be. . . ..

- 25 109849/1688 BAD original

Example 2

The procedure described in Example 1 was repeated, except that the talinic anhydride / ethyl vinyl ether lipolefinic polymer was replaced by a maleic anhydride / styrene polymer having an average molecular weight of 1000CO. In this way, a correspondingly modified Italian-styrene hydride / styrene-iv'ischpolyriieres was obtained, in which about one of two units of the i-orniel recurring in the chain:

CH

COOP.

CH

C ₈ H ₈ CH -

CHa

COOQ

where one of the! keys P and ^ for a hydrogen atom and the other door a remainder of the formula:

O j κ

CHd-CH ₃ O -C NH ([ 7 "

SO ₂ N ₃

and one of two recurring units in the chain the jOrrr.el:

CH

\ COOA

CH -

COOB

C ₈ Hg CH-

CH ₃

where one cer leaves α and B for a '.VosserGtciTstor and the other for a remainder of the' torinel:

CHa-CH ₂ -N

N = N

rteht, er.tr or-eh.

BATH

109849/1688

In the '.'. Described in example 1, .but under Replacement of the 2-H; yaro; xy £ ith; yl-4-azidosulfonylcarb £ .nilats by equivalent amounts of 3-Hydroxypropyl-, 4-Hydroxybutyl-, 3-hydroxypentyl, 3-hydroxy ~ 2-methylpentyl, 5-hydroxyheptyl, 6-Hydroxy-2, 2-dimethylhexyl and 6-hydroxy-2,5-diethylhe3jyl-4-azidosulfonylcarbanilate the appropriately modified copolymers of laleic anhydride and », thy lviny lather obtain.

Example 3

Using the solution of the photosensitive, modified liquid polymer according to Example 1, a film was cast on a substrate made of a polyethylene film. On top of the film in question, a template was placed, which was a negative of a dot pattern to be reproduced. The film was then exposed for 2 minutes using a mercury arc ink sold under the trade name Hanovia Type SH, the exposure plane being 15 cm in front of the lamp. The exposed film was developed by immersing it for 1 minute (with agitation) in a mixture of acetone and N, ϊΤ-mmethyl formamide (100: 1 volume ratio). The thus obtained SIID besa- ^r i a high iiuflösung.

Example 4

A mixture of 1.7 g of an all vinyl ether mixed polymer with an average; it bluish dissolved molecular weight of 25OCCO, 0.55 g of p-Äminophenol and "\, 43 g of 2-IIydroxyäthyl-4-a2idosulfonylcarbanilat been ml anhydrous in 30th pyridine, and the resulting solution 12 otunden long to a temperature of SO ⁰ G The reaction mixture thus obtained was evaporated to dryness and the residue was converted into a mixture of equal parts of acetone and

1 09849 / Ιβββ _BAD0R .G.HAL

V / ater resolved. The solution obtained was by adding 1CO ml of 5 η hydrochloric acid acidified. The one here deposited precipitate was filtered off, dried and dissolved in 50 ml of a mixture of acetone and methanol. Here, a solution of a light-sensitive was created Ivlaleic anhydride / Letliylviri ^ läther-Mischpolyr.eren obtained, in which one of two recurring units in the chain of the formula:

OCH ₃ CH CH CH CH ₈

COOP COOQ

wherein one of the radicals P and ^ is a hydrogen atom and the other for a rest of the. Formula:

O CHa-CH ₈ -OC -NH (' ^X V- SOaN ₃

and one of two units of the formula that appear in the chain:

OCH ₃

_CH CH CH CH ₈

I I

X X ¹

wherein one of the radicals X and X ^{1 is} a radical of the formula -GOOH and the other is a radical of the formula:

- CONH

stands, corresponded.

From the resulting solution was on a polyethylene existing substrate cast a film. On top

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109849/1688 _klil

BAD ORIGtHAL

of the film obtained became an original which was a negative of a dot pattern to be reproduced, placed. The film was then held for 2 minutes by means of an under the trade name 'Hanovia. Type SH distributed mercury The arc lamp is exposed, the exposure plane 15 cm in front of the lamp. The exposed film was then immersed (with agitation) in a mixture for 1 minute from acetone and Κ, Ν-diir.ethylformamide (100: 1 volume ratio) developed.

The exposed film was then briefly converted into a p-phenylezoaniline by diazotizing a solution of 4.84 g (0.02 KoI) obtained in 20 ml of 2η hydrochloric acid Solution immersed. Then the treated film was washed with water. It was found that a The dark red image corresponding to the negative used in the exposure was anchored. This picture was neither remove by abrasive forces or with solvents.

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10 9849 / T688 BAD ORIGINAL

Claims (1)

Patent application 1.) Sensitive to radiation ^ Polymers with recurring Units of the formula a.) R, _ _CH CH CH CH ₃ I I X Y wherein Rp is a short-chain alkoxy radical or a phenyl radical and one of the radicals X and Ϊ represents a radical of the formula -CJGOR, in which R in .jedemfall is a radical of formula 0-C-NH- / ' \ V ^R y is where mean: A is an alkyl radical with a total of 2 to 10 carbon atoms, with 2 to 6 carbon atoms between the Valence bonds can lie; R ^{y is} a short-chain alkyl radical or a halogen atom; χ = 1 or 2; y = an integer from 0 to 2, with the proviso that χ and y is not greater than 3, and in which the SOoNy substituent of the phenyl radical in 109849/1688 BATH ORIGINAL - 30 - one of the 3-, 4- or 5-positions of the phenyl radical hangs and at least one of these 3, 4 or 5 positions is unsubstituted is; and the other of the radicals X and I stands for a radical of the formula -GCIL, in which R ^ in each! '' all a dye containing such a group by removing the hydrogen atom from the primary hydroxyl group, from the amino group of a dye containing such a group or from the amino group of an azo coupler is formed residue; or a combination b.) of (in the same polymer chain) recurring units of the formulas: R ₃
I.
-CH —-—— CH —— CH - CH ₈ Xl Z ₁ where R2 ^ ^θ a ^ has a given meaning and one of the X ^ and Z ^ radicals for a radical of the formula -GCCH and the others for a remainder -GOQR, in which R the given Has meaning, stands, and R ₂ _ ^ CH - CH CH - CH ₃ Xa Z ₃ wherein R _{2 has} the meaning given and one of the radicals X ₂ and Z _{2 is} a radical of the formula -CüGH and the other is a radical -COR ,, in which R ^ has the meaning given. 2.) Polymers according to claim 1, characterized by that they are a combination of recurring units of the Formulas: OCH ₃ I CH - CH -—— CH - CH ₃ - i I COOP COOQ 1G9848 / 1688 bad ORIGINAL where one of the beds P and Q for a hydrogen atom and the other for a remainder of the formula CH, -CH _8-0 ~ C-NH stands, and OCH ₃ CH CH CH CH ₈ —— II XX ¹ wherein one of the radicals X and X 'is a radical of the formula -COCH and the other for a reed of formula —CONH is included. 3) Polymers according to Claim 1, characterized. that they are a combination of recurring units of the formulas - CH CH CH CH ₃ COOP COOQ wherein one of the radicals P and Q represents a hydrogen atom and the other represents a radical of the formula: SON ₃ stands, and CH ₈ -CH ₈ O-C-NH 1088 * 9/168 " wherein one of the radicals A and B represents a hydrogen atom and the other represents a radical of the formula: -CH ₈ is included. hu) Process for the preparation of radiation-sensitive polymers according to one of the preceding claims, characterized in that a copolymer with recurring units of the formula: R ₈ -CH CH CH -CH ₈ jl IV CO _ ^ CO wherein Rg has the meaning given, in the presence of a tertiary base and preferably an inert organic solvent at elevated temperatures with an alcohol of the formula ROH and an amino- or hydroxyl-containing dye and / or an azo coupler of the formula R ^ H, in which H and R * have the meaning given. 5. The method according to claim 4, characterized in that the reaction is carried out in excess pyridine. , 6.) The method according to any one of claims 4 and 5, characterized characterized in that the reaction is carried out at a temperature 109849/1688 -33 BATH ORIGINAL - 55 - performs from about 50 ° to 15O ⁰ C. 7 ·) Use of a radiation-sensitive polymer " according to one of claims 1 to 3 for (chemical) anchoring from dyes to polymers otherwise not absorbent for dyes, with the polymer combination under Activation of the light and heat sensitive polymer, is irradiated in a suitable manner. ι · 8.) Use according to claim 7 »characterized in that the radiation-sensitive polymers of a coating is applied to the polymeric substrate in the form of w. 9.) Use according to one of claims 7 and 8, characterized in that the irradiation of the radiation-sensitive Polymers is done in accordance with the image and the non-irradiated Then place the radiation-sensitive polymer washed off with a solvent. 10.) Use according to one of claims 7 to 9 »thereby characterized in that a polyolefin is used as the polymeric substrate. # 11.) Use according to one of claims 8 to 10, characterized characterized in that one of polyethylene fls polymeric substrate goes out. 12.) Use according to one or more of claims 7 to 11, characterized by 'that the polymer combination in contact with a biazonium salt solution after irradiation is brought. 109849/1688