DE2417278A1 - ERASABLE SHEETS - Google Patents

Description

Andrews Paper & Chemical Co. Inc., Port Washington NY, USA

Erasable Blattraterii ?!

The invention relates to an erasable sheet material, namely printing and especially oiazo material.

The blueprint process, also called diazotype "is a &■> - piercing process in which a translucent original is laid on zin diaso-copier paper, this is illuminated with ultraviolet light and then ammonia drips or © inera i'lüseigen draft:". Icler is exposed. Due to its simplicity and cost-effectiveness, the blueprint method has found widespread use over the last *> 0 years.

Dlazo copy material is produced in that a light- sensitive diazo coating on the surface of an SS base material, For example, a slide, a transparent one or opaque paper or fabric. The active components of the photosensitive layer are mono.ioiskulaFj crystalline, not self-supporting and need c-in foiled or aqueous substance alti carrier material,

If Pr.nJör is used as Qr-undrcmaterial _s bo the diaso-layering goes into the top layer of the breading and distributes: jich in it, and the color lines in the finished copy. are ii; a? r paser structure. of the paper nehv well vcrankor'c. bie.htp>'. i3kopisn of construction drawings are h

403845/0984

BATH ORIGINAL

Advancements used _s and it is erwüru-isht, Daae corrections of color lines can easily be made without daö deep incision in TFAS Pawlar necessary are ^wele. "I it for other markers over-chädicen impose" corrections have been using chsrisl3ehen-erasing solution no. '? - n; which destroy the color lan aurei reduction or oxidation of the printing ink. However Soleis chemicals also draw the paper to a certain Gi ads to ³ and leave a curled decolorized and stain that occurs during re-copying as an undesirable mark. Corrections to Liehtpaus & n are often needed in ZvieLtovigi.Yuilcti , al3O Lichtpauawatsrial with a thin or transparent support, and the color lines consist of one or more colors, which for ultraviolet light! ■; are impermeable.

It obviously ^ that a great need for mechanically erasable Diaac-Transpai ^j sntpav.sen is that no chemical Erasers require "I3T to DurcJiführung of corrections of the Parblinien, 3ondern where corrections can be carried out mechanically by means of a pencil eraser, the surface of the ohns Basic materialB is attacked.

As previously explained, this can * n .cht me the usual D Beschicatung'sverfahren reached v;? Ground, b ^ i which the bring the color lines forming components in the upper fasexfSrmigcn layers of the base paper. A known method of generating r-adierbax-ei *! 'Iako marks on paper is ₃ to coat the first with a film-forming cellulose Grundmatsrial ^ Vcerlösung in an organic solvent, and finally v-.ac'n ^ nce ^ mi of an organic i: .Qsun £ i './ 5: it1; ellSeimg fier Γ-iiisc-V * ^ blna'ms clt od? r v ^ a: * Harze su bes ^ ii-ichtan. D5.a selection &; hv.j / zo and clsr solutionc-

4093 45/0964

BATH ORIGINAL

medium is critical as it is necessary that the top Layer in the celluloeeeetariilia are rings without going into the penetrate the lower layer and resorbed by this eu will. In addition, the surface should be sufficiently hard and not during the passage through the copier smear or scratch. This process is very critical and it is also very expensive because of the coating systems with organic solvents that are necessary and dio su a contamination problem for the environment will know.

A general phenomenon of Diaao-Transparent copies iet the tendency of the developed printing inks with time in the deeper layers of Papiereabstrates _s hinelnauwandern since the Papieraubstrat a certain degree of solubility for the azo dyes of the color lines has. As a result, earlier attempts to use separating layer ««! Watching for erasable blueprints, not to be successful, because these rests could be erased immediately after they were made, but after a few days or weeks the azo color waned into the deeper layers, so that only partial etching was possible, with the deeper one penetrated part of the printing ink remained visible as a phantom effect * Some resins, which were used as intermediate layers, even dissolve the aco color after a certain time and accelerate and intensify the penetration of the azo color into the paper substrate, so they cause a stronger phantom effect when erasing than if they were no intermediate layer would be used. The reason for this effect has not been fully clarified, but it is assumed that such intermediate resin layers εν. Extract certain components from the paper substrate, which show solubility for the asophytes.

Another disadvantage of previous attempts at creation; easily erasable Dlazo-Kcpian var die missing

persistence. Easier erasability was achieved by manehisaX, with humidification and even low mechanical stress however, the whole shift came off with everyone Color markings. The resistance to rubbing in a damp place So the condition was not sufficient.

The invention is the basis of the task, the difficulties and avoid disadvantages of the known materials and * an improved, mechanically easily erased'b & .rea sheet material, in particular, Dissc-Materlal eu create which Canoeing can be produced economically and not necessarily requires the use of volatile organic solvents which can cause security problems.

It was found that

Harse either from aqueous dispersions or sus Solvent solutions very easily produce a continuous one. on a substrate and, when viewed with a slide, substances are withdrawn, an effective barrier against ο as intrusion öer Diasso-Beatandteile and Azofai'ben of manufacture Make copies in the substrate. Their adhesion type to the substrate and the upper part is sufficient for one satellite probe Resistance to rubbing when wet and when other mechanical stress during the copying process », however, the layers can be physically easily removed by means of a common eraser or the like without damage of the substrate can be removed.

The coating of a transparent substrate can be performed with a one Acrylatvinylehloridcopolywerisat containing Bq schichkungSBittel. This then wi.rd dried with an brown lines erzeug & ncLer ^{"Zwi.-.?.hen:} oesehichtung avs DiRsoniateri ^ X ^ s übsrso and wi.ed ,? ^ s'yvoih-ict. This Diaso-Topierißaäfriel we *} -5asu vcvven -: '£ t, sir- Di »f; c · -

409845/0964

BAD ORiGiNAL

Making a copy by bringing it into contact with a translucent original, exposing it to ultraviolet light and exposing it to aaunonia smoke. A copy is obtained which has deep brown lines on a translucent background. The colored lines are easily removed by mechanical rubbing using an eraser guöimi yr & r & em without damaging the translucent substrate. With a material which is identical to that described above, with the exception that the first coating with vinyl chloride-acrylate copolymer was omitted, a copy was obtained from which the colored lines can only be removed mechanically with simultaneous destruction of the transparent substrate.

The vinyl chloride acrylate polymers with fewer acrylic components will be riding; Dioetyl phthalate or phosphate whitening mashers swecks formation of a film externally plasticized. Vinyl chloride-acrylate copolymers wit a large number of Acjpylbeotandteile are internally plasticized due to of the copolymer composition and do not require any Sweeter plasticization. Both types of fabrics are for the Purpose according to the invention can be used.

Although the yinyl chloride-acrylate copolymer resin alone uses all of the interlayers; may be, it is desirable _t other components of the intermediate coating involvement just as V / axis, pigments, flow-promoting and schaumverhOtande reagents to the Orad the Adhäoion, de. · * Kohäsiun ₉ DAR Rcdierfähigkeit and the capacity for Außenachici.t assemble.

Obiü.e - .. ch the main piece of experience creating eir.03 w. '+ I:' ^: i0 \ - isch easily rac f.ar "jf.i-ei'i diszo-copy-i'reuterials -st , be J'-T-fei, go?;,. "nasty, öuä die K-fir.dun. ^ also : 'Ur z.nd * ■> - Frc lukte,

BATH ORIGINAL

as parchments, writing _paper's printing paper and other Dru; ';: - materials used _s itt where corrections erfordei-borrowed are.

The substrate for the finishes ₅ easily erasable diazo materials can correspond to the usual substrates for blueprints such as transparent, oacundur-correct paper, gsmels, foils, tfiliRe and Metal. In the case of metal substrates Imoe bestiranten films, such as polyester-based, t ~ .s.nn not take place penetration dsr Diaaio-Baaehichtung in dae substrate, but is a erfindunga £, ersäß-s Zwiseheanehichä trotsösrc useful because the Gred usr adhesion of rilmbilÄc ·· ^ η Beschichtungsn ait dan Diaso-Koiponenten stsusri uun de? : ". ΐ influences the redaction ability. Ra's preferred substrate £ * ■ & the invented material is ?: however you ?? chsichti?: - ·. ;; or paper made transparent.

The application of the intermediate layer of vinyl chloride -Aeryln ¹ II "Copolynarisat on a usable substrate can be done with the feather of the usual Beschlehtungsr * n, depending on the amount * before the coating material is applied. An orphan application machine with An air knife or wiping device is useful when the vinyl chloride-acrylate copolymer is used in aqueous solution. Roller application screens or counter-roller viewing devices can also be used. Diaao or blueprint inspection machines, which are equipped with job inspection devices, are very useful for the application of the intermediate layer, as they are also used for the subsequent coating of the; Diaso shields can be used. The damp layers that are cracked open in a sneeze-out dry very quickly, but they naturally open up

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BATH

Krat sensitive and care must be taken that the Coating as it dries and until it is coated is not scratched with the diazo coatings.

It should be noted that the intermediate layer au3 Vinyl chloride-acrylic copolymer with so many layers ·.! can be overseen as it is for the specific application necessary is. More is possible for slide paper a primer layer can be provided.

In the drawing you can see some examples of ®r ~ inventive materials, for example dargoste.'11-c. Eb shows:

1 shows a slide copy material according to the invention with one-sided copying view

Fig. 2 shows a erfindungsgeiaäßes material, the substrate on coated on both sides}

Fig. 3 shows a material whose substrate is only on one string and Only with two layers, without a light-sensitive one Diaso-Schicht, is coated; and

4 shows a material similar to FIG Apply two layers to the substrate on each side is.

In the setup according to FIG. 1, there is a blueprint 10 inclined * at the fully developed characters 12 and lines are present in the developed diazo layer 16. A Substrate 16 made of any material that can be used for blueprints ! '«Is placed on the surface with an intermediate layer 20 coated. The intermediate layer 20: dissolves in the form of an aqueous dispersion or emulsion of a ^ 'iny Aeryl & t-Copolytnerisats applied, and they can other ingredients contain, among other things, the properties <Sei »SwIs ^ hensehi Modify 20 su.

4098A5 / 096A

Between the intermediate layer 20 and the diazo lens 16 a primer layer 22 is provided * that of ier Interlayer 20 is wegradiarb & r if any of the in the * diazo layer 20 formed characters or lines vr & graded must be, and awa? without destroying the intermediate layer 20 or the surface of the substrate 12. The foundation layer occurs 22 can one of the Zusaaanfcnaetevingen have-v which applies to primers for Diaso materials V5 »rtfsnäst tr & i-ivn.

A coating 2- ¹ I on the back of the substrate II is provided in order to prevent the coated substrate from curling up after drying.

In Pig. 1 watching 26 has been established. As a result, a depression 28 was created, which extends through the diazo layer 16 and into the greening layer 22, while the intermediate layer 20 has remained unaffected. It should be pointed out that in practice the DiuEo layer 16 and the primer layer 22 are so well connected to one another that no abrasion or flaking can occur. Wis Pi ^ r. 3. The color forming the characters 12 and the lines 14 tends to extend into the primer layer 22. There is also a sufficient bond between the substrate 18 and the intermediate layer 20 to prevent wicking in the wet state during manufacture and also during the process Re-Kcpieren », after which a new symbol was added instead of the ftvjradiej. · - th symbol 26, eu prevent. Since the color, as said, cannot penetrate the layer of the substrate, no "phantom" effect can occur after erasing, as would be the case if there were no intermediate layer 20.

In Fig. 2 iöt «ine Fiichtpsue ^ i?" Derget -Share., At v dt * Ofcerseive iles Sub jt? At? -> 7.! G ^r like bc * *. Άον * '-Oi'-h ?; ·

A09845 / 096A

BAD ORiGiNAL.

Example is provided with an intermediate layer 20 ', a primer layer 22' and a Dia-zo layer 16 '. Instead of the back coating 24, however, the same coatings as is provided on the front, that is an intermediate layer 20 '·, a primer layer 2 £ ^{Esch and one diazo layer 16'. This material can therefore be used for two-sided copies.

In Pig, 3 iet a. erasable «» s sheet material shown, which as drawing paper, as transparency oöe? as typewriter paper yervrendafc can turn. A substrate 18 " _f, for example, made of transparent paper or letter or bank note paper which can be used as a scrapbook or typewriter paper, is seen on one of its" sides with an intermediate layer 20 ", which in its composition is a layer i: 0 of Fig. 1 or the layer 20 'of Fig. 2. After drying, the greening layer 22 ", which has the same finish as the priming layer 22 or 22 'by Pig. .. I or 2 applied over the intermediate layer 20 "The material of 'Pig 3 takes pencil and ic * .fce well and can easily sebx ·;? Oricittel contact etched with a mechanical-Hadi _s ohrudaß Cuss substrate is damaged.

In the case of Ct-sa embodiment example, Fig. K is the bt-layered sheet of fig. 5 also a-.if aeinsi: other. Side coated with the same layers as in Fig. 3 'it consists alao of € i! .Ii "em substrate 18'" and intermediate layers 20 * "and foundation; s layer on 22" r-. On each side d

In the following wex- (J «i? Agree? Examples of the preparation of the

^. ". ^ n given.

A098A5 / 0964

BATH ORIGINAL

example

A lOOJS of rag paper with 50 g / qai basic weight is put through Treatment alt a reaction product of a 'polyol derivative ait a poly-H-methylol derivative of a polyamino compound treated, whereby a highly transparent paper with a basis weight of 58 g / m. This transparent paper is made in a single pass on a blueprint paper reporting process that includes Order orphans and Abstreifmesserη provided iat, coated and dried in a hot air convection dryer The following coating formulations were used:

1. Intermediate weighting:

Water,

non-colloidal silica, anti-foaming agents, a 55% aqueous dispersion of vinyl chloride-acrylate copolymer, which is externally plasticized, and 5 grams of methyl violet

Kaeh coating and drying, the Papiev aufgeuicksl ": and a Diato-Beschiehtungsaiaechine sugefOhrt, άίζ- with drni conventional Schlitsdaeen-Auftragestationen for <5ie Gi ^ un ^ - dierungabecchichtung, the diazo B & coating and the rear. Ite coating and provided with high-speed heating air con -. Wection drying in each coating station. In dieetr Mtechin · the paper is continuously coated

15th , 000 ml 300 G - 35 G 15th , 000 al

t «t: and dried, in such a way that the primer is applied

the Diaeo coating is applied to the side _; ? li »leli«! the. Interlayer aue vinyl chloride-acrylate-CopolyÄeri ^ -> at-KRra has received and then the back is coated and dried.

■■ ■ '' - ι ·; -

409845/0964

The paper provided with the intermediate layer was in the previously described manner with the following coating recipe · » treated:

2. Priming coating:

90,000 ml of water

300 ml of ammonia

8,000 g of non-colloidal silica,

1,000 g of polyvinyl alcohol

7.500 ml vinylase set & t-copolymers (50% aq

Dispersion)

1,500 ml Mineral-Waohs (50 # aqueous dispersion)

100 ml Schaia contraceptives, and

5,000 ml of QIyserin

. Diazo coating:

90,000 ml of water

3,000 g of tartaric acid

1 * 500 g boric acid

6,500 g of l-Dlaao-J-methyl-iJ-Iyrrolidint-jnso. "

2-000 g Tlilo & arneioff 1,000 % ^ -

500 g Alpha-2 ί, ΟΟΟ ml isops? Dpt.v-ol

1 * 500 g nic ^ ir. "KoXloldtile K 5 _: .000 ml FolVTiiiyliiAeitt * {50'ii.gc aqueous di-

- 512 -

409845 / 096A

BATH ORIGINAL

. Back coating;

90,000 ml 3,000 G 2,000 G 6,000 ml

water

urea

non-colloidal Kiaselm-de

Vinyl acetate copolymers (50% aqueous

Dispersion)

The finished paper is used there, a K το ?! a translucent original in uiner * he.; adeIsübli2i «-Mi Liehtpauemaschins hsr ^ wstelien, and it rlrd sine copy-relü deep brown lines ^ on a ciuPch & ehelneKrisn Ym'a sgrv.xA. The treated paper cl? Ji? EnXie? ÖIE Sn jifiJ-.lvir.r: "machine d <sa copier without; Difficult b & n XINC dia surface is not verachraierte The erfsalfcrr © looS.o can readily than Zveitori ^ inal fti :? äiö lUrt'sktllv... nz other copies used ^ ssrcitevi. Ee ha ·; e5.eh ί si'ti-. t ^ ct-i »i that the P & rblines aoittela of a P.adjlei'guroFiiB cdc? ^ of a Rc ·· dierrtasohine iconnten easily removed, ol:; ie C. that the transparent paper was damaged. Corrections can be carried out and copies of the critical copy were made, without PhantoEBs & jPkiarur.gen 5.id »n erased areas

B © i β ρ i;

A Di & zQ transparent copy paper t / ra-de in '5 equal -Yz. i ti as in example 1, but untus? Omission of car Zwia: heaschichfc. Eina Eonie with dieeeia Fap5.wP- _t -satt * de »gli.lchs Failed e: i like a copy with a? * Paper seraäS example!“ However-verXr'.ef dsr Eraser-fc © 3t negat.lv. 5cirblinien '.nnt-r _ä only n.it sizitsn h & i-fcen- Radii., -Giirard un ^ er ijr-hobHehe.i η net ^ εΛ-gi ^ p.gfcn wntft'-ii-nt wexäcä, where <? ie · O'-s-pfXüch ^ * 1s-s Ί :. urio. ^^ l. «? · Ri & lw büscl .diyfc wurli.

409845/0964 _.

BAD ORiöiNAL

example

A $ 100 rag paper with a weight of 53 g / m was with an AOSigen solution of styrene dimer in toluene impregnated and dried. Ea resulted in a translucent Paper with a Grunago weight of 60 g / m ^. This Paper was then treated in the same manner as in Examples 1 and 2 and tested for erasability A very similar result was achieved.

Example 4

An opaque Diaso-Fapier of chemically strongly reinam _s bleached kraft Sell fabric was coated successively with the following formulations and dried:

1. Diaphragm coating:

400 ml

* 100 mils of a 50-56% aqueous dispersion of

Vinyl chloride-acrylate copolymer with

inner softening

2. Foundation coating;

5 dl ammonia

20 g colloidal silica

80 g non-colloidal silica

100 ml vinyl acetate copolymer (5O3tige

Diepersicn)

Iu ml wax (5ΟΪ1ε <Β aqueous diapereion)

900 g tfasiior

-It- 4098A5 / 0964

3 »Diazo Beach Sight;

20 g citric acid
10 g of I-Diazo-H-Di

Zinc chloride double salt 20 g of 2j3-DihydroKy-K & phta2in-6-SulT

Sodium saia
30 grams of thiourea
30 g zinc chloride

^ O ml of polyvinyl acetate (SO ^ liquid dispersion) ₃ and 1 g of saponin

The diazo-coated sheet was used to make a Blueprint from a clear original in a commercially available one Cut out the blueprint machine. It was sin? Copy rait deep blue lines on a white background. The color lines could be drawn with an eraser without Damage to the paper can be easily erased.

example

Example 4 was repeated in all details with the exception of the application of the intermediate layer 1. The copy with an a such paper completely conformed in appearance the copy with the paper according to Example 4, but was again the eraser test negative. The parcel lines could be one Eraser GUHini or with an eraser not removed without breaking the paper.

Example

A 1001 rag paper with a ■ -rundge -? Ich-i of 50 g / a ² was made transparent by Behmd / .uns ni.t ols &&

A09845 / 0964 - 15 ~

Reaction product of a polyol derivative Eilt · a poly-N-methylol derivative of a polyamino compound, and it became a very transparent paper with a basis weight of 58 g / «2 was obtained. This transparent paper was made on both sides on a loading machine with a gluing unit and a web dryer with an intermediate layer using the following guidelines

3,000 al water

30 g non-colloidal silica 3 g antifoam,

550 ml polyvinyl acetate (50% aqueous solution) 1.300 ml of 55% aqueous dispersion of yinyl chloride-acrylate copolymer

After coating and drying, the paper was on both sides in the same coating machine nit a coating using the following coating ^ * coated recipe:

5,000 ml water 100 G finely ground quarsa nut with 5 ~ 10 microns Particle size 200 G casein 50 ml Ammonia ' 200 ml Glycerin

The paper coated and dried in this way accepts pencil and ink well and can be easily erased with a mechanical eraser without damaging the paper will.

- 16 409845/0964

2A1727R

Example 7

A writing paper made of cellulose with a basic weight of 75 g / τπ ² is coated on both sides in a coating machine with a Leiowerk and a web dryer, using a Baaehichtung recipe: ·? Οΐ · gender composition:

1,500 ml of water

JiO g non-colloio. & L3 silica

3 g anti-foaming agent 7f; 0 ml Polyvinylazeti.t (SC ^ ige aqueous dis 1,500 ml of a 55% aqueous dispersion of Vinyl chloride acrylate copolymer alt external tarpaulin. and 200 ml of glycerine

After coating and drying, the bahn «: u standard sheets for SchröibmaBChinenpapicr cut.

The coated paper surface absorbs: the color of the typewriter ribbon and the oil color of the carbon paper ?, well. The written symbols can easily be combined with a. Mechanical eraser away r "r" ien ohna, ru damage the paper.

Claims -

409845/0964

Claims (1)

Claims 1. Eraserfahip.es sheet material, characterized by a Substrate, which on at least one side at least has two layers, at least one of these Layers an intermediate layer, the vinyl chloride-acrylate copolymer contains. 2. sheet material according to claim 1, characterized in that that at least one of the other layers was diazo-sensitized Has components, 3. sheet material according to claim 1 or 2, characterized in that that the substrate is paper. H. Sheet material according to claim 1 or 2, characterized in that the substrate consists of a transparent sewn base material. 5, sheet material according to any one of claims 1 to 4, characterized characterized that the vinyl chloro-acrylate copolymer externally plasticizing fc isi. 6. Sheet material according to Anapx'-uch 2, characterized in that that between the intermediate layer au? Vinyl chloride-asrylate copolymer and the fliaEO-sensitized layer a Qr-undierungsachich-: t 'is seen. T. sheet material according to one or more of the preceding claims _3, characterized in that the substrate is on its reverse octait. 'iaachicliturg is provided. 409845/096 4 _4g Process for the production of erasable Piaso materials , characterized in that at least three layers are applied to at least one side of a substrate, of which at least one layer forms an intermediate layer containing vinyl chloride-acrylic copolymer and another Layer contains diazo components . - 9. The method according to claim S, characterized in that a priming layer is provided between the intermediate layer and the Diazc layer. 10. The method according to claim B., characterized in that the vinyl chloride-acrylate-C.TpolyjTierigat is externally plasticized. 409845/096 4