DE1220447B - Thermoplastic recording process - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

B 41m

German class: 15 k-7/05

Number:
File number:
Registration date:
Display day:

M45435VIb / 15k
May 27, 1960
July 7, 1966

The invention relates to a thermoplastic recording method with generation of a deformation in a polymer material, which in or over itself is a material which absorbs radiation energy having. The method is characterized in that this radiation energy-absorbing Material directs radiation energy only in such an amount that sufficient heat is generated in the material is to avoid a non-continuous deformation on the surface of the polymerization material to evoke.

Thermographic processes for copying originals with different image absorptivities for radiant energy on heat sensitive copy sheets are per se from U.S. Patents 2,740 896 and 2 699113 known. In the method of U.S. Patent 2,740,896 a visible change on the heat-sensitive copy sheet is caused by image-wise exposure causes. However, this is a change in color in the thermosensitive coating, which is located on the paper carrier film of the copy sheet, and not about a deformation of a polymer material, as it is done according to the invention. In the method of U.S. Patent 2,699,113 a polymer film is irradiated for so long and with such strength that the polymer film is perforated and a stencil is created.

According to the invention, the thermographic copying or recording process is also used in principle worked, d. H. for the production of copies or matrices, which are then used for production can serve further reproductions - is briefly exposed to intensive radiation. In contrast to the method of US Pat. No. 2,740,896, however, this is done according to the invention no conversion to a visibly different product or no melting of a fusible, waxy powder coating containing dye particles to form a flowable mass Appearance of a more intense color; and there are no openings or holes in an oriented, an ink-impermeable film was formed as in the U.S. patent process 2 699113 is the case. In the method according to the invention, there is a superficial deformation instead of a smooth, deformable polymer film without perforating the polymer film will, d. That is, a coherent uninterrupted film remains, which is only connected to the Surface has undergone changes in places (according to the picture). Surprisingly differ

Thermoplastic recording process

Applicant:

Minnesota Mining and Manufacturing Company, St. Paul, Minn. (V. St. A.)

Representative:

Dr.-Ing. H. Ruschke, patent attorney,

Berlin 33, Auguste-Viktoria-Str. 65

Named as inventor:

Emil William Grieshaber,

Township of White Bear, Minn .;

Donald John Newman, City of White Bear Lake, Minn. (V. St. A.)

Claimed priority:

V. St. ν. America dated May 28, 1959 (816 640),

dated March 21, 1960 (16 267) -

the deformed areas are not only visible from the unchanged, smooth surface parts, but they also have different, and indeed directly opposite, wetting properties.

In the process according to the invention, the surface suffers from certain polymer films or -bodies undergo significant changes in both physical and chemical properties. The thermoplastic record can be based on a predetermined pattern Polymer surfaces are made with a relatively low radiation energy absorption capacity, by these surfaces in the desired pattern with a material with a relatively high Radiant energy absorbers are covered or brought into contact with it, and then Radiant energy is directed to this absorbent material to such an extent that it generates heat as well as non-penetrating deformation of the covered or touched surface area is effected. If the polymer surface itself has a high radiation energy absorption capacity possesses, the thermoplastic recording can be carried out in a simple manner in such a way that that the polymer surface in the desired pattern, for. B. through the openings in a template with relatively low radiation absorption capacity, is irradiated directly.

609 588/266

3 4

The causes of the deformation have not been precisely applied to one or more of the first substances.

known, but there seems to be at least one upper part, and also shows a receiving or

surface disturbance to which a removal of copy sheet, which is made with one or more two-

or rearrangement of polymer material, th substances have been coated, which in contradistinction

whereas in thinner films a discarding of the first substance evidently became a color-producing one

of the deformed portion of the film are capable of being implemented inwards, and

pull on the opposite surface of the film Figs. 13-15, which follows Figs. 10-12. If the polymer to be deformed speak, explain the production of copies of a material in the form of a thin surface film on a graphic original with the aid of a receiving or a carrier sheet, is made by the deforming copier sheet, in which the color-generating umums of the surface area in the deformed areas of settlement participants have been impregnated,
completely removed, so that the carrier sheet in sol- In Fig. 1 of the drawing, the reference numeral denotes Chen areas. 25 a film or sheet of a preferably

The present invention is based on numerous transparent polymer material, which in Oberreich embodiments and for a number of 15 surface contact with a printed character 26 Uses explained, some of which is arranged in FIG shown in the drawings. In the drawings it is worn and with this carrier layer one is graced forms similar reference numerals for designating the same original 28. Compared to that rather parts in various embodiments carrier sheet 27 has the printed indicia 26 a used. 20 relatively high radiation absorption

Figs. 1 and 2 are fragmentary, strongly contrasted, ζ. B. for infrared rays, with an enlarged Cross-sections showing the execution of the relatively short irradiation of the structure Method proposed according to the invention for producing film and graphic original by means of a (not position of a transparent image in full size or <~ shown) strong radiant energy source that appears Explain the duplication matrix, which has been indicated to a 25 at 29, in the graphic Original match; phic signs 26 as a result of the absorption of

Fig. 3 illustrates a transparency or a radiation energy heat is generated. The irradiation

Diversity matrix of the in F i g. 2 type shown, on ment of the structure can, for. B. after a process

the deformed surface of which a coloring substance takes place, in which it is caused by a thermographic

has been applied, and also shows a copier is sent in which the structure

Corresponding recording or copying sheet on which the rays of a lamp with a 25.4 cm long

The positive image corresponding to the deformed surface is exposed to tungsten filament which is 0.95 cm from the

removed by contacting with the associated structure and placed in a reflector

Die has been transferred; is that the radiant energy in a narrow band

F i g. Fig. 4 illustrates a see-through image or wrapper approximately 0.65 cm wide and is aligned

Diverse aging matrix of the in F i g. 2, extends across the structure when the structure

whose exposed surface or base surface is moved past the lamp device. the

a coloring substance has been applied, and the lamp has a power consumption of 1350 watts

also shows a recording or copy sheet on which and a voltage of 280 volts, while the thread

one of the undeformed surface or the background 40 has a color temperature of 2750 ° Kelvin. The GE-

A negative image corresponding to the surface area is created by touching the lamp with a speed

with the associated die, moving it over at a rate of 3.2 to 11.4 cm per second

has been worn; · Can be changed.

FIGS. 5 and 6 correspond to FIGS. 1 and 2 and are carried out under the conditions just described

explain the formation of the deformed surfaces, at 45 a chemical and physical change in that

which is penetrated by a thin surface film and part of the film 25 that is with the printed characters

while a carrier film is in contact with such physical 26, this change in

and / or chemical properties is exposed, FIG. 2 as a rejection of what is in contact

which differ from those of the surface film under- the proportion and formation of an irregular or

divorce; 50 deformed surface 30 is shown, which, as

FIG. 7 is a transverse view corresponding to FIG. 3, which can be a depression. The graphic section, which the deformed sheet of Fig. 6 with an original28 is not adversely affected, substance applied to the deformed surface. The lowest thickness of the polymer film 25 without shows and in which also an associated receiving carrier sheet is in the order of magnitude of sheet is shown on which a positive image through 55 0.0013 cm, because thinner films bring partial or full contact with the deformed sheet continuously with the described irradiation treatment has been; displaced or removed on the heated surface

F i g. 8 and 9 correspond to FIGS. 1 and 2 and are, so that such perforated films for the

explain the execution of the inventive method proposed according to the invention for

proposed process in which a polymer 60 imaging are not suitable. Thinner poly

blatit, of which at least the surface is a memorized film, the z. B. a strength of about

have a relatively high absorptive capacity for beam 0.00064 cm, but can be used

energy, through a stencil, if it is on a suitable carrier sheet,

relatively low radiation absorption inherent z. B. made of parchment or another polymer

is irradiated; 65 satfilm.

10 to 12 explain the production of co- The radiation intensity and the period of time during

pien a graphic original with the help of a ver the structure in the execution of the invention

Diversity matrices, whose deformed surface is irradiated according to the method, are of this type

5 6

sized so that the deformed surface 30 resized with a source, e.g. B. infrared rays, are effected

and shape an accurate reproduction of the graphic den can.

Sign 26 is. The deformed area is from the to the polymers that are used in the execution of the

non-deformed surface of the film visibly different- method according to the invention satisfactorily

which can be turned and characterized by a high resolution, 5 include cellophane and syn-

when the best values for strength and exposure are thetic polymers such as cellulose acetate, poly-

time have been used. If you are using vinyl alcohol, polyesters, polyamines and polyolefins,

A certain combination of radiation intensity and specificity are certain examples of suitable polyesters

speed of the image to the lamp a perforated polyethylene terephthalate and the reaction product

tion of the film and poor resolution in the io of ethylene glycol and terephthalic and isophthalic

deformed surfaces is achieved, an optimal acidity in a ratio of 9 parts terephthalic

Irradiation of the structure can be achieved if acid and 1 part isophthalic acid. Suitable polyols

the speed of the structure compared to the fine are polystyrene, polyethylene, polyvinyl chloride

Lamp is increased. In devices that make up and mixed polymers of vinyl acetate and vinyl

to reduce the chloride generated by the lamp. Suitable substituted polyolefins are

th radiation intensity that z. B. by Verrin polychlorotrifluoroethylene and polyvinylidene chloride

like to be achieved by electrical recording and polymethyl methacrylate. Suitable polyamides

can, the optimal amount of radiation for that are polycaprolactam, a polyamide made from m-xylylene

Formations also set with the help of these means diamine and adipic acid and a polyamide made from hexa-

will. 20 methylenediamine and sebacic acid.

The deformed film is for use as With the exception of polyvinyl alcohol and cello

Projection transparency well suited. The proji- phan have the materials specified above in

ornamental light is scattered in the deformed surfaces, a film forms a smooth surface that

so that these areas on the projection screen are not as comfortable for powder and aqueous liquids

blackened areas with good contrast and good 25 absorption capacity, however, for oil-like materials

Resolution can be reproduced. Furthermore, if he is receptive. In the following examples

deformed film is illuminated from the edge, which some typical embodiments of the

the deformed surface is explained in relation to a modest method,
shining brightly lit on a dark background,

so that the deformed film is suitable for use as Example 1
illuminated sign is well suited. By im- A sheet or film of polystyrene, like the one in impregnating the deformed surface with fluorescent- F i g. The film 25 shown in FIG. 1 is covered with a radiative pigments which are activated by light, absorbing graphic indicia 66 or is the effectiveness of such indicia further brought into surface contact, which chemically increases. 35 is constant and by during irradiation

Surprisingly, the change in the temperatures generated does not go melted or Properties of the film surface in the deformed is discarded and the z. B. from a carrier sheet Area over a merely visible or optical 27, the z. B. can be made of paper, worn Change addition. By deforming the surface 30. A sheet of paper written on with a typewriter the film surface is such a strong change of 40 is z. B. a suitable graphic original. That chemical properties causes certain characters 26 can also be applied to the sheet 25 by on-films, which are normally hydrophobic, printed on or otherwise, e.g. B. with the help of deformed surface become hydrophilic, and that India printing ink is applied, with the agreed films that were previously made for the purpose of producing an irradiation by the method given above thin hydrophilic surface film, the radiation energy is pretreated, preferably by the graworden are absorbed on the deformed surface hydrophobic phic characters 26 and generate heat will. In the case of the last-mentioned execution, so that a non-penetrating deformation The form is evidently the thin hydrophilic upper surface of the polystyrene surface in contact with it Surface coating in the deformed surface is destroyed, so graphic characters are effected. After the bedass If the hydrophobic underlay film radiates in this area 50, the sign 26 is exposed from the sheet 25 or this phenomenon can also be removed by removing the carrier sheet 27 or Reversing the properties of the surface by brushing or washing it off, if in addition to the original hydrophobic state it has been applied directly. The deformed matron explained to the deformed area. area, which at 30 in FIG. 2 has been shown, under-

The 55 proposed according to the invention is visually different from the subsurface surface,

The film or sheet used in the process is so that the polystyrene sheet or film can be used for illuminating

preferably made of a deformable by heat, tete markings or signs are used

film-forming polymeric material. This can can. When wiping over the deformed surface

oriented or non-oriented and need not be with an aqueous colored material or one

necessarily be thermoplastic. The printing ink used here, e.g. B. an organic dye

Deten, thermally deformable films can be found in an aqueous solution of a soluble binder

Films are viewed in which the here described, such as polyvinyl alcohol, contains dissolved, this

physical and / or chemical changes, the material or the printing ink of the deformed

gen as a result of the absorption of radiant energy surface 30, as at 31 in FIG. 3 shown, recorded,

a radiation-absorbent material or 65 because the deformed surface is now hydrophilic and

can be effected within the film, which is easily moistened by aqueous materials,

preferably by a relatively short, while the base area is hydrophobic and

strong irradiation of the absorbent material is therefore not wettable. That after this

7 8

A modified polystyrene sheet can be used as a positive for a relatively short exposure of the Ge projection transparency or as a replica image from film and stencil with a strong transmission matrix. In FIG. 3, radiation source 29 becomes a non-penetrating receiving or copying sheet 33 after deformation of the exposed surface, as shown at 55, generating a positive image 34 shown by overlaying 5 in FIG. 9, causes. The deformed film 52 wear from the film 25, which can then be applied to the deformed z. B. as a reproduction stencil or as a surface carrying the printing ink 31, printing plate has been produced in the same way as the films 25. Ink transfer can be used either and 25a in Figs. The radiation energy-absorbing film that is captured by direct contact with the deformable film or by dissolving it in a curd can optionally be in the form of a surface solvent that is supplied from the receiving surface or a layer structure on a carrier while this is arranged with the sheet The deformed FUm with the same or different printing color is in opposed wetting properties or optic guidance. can see properties. If the upper-If the deformed polystyrene sheet 25, which in 15 sheet film is sufficiently thin and z. B. the one in F i g. 2 has been shown, not with an aqueous F i g. 5 to 7, the colored material can be wiped off, but the carrier sheet in the printing press can be brought into an area irradiated as a planographic printing film by the deformation, so that a printing inks 32 are obtained on an oil base-negative see-through sheet is that the layer of the hydrophobic base surface, but 20 image and the base surfaces of the template 53 is not doubled from the hydrophilic deformed surface when the carrier sheet is transparent.
taken that the aqueous applied when printing.
gene treatment solution absorbs. Example 4
Received negative prints that are shown in FIG. 4 has been shown. 10 to 12 shown sheet 40 are, in which a copy or receiving sheet 33 α 25 a polyester, for. B. made of polyethylene terephthalate, after receiving a negative image 34 a from a, as shown at 41, by irradiating in contact plate 25 a is shown, the on the surface with a graphic original in the same way printing ink 32 and an aqueous treatment solution as the in F i g. 1 shown film 25 deformed, whereupon 30 a carries in the deformed area. this sheet on the drum of a (not shown) “. . .. 30 duplicating device as a die with the example l deformed surface attached to the outside. The sheet (or while the drum is slowly rotating who plate) 35 shown in Figs. B. pyrocatechol cellulose acetate, one surface of which is directed against the matrix by vapors, which condense in the hydrophilically deformed surface 41, as shown in the case of a thin hydrophilic surface film 36 45, which is previously treated with sodium hydroxide solution for the purpose of generating. The template is then hydrolyzed in. The treated surface, in the presence of heat, which is indicated by the wavy arrows of the plate 35, is brought into contact with the surface of a graphic original 28 which has a sign 26 which is coated with a surface of a receiving radiation absorbing mark whereupon 40 sheet 42 rotated, which has a surface coating 43 the structure, for example by the action of rays from a metal soap, such as iron (III) stearate or from the lamp 29, is irradiated, the ray silver behenate, or from a metal salt such as iron lungsenergie from graphic sign 26 from (III) chloride or cobalt nitrate carries. The phenol is sorbed and the plate 35 is deformed. As described above and the metal ion reacts to form color, it appears that either the proportion of 45 of surface 44 of coating 43 that is to deform surface film 36, which is aligned with graphic th surface 41. The images 44 that are in contact after this marking 26 are deformed or broken up have a high degree of disturbance, so that the hydrophobic underlying film 35 dissolves and strengthens. By continuously condensing the heated surface, as at 37 in FIG. 6, phenolic vapors are exposed on or the heated surface film spinning die and conversion part is converted back to its original hydrophobic capable coated sheets 42 in time. When the plate 35 is placed in a stand in the copier, any planographic press can be used to produce the number of copies desired for printing. Oil-based paint 24 of the hydrophobic, if necessary, a receiving or copying sheet surface 37, but not of the hydrophilic surface 55, in which the metal soap or the surface of the film 36 is received, on which the (non-metal salt during the manufacture of the Paper adheres to the aqueous treatment solution shown, so that paper fibers have been incorporated, in which case when printing a positive image 38 on a copy or the impregnated receiving sheet, such as one on both receiving sheet 38, as in FIG. 7 shown, sides coated receiving sheet, images on both will be given. Can accommodate 60 pages, which when the treated die is acted separately on each side.

are independent of each other.

The in the F i g. 8 and 9 shown sheet 52 from _R. .

Polystyrene, which is a radiation energy absorbing example 5

Pigment, e.g., an infrared absorbing material, 65 In Figs. 13-15, a deformed poly-

like soot, is applied to a template 53 from a styrofoam die 46, which is the same as that shown in FIG. 2 shown

relatively little radiation-absorbing metal speaks, with an aqueous solution of acetaldehyde

placed, which has one or more openings 54. ammonia, e.g. B. by wiping or rolling

Claims (1)

9 10 zen, treated. The solution is contained by the hydroformed surfaces of the die, a philic deformed surface 47, as shown at 48, does not produce coloration. Although the polymer also leaves the hydrophobic surfaces or films as self-supporting and retained in the surface. The treated template is then shown in most cases to be practically homogeneous and brought into contact with a diazo copier sheet 49, 5 have been described, the inventive method can contain both a stabilized diazonium salt and the proposed method equally well with the aid of a coupler conversion participant. In the case of the layer structure of a carrier film, which must not be deformable due to the action of heat, and a polymer ammonia is decomposed and ammonia is released, which, as described here, is deformable, coupling the diazonium salt with the coupler - io be carried out. Although the component according to the invention effects the formation of a color in the method proposed above on the basis of the front surface area 49, which has been described for the deformed image side printing method, the generating surface 47, as at 50 in FIGS. 14 and it is also shown executed as a back side printing method 15 is properly arranged. When the die is made by e.g. For example, if the exposed printed pre-46 is placed on the drum of a duplicating surface (not shown) of a typewriter-written folder, any original can be irradiated while the desired number of copies are made of the polymer, in-film against the back surface kept therefrom which is incessantly during the rotation of the drum, so that such an embodiment also includes acetaldehyde ammonia solution and is within the scope of the invention in time. However, the front clearance treated copy sheets 49 of the 20 page printing processes are preferably fed to the apparatus while being used because thereby e.g. B. in the deformed contact of the matrices with the copy sheet heat film a superior resolution is achieved,
is fed. When performing the in the above If, in the embodiment described, examples of the inventive method Place of acetaldehyde ammonia ammonia water 25, in which for the purpose of producing a color-producing is used, the color-producing reaction may be lowing reaction heat may be required in the diazo paper even without the action of the heat required for the conversion also there- Heat can be caused by the speed delivered by that to the deformed surface the drum is possibly reduced in order to move the die together with the described Ma- a reasonable contact time of the treated material with an infrared rays absorbing material, Ensure die with the diazo paper. like soot, is deposited, whereupon the treated . . Die with a treated copy sheet in loading W hen play brought six emotion and the formation of a short rigid A deformed die such as that shown in FIG. 13 is exposed to radiation. With such a showed die 46, the required heat is generated by dusting with a 35 irradiation, powdery reducing agent which, upon oxidation, takes this heat in the deformed surfaces of the is colored, in the deformed area 47, as is concentrated at die. The color-producing 48, treated. The powder does not adhere to the non-settling so occurs without substantial heating of the deformed surfaces. Such a reduction- non-deformed parts of the die or of antionic agents is 2,6-diaminopyridine. A receiving 40 share the copy sheet with the deformed or copy sheet 49 which is not in contact with an oxidizing surface of the stencil. tel, like potassium persulfate, has been impregnated, becomes _.
then with the treated surface of the die Example 7
brought into contact, whereupon upon the action of the deformed surfaces of a stencil, such as the heat from the resulting conversion of a black stencil 25 shown in FIG Material as shown in carbon black, Figs. 14 and 15, is generated. The binder in which the receiver or copier sheet shown in a fusible, normally solid Figs. 13-15, such as polyethylene glycol, is dispersed, 49, which is applied to the implementation participant (s). The die is then calibrated with it Contains dispersed therein, can of course 50 molded surface with a copy sheet in touch both sides take a picture by bringing each rung, whereupon the structure emerges from the die Side is irradiated separately with a die, which and the copy sheet of a short, strong irradiation the deformed surfaces are exposed to one or more envelopes. By absorbing the Contains settlement participants. Infrared rays through the soot generate heat, If, in the case of the method proposed according to the invention, the binder softens, so that a portion of the process involves using a deformed polymer matrix with the dispersed carbon black on the copy sheet, one or more can be transferred and there an exact copy of the origination participant for one color-producing umnal, with which the matrix was made, replacement in the form of a vapor, a liquid. A number of such copies can be easily applied to the template with one or a solid substance, and legible copies can be produced, while with successive actions of the template treated according to this process any number of Copies her-Matrfce a copy or receipt sheet can be made on account,
tion is brought to one or both _D.
Surfaces with one or more um- 65 patent claims:
Settlement participants impregnated or coated 1. Thermoplastic recording process has been produced by reacting with the or with generating a deformation in one of the reaction participants, the z. B. in the ver Polymerisatmaterial, which is in or about itself having radiation energy absorbing material, characterized in that one on this radiant energy absorbing material radiant energy only in such amount directs that sufficient heat is generated in the material to prevent deformation through it on the surface of the polymer material. 2. The method according to claim 1, characterized in that the polymer material in In the form of a thin layer on a carrier sheet, and that one radiant energy in the amount used is sufficient to remove the polymer and expose the carrier sheet sufficient. ' 3. The method according to claim 1 and 2, characterized in that the polymer material, the contains a radiation energy-absorbing material, through a stencil made of less radiation-absorbing material Material is irradiated. 4. The method according to claim 1 or 2, characterized in that the polymer material heated by irradiating a graphic original with radiation-absorbing surfaces will. 5. The method according to claim 1, 3 and 4 for the production of a duplication matrix or Planographic printing film, characterized in that a polymer is used which, according to the thermoplastic recording on the deformed surfaces different affinity properties than has previously. 6. The method according to claim 5, characterized in that a polymer material with hydrophobic surface is used, which after the thermoplastic recording on the deformed surfaces is hydrophilic. 7. The method according to claim 5, characterized in that a polymer material with hydrophilic surface is used, which is deformed after the thermoplastic recording on the Surfaces is hydrophobic. 8. The method according to claim 1 and 2, for the production of a duplication template or Planographic printing film, characterized in that one polymer material is used, the other Has affinity properties as the carrier material. 9. The method according to claim 8, characterized in that a polymer material with hydrophilic surface is used, while the carrier sheet has a hydrophobic surface. 10. A method for reproducing a graphic original according to claim 1, 5 and 8, characterized characterized in that an ink is deposited on the deformed surfaces, whereupon is brought into pressure contact with a copy sheet. 11. The method according to claim 10, characterized in that on the deformed surfaces a first substance is deposited, which is then brought into contact with a copy sheet, which carries at least one second substance, which by reaction with the first substance a Color can form. 12. The method according to claim 10, characterized in that that on the deformed surfaces an infrared absorbing colored material that is dispersed in a fusible, normally solid binder, is deposited, whereupon one brings into contact with a copy sheet and for the generation of heat in irradiated the infrared absorbing material and softening the binder. 13. The method according to claim 10, characterized in that on the deformed surfaces at least a first substance and an infrared absorbing material is deposited that one brings into contact with a copy sheet that contains at least one second substance that is at Can react heat with the first substance, contains, and that one for Heat generation irradiated. 1 sheet of drawings 609 588/266 6.66 © Bundesdruckerei Berlin