DE1572199A1 - Non-slip azographic film - Google Patents

Description

Tecnifax Corporation Holyoke, Mass., USA

Fixed azographic film

The invention is in the field of the reproduction of - • tjproduzieroarem material, δ.B. photographic film, there are "image recordings with the help of light-sensitive diazo compounds, as they are used for so-called" azographic " ₍ processes of the type of diazotype, dlazourism, diazothermography and the like) , razor sharpness and reduced risk of double image evocation, with the help of rotary: .drum contact copier s.

In the diazo multiplication of image-bearing recordings and in particular photographic films with the aid of a rotary contact copier, it has hitherto made difficulties Diazo copies of pin sharp sharpness and high resolution, i.e. those without double or blurred image contours to be achieved., It is true that i-ian received such sharp and resolute -., '; - lne on a random basis Prints, but had to take a high percentage of rejects, which in particular lead to losses of diazo film and Corresponding double arboit resulted when the film width exceeded 35 mm. This meant that every single diazo copy was accurate

.) · Had to Ufen in order to ensure an acceptable quality of work. co

In order to reduce this high reject rate

^ I've tried many ways so far. On the one hand, the Ό ah troi; i; .i ^r il copier has been given various special designs,

co., ir, Dianofiliii and photographic film in non-slip and separable cn

^ ' : kun; r olieben. 'Ji-ot, ·, df. ν so he /, direct improved registration ι- 'iji-äno blien the Aus3 (jnuujü'iuoi; e but still unbearably high.

f the other "Jeite tried to lower the committee loss Modifierung the footage. All in all but one can very v / eni ^ change of Filmzusamuiensetzung without the numerous, matching balanced variables jor considered and must Readjust. went Again .nan again in i, v / eierloi manner · by adding ι either ..sin fil.ijüildt-.nc'-i'i n ^ iiiehö-n aui * der ΐΛ <: ...:, ί'ϋ, obe. · Λ'1'dchi : -r without sclj'ic-, a ar- .Λ ~, additions to light-sensitive layers.

In the first case, you have to go exactly to a) Ruftfe_; tigkeifc -see top layer and light-sensitive linofilm, b) ¹ Md c) "over chlässigkoif. aei Deekcchiehc for Auiioniai: and iJtiukstoff, d) Voccc-'ti ^ - : hkeit der Le ^ Iuchloh "i..it üe.u light sensitive approach, e) Kraozer- • tigkeit, f) optical .Kj.ai-hf. -it ^ nä g) chemiijhe neutrality g = r Le:; kicht against dan liolir.e.npfindliehen material eighth Di ^ Fcrderunger: apply to g) uoh "St. · the ^ / nits case... · Inl'-jlgtd: ssen rui t j ^ cie erung im Dia ^ ofil: n approach often more problems than 31ε.

knows, for example, the gun.rüiar: the properties of styroladiene Copolyrneren, which you can recommend as a Russian marriage agent let it shine. Contrary to all expectations, these materials show insufficient solubility and poor compatibility would succumb with the consequent deterioration in transparency, so that they are unsuitable for this purpose.

In accordance with the invention, it was found that one is one like material combination using a film former novel film material that not only contains the diazo film * .amations due to poor resolution and sharpness due to slipping "■ ingers, but also the mandatory £ ri'of-.isse listed above Fulfills. 909687/1359

BATH O.

More precisely, according to the invention, the copying losses can be reduced considerably by using a diazo-film, if the photo layer contains a diazosal, a coupler and stabilizers, and on its surface a thin adhesive layer made of a slip-preventing and contact-maintaining agent having. This photo layer can either be on a support made of paper, cloth or film, or it can itself form a part of the same support material, for example cellulose acetate. This modification of the diazo film produces copies of increased sharpness and resolution that are free of double and blurred contours.

The invention will become apparent from the following description together with the attached drawings can still be seen. Show it

Fig. 1 is a schematic cross-section through a rotary drum Kontaktfilmkopitrgerat, which consists of an elongated, axially rotating, translucent cylinder, an axially aligned housing fixed therein Light source and a belt that holds the photographic Introduces the film and the slide film and at the same time the translucent Cylinder drives.

Fig. 2 is a part of a section through a U.nfanosabschnitt Cylinder, from which you can see how the image-bearing material through the textile belt with a.ii Diasofil.nträger is in contact,

Fig. 3 tinen ku ^ rsohnitt by the inventive diazo filter, its photosensitive layer of polymer substance with its support uniformly related to the material and the anti-slip layer on top carries, and

Fig. 4 shows a similar cross section through a modified / msführungform of the slide according to the invention, which consists of a layer

carrier, a light-sensitive slide layer and a slip protection

_s , _w , _t " _t5,. 909887/13 59

BAD ORIULNAL ^C0PY

According to FIG. 1, the photographic film used as a template md the image-receiving diazo film inserted into the device in such a way that If you first bring the two films into intimate contact, then Threading it in without slip and leading it around the rotating drum and under permanent, firm contact with a suitable radiation source, e.g. in a high-pressure mercury vapor lamp with a normal output of 100 watts / cm, exposes. After exposure has taken place, the two films are separated from one another and the diazo film is treated with moist for the purpose of image development , iMionia vapor. Obviously, the invention is also applicable to copier machines applicable where the light from the outside hits the silver halide-containing Original hits.

The copying process carried out in this way is now invented improved by the fact that one with a photocopier with translucent Rotary drum and internal light source improves the assembly, threading and transport of the two films. Evidently The new type of film material is also suitable for copiers with a fixed light passage surface in the form in a transparent plate and fixed or movable light source.

A film according to the invention has a diazo layer as polymer substance, generally composed of · a cellulose ester, such as ellulose acetate, cellulose acetate butyrate or cellulose acetate propionate, exists, but also a cellulose ether, such as ethyl cellulose, an acrylic ester, ie polymethyl methacrylate, a vinyl acetate, e.g. polyvinyl acetate, or generated cellulose, e.g. saponified cellulose acetate, or one of these substances. This Polymerkompenteri the iazoochicht can either be the continuation of the carrier film, whereby then sometimes speaks of a strapless film, or of one flexible, plastic film made of polyester, polystyrene or polycarbonate > jie it e.g. the company General Electric Co. under the protected

909887 / 13S9

^C0PY BAD ORIGINAL ■. "- 5 -

Viarenname "Lexan" brings into the trade) are carried.

The invention can also be carried out in such a way that i
the emulsion side of the photographic film is covered with the anti-slip layer for the purpose of improving contact with the diazo film before copying. Obviously, only flexible photo and diazo films come into consideration for carrying out the invention.

The thickness of the diazo layer can be varied to a large extent. It can be between about 3 and about 30 u and preferably between 5 and 23 u. In contrast, the thickness of the anti-slip layer is extremely small and does not make up more than about 0.1 % of the total weight of a 0.19 mm thick cellulose triacetate film.

The anti-slip film-forming agent can be used in

apply two ways. Either they are applied in a separate operation as a top layer to the previously prepared diazo film, or they are applied in situ, i.e. they are added to the dlazo mixture in one operation using a suitable solvent. The second method is the cheaper and therefore ¹ ^ u prefer. In both cases, the ruts on securing film remains in the released state on the diazo cliioht surface and contains only negligibly small amounts of the constituents of the light-sensitive layer.

From the variety of diazonium compounds are suitable for example, the following are used to copy slides:

4-N-methyl-N-hydroxyethylainino-benzo Id iazonium-ohlo-rid, ■ lN, N-diethylamino-2-ii] ethylbenzoldiazoniani-chloride _f 'lN - /', thyl-N-ben ^ ylaiUlno-b £; nzoldiazoniuiii-chlorld,

° '4-11, U -Bis- (/ $ -hydroxy-ethyl) -amino benzo Id ia "ionium- chlorid,

^ ^ -N-Pyrrolidino - ^ - methyl-benzoldiazonium-chloride,

^ 4-N-Mo rpholino-benzenediazonium chloride, t *> ^ -N (2,6-Dl ₁ iiethyl-morpholino) ben2oldiazonium chloride, cn

^ -N-Pyrrnlidino-benzene diazonium chloride, ^ -W-Piperioino-benzene diazonium chloride

- 6 - ORIGINAL BATHROOM

-O-

and preferably -.

4-N, ND i ät hy la.iiino-ben ^ o ld iazonium ^chloride:

4-N -? \ Thyl-hydrOxyäthylaniino-benzoldiazoniuni-chloride and 4-NI »io rpho lino -c. , 5-diethoxy benzo Id iazonium chloride. For example, they are suitable for the many couplers used for 3ildontal development

4-methyl resorcinol,
2,3-naphthalenediol,

* Acetoacetanilide,

aacet
AcefUo-toluidid,

Phloi-oglucin,

5-methyl-1-phenyl-5-pyrazS.lon,

l-naphthol-3-sulfonamide
and preferably

Resorcinol,

2,2 ', 4,4'-tetrahydroxy-diphenyl sulfide, 2-hydroxy-2'-kiethyl-3-naphthanilide and 2-hydroxy-2'-methoxy-3-naphthanilide.

The photosensitive layer can furthermore also contain the usual ones Contain stabilizers which act as coupling inhibitors and prevent premature reaction between the diazo salt and the coupler. · You are more acidic Nature and consist of inorganic, aliphatic or aromatic acids or acidic salts, e.g. citric, tartaric or sulfos'alicylic acid.

When selecting the individual approach components

you of course pay attention to compatibility with the anti-slip agent. When it is introduced in situ, compatibility is shown by the clarity of the light-sensitive batch or mixture. compatibility The light-sensitive layer can be determined by examining the diazo

-) Other, equally suitable diazo compounds are too numerous, to be enumerated. . '·

copy MD orkmial 909887/1359 -T-

layer to determine clarity. · The film must not be reddened or cloudy still have a veil. .

So that an anti-slip device can be used as a

If contact copiers prove to be suitable, the following tests must be passed:

It must be resistant to damp ammonia, so it must not • are softened in such a way that it sticks and comes off during the development process , and / or otherwise spoiled. In addition, the Ruts must chsichei'ungsschiclit Enough ammonia vapor permeable to allow one of the exposure times when copying to ensure that the development time is adjusted can be achieved through modifiers if necessary.

Furthermore, the anti-slip film must adhere so firmly to the diazo layer that it will stick during normal processing and storage does not detach from it. This adhesive strength is established with the help of the usual Klcbbandtestes firmly.

There is no satisfactory laboratory method for determining whether a potential film former is slipping or non-slipping when used in conjunction with a photographic film in a rotary drum contact copier, nor is there any obvious explanation for the slip or loss of contact. Occurrence. The usual tests, for example the friction test on an inclined surface, are not related to the results that are actually obtained in the copier. This lack of correspondence between the results of the inclined surface test and those found on the copier is surprising, since some compounds which appear useful according to the first test are completely useless in practice. For example, a top layer of colloidal silica on the diazouuhijht gives its high coefficient of friction in the bevel surface test, but contrary to all expectations, it causes an increase rather than a decrease in slipping in the rotary drum copier, so that the advertising quotationC hcM - »- a.LS if the control layer is free of

909867/1359 _οοργ _ ₃ _

BATH ORIGINAL

is.

Because of the impossibility of obtaining evaluable results by means of conventional tests, various compounds were statistically determined on the basis of their evaluation factors in a commercially available rotary electronic contact copier of the Technifax Hi-R type, as described by Tecnifax Inc. under this protected J,:] siiua.iien offered in trade wi "» "d and is shown in FIG. jr-ivei one found preferred connections, which for all practical purposes worked on properly operated rotary drum copiers of the usual j'auart iCOpi without any rejects. Anti-slip bindings oind abui 'also then not acceptable if they have a double shot factor untoj 5 / _ or in the sense of the invention identification abbreviated the AuoC jhur ^ factor 5. The Ur factor should preferably not be greater than l (l '/ _) , which is still too high even in certain cases.

The reject factor is set with the above

'.opierGC- ^ ät ge.iiäs.'"; Fig. 1. Adjust the conveyor belt to a constant and optimal tension, send the non-slip film containing a non-slip oil together with a photographic, image- Fil,.! With HalogencilLergelatineschicht the variety Kodak AHU lit- -about 2.5 to 7.5: n / .. iin speed through the machine, jie FiliJie are each ^ C ..i long and 105 πμ wide, and for each Ausvjertung egg-Cen three such l) ia: - ofilnie with the same measuring image original copies; nd field for Bildicle on measuring image resolution sharpness investigated _J v ei bad Eilder per frame are considered barely acceptable - :: 'a bad image.. viewed as tolerable. Double images always extend beyond a field of view.

With the help of this evaluation method turned out to be

-ac- preferred slip protection means with the reject factor O, i.e. • "a ;; v, iüch no measuring diaphragm when the device is running properly 'iir-licenublorid-Acrvlni-ril-Ccpolyrfier with preferably 80:20 Monorner-

COPY BADORiGlNAL .- 5 -

relationship.

To modify the film material with this copolymer, ι
the latter is added to the diazo batch components in the appropriate amount and everything is dissolved in a suitable solvent. The proportion of copolymer is, based on total non-volatile solids in the diazo mixture, between about 10 and more than 100; and, based on the weight of the solution, between about 0.5 and about 5 Γ '»where viscosity points make 1.5 fn appear practical. If other anti-slip components are used as a film-forming agent in addition to the above-mentioned copolymer, Ie cc te res - based on the weight of the solution, can be reduced to 0.2> 1. If the anti-slip cover film is applied in a second discharge clu-irt, there must be only 50 £ of the addition that? oci V.:i-vjendung of the same 's in situ angowond- ^ b .-; ird.

As Z ¹ IoCt -JU di, .i vor, jälinten jc-lyvin./lidt.'ichlürideiy,nin are polyvinylculoride bonds, 2.B. '^ hears, polyvinylpyrL \ jlidin, .i.ü because of yes and no- ~ r

'Jvii'jLlao.'. IgiL-it under- ^^ wioöen Um ^ x, Lind an even: ia.l-in v: - .vciic: -, j; rden kaiia, so.ji3 ano .'-.- : ll'i.-j ^ t, v ^ n den ^: sn marx only üoviil ν.- ν-; . "-.- Uw - υ, dadö dk- Hu; ö2L i ι ^ ίγ! • ■ n ^^ '- i ^ cruakeiften des Hrupt-

Mn strength C - P-Iy-SCE, for example, the above erwälinte from vinyl ■

century!. j 'it .. u.'jü'-'iiv Lncetac, k "nncn _ilo oolo-.ie- ver-vjende" will be, provided you have oil · - ^., i ", j-ei, - .. Ii vr c.!, "'sungs TiItOiLiVoCe-Ie .jö«, ··' ioer ^ agslosurigen adapts unn di.r · 'iV .j- ^<T iii.r e FiI .lüchicht c1: .a oax ^ en requirements.

L'i ^ nticriotenundsn I-x-ispielüfcn the invention

.l.Cji; jlich "u?, .. Vx ^ l i αία special-D gunii ^ ig bet ^ aahtetei 'execution -.,".;-;.!. i: i] -: - ii, -; r ei-l; iur, ecii nvicJ kcli ^ if necessary narrow their ochut 'circumference.

ße isn le] _ 1.
,, a, L ·.: ,,. 9 0 9 8 8 7/1359 BAD ORIGINAL

COPY

- 10 -

- 1υ -

Polyvinylidene chloride-acrylic-acrylic copolyir.er

Sulfosalicyloic acid 500 g

2,2 ', 4, -4 ·· -T ^ trahydroxy-diphenyisulfia ", 00 _fe ;

Zinc chloride. 500 g

Thiourea 50µ "g

2-Hydroxy -? '- methyl-3-naphthanilide 900 g

4-N-ethyl-N- (2-hydroxyethyl) -amino ben-aoldia.ioniurachlorid as zinc chloride sala 500 g

4-N, N-diet hy lamino benzo ldiazoniu.ii -chloride

as zinc chloride salt 600 g

in acetone '65 liter

Methanol 15 liters

and carries the freshly prepared solution with the help of conventional meniscus application methods on a 0.19 - ^ n strong cellulose triacetate: on.

Example 2
One solves

Polyvinylidene chloride-aeryl nitrile copolymer citric acid zinc chloride 2,2 * , 4,4'-tetrahydroxy-diphenyl sulfide thiourea 2-hydroxy-2 ^! -rnefchyl-3-naphthalitide

4-N-ethyl-N- (2-hydroxyethyl) -amino-benzenediazoniuin-hexafluorophosphate 500 g

^ -NiN-diethylaminobenzoldiasoniuir-oalorid

as zinc chloride salt2 600 g

Q in acetone '' 85 liters

oo methanol 15 liters

-J on and carries the freshly prepared solution jiit the usual help · "- ^ Meniscus application process on a carrier that consists of a composite

J ₇₁ "aiAS one

^ slide / 0.01 times strong gelluiosis acetate batyrate and a '0.12? ηΐ, η

strong Pclyesterschioht consists. «^ P qRIOINAL _;

1500 G 500 G 500 G 700 G 500 G 900 O*
O

Man l'jst

Folyvinylidcnchloriä-f -ryliiitr-ilpoly.ner ΙΟϋΟ g

Polyvinyl chloride pol ;; vii ^ vlacetpr, copolymer 500 _t ;

Sulfosalycilic acid 500 g

Zinc chloride 500 ^

^m hioharns off. 500 3

2-hydro ;; y-2 ^! -.iieTiiyl - ^ - naphthaniJ id 900 g

luil-'tthy 1-L ^T - (^ -hydroxy t liyl) -ü.d

diazoniu.n -. ^ hlorid as Zini :. jnloridsal ^ ^ 00 g

4-II, lI-I) iäi h-'la: iin-> ben , ■: 161- :. onivi ri-chloi'ic

as Zln & .i \ I>) idc ^ .J-, 600 3

in methanol 15 Licar

on and z: - '. l. ^ ni: _' ·· χοοη .υ ι -rite te L: sun, 5 .iiit Hilfe üblijiiS "Men it Im f

aul '^ racsvcr'. 'ears on a' -, 1 ¹ ^ -nii strong collulose triacetate fil. ι on

3 ippivl 4
One steep-: u: iä.iJx.3t a L'Jo c ..: from

Lemons..; Whore lUOO g

Prong!: Io; id '1000 g

2,2 ', -, -i ¹ -Tatrah-dt-riy-niphenyl sulfide 700 g

- ^i- Hydro :: y-2 '- .. iethyl-5 -..-. T luhanilide .300 g

Ut

as zinc chloride: 50 g

in methanol 67 liter

η- ^ UtaiW 3 Lite-i-

Acetone 20 liters

Methyl ethyl ketone in liters

here and wear them freshly juberoi ^ eta:, ·. Z ^- ic ■; and ... it Hilie usual

ftcni £ kusauf ~ rv; .iv?: u'ahren on a "^ -. Oanifil .i from a · 0.01 ..".,. strong cellulose a ^ etatbutyrat-- ur.c a ^: r 0.127 .ii.n strong polyester layer on.

üaehoeji this approach aufgerr-a ^ er, uno dried, lot,

90 98 87/1359,

OK ORIGINAL

jird he again by means of meniscus application with a solution of 750 g poly. / inylidene chloride-acrylonitrile copolymer coated in 100 liters of acetone. ) The thus formed copolymer top layer adheres after drying out as : larfilm on the top of the diazo layer.

Example 5
lan first presents a solution for

Sulfosacylic acid 500 g

Zinc chloride 1000 g

2,2 ', 4 _f J <' - tetrahydroxy-diphenyl sulfide 700 g

2-Hydroxy-2'-methyl-2-naphthanilide 900 g

4-Ν-Λ * thyUI- (2-hydroxy ethyl) -aminobenzene-

diazonium hexafluorophosphate 500 g

^ -Ν, Ν-diethylaminobenzene diazonium chloride

as zinc chloride salζ. 600 g _t

In acetone 80 liters

Methanol - 20 liters j

ier and wears them freshly prepared by means of the usual leniskus application process on a 0.19 mm thick cellulose acetate film c / In this layer, after drying out, a mixture is applied Polyvinylidene chloride latex. 20 liters

Water 80 liters

Isopropane 5 liters

on. The Poijrm'erde'ckBohicht formed in this way adheres after drying out

t; as a clear film on the difezoechichtobferseite. y £

On these films produced according to Examples 1 to 5 '- "" -. ■ ^ URDT nit de Help "above Technlfax copying machine photographic \ .. ·"'{• lessbildpoBitive aufkopiert to give copies with a Ausßchussfaktor · j inter 5. In accordance with Example 1 Films made entirely delivered'

Double-image free copies with an extension factor of 0, i.e. the loss of resolution ag between measurement image 7.9 and 7 # 1 according to measurement on an 18-fold : Cleaned Mot'm-liDS resolution measurement image.

90988771359

BATH ORIGINAL- ^{J 5} "

■. ._ COPY

Claims (8)

Pat B-η t 1) Non-slip azographic pilm product made from a light-sensitive, image-forming diazo layer and a support for them, the layer made of a cellulose ester or ether, acrylic ester, • Vinyl acetate, regenerated cellulose or mixtures of these substances and their light-sensitive, imaging substance - from a diazo salt, an associated coupler producing the visible image and a stabilizing compound consists / characterized in that it has a cover film bonded to the layer which is in contact with the gelatin layer of a halide silver photographic emulsion film shows a slip resistance, which is defined as a reject factor below 5. 2) Product according to claim 1, characterized in that the layer support from a cellulose ester or ether or acrylic ester or a mixture of these substances. 3) Product according to claim 1, characterized in that the layer support made of paper, metal foil, cloth or flexible plastic Film exists. 4) Product according to one of the preceding claims, characterized in that that the cover film is made of a vinylidene chloride polymer consists. 5) Product according to one of the preceding claims, characterized in that ■ jt.iuhnet, datja der- Dcckfilin from a vinylidene chloride-acrylonitrile- oopoly,., he insists. 9 0 9 8 8 7/1359 COPY
BAD ORDINAL _ U. - IH - 6) Product according to claim 5 »characterized in that the _; Cover filiii 10 to 100 wt .- ^ of the non-essential portion of the photosensitive approach. 7) ^ r'aeugnis according to one of the preceding claims, characterized in that dasfi the layer of cellulose acetate'outyrate and the The substrate consists of polyethylene terephthalate film inside. 8) Aaeographic process of reproduction and use of a product according to one of the various ^claims: n claims in which ciino transparent picture template with an a ^ ographic VJieder-gabefil..i brought into contact and the so in contact materials in non-sliding relationship around the beginning of a circumferential zone led around, a radiation source that activates the diazo reaction and then separated from each other again, characterized in that the two materials are in non-sliding relationship that prevents slipping, maintains contact, on at least one surface of Original image or display film is located and made of a vinylidene chloride polymer received '. BATH ORIGINAL 909887/1359 L «erceite