CA1108018A - Sheet containing sublimable dye and blocking agent for heat transfer printing - Google Patents
Sheet containing sublimable dye and blocking agent for heat transfer printingInfo
- Publication number
- CA1108018A CA1108018A CA314,436A CA314436A CA1108018A CA 1108018 A CA1108018 A CA 1108018A CA 314436 A CA314436 A CA 314436A CA 1108018 A CA1108018 A CA 1108018A
- Authority
- CA
- Canada
- Prior art keywords
- dye
- blocking agent
- deposited
- heat transfer
- heat
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/025—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet
- B41M5/035—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet by sublimation or volatilisation of pre-printed design, e.g. sublistatic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/003—Transfer printing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/913—Material designed to be responsive to temperature, light, moisture
Abstract
Abstract of the Disclosure This invention concerns transfer sheets which include a blocking agent and which are useful in the heat transfer dye printing of various materials such as textiles. The blocking agent is capable of completely or partially blocking the transfer of heat transfer dyes which have been previously imprinted or coated on the transfer sheets. By using such transfer sheets, designs can be printed which are not otherwise obtainable by coventional techniques. The invention further concerns the method of making such sheets, their use in the printing of various materials, and the materials which have been so printed.
Description
sackground Of The Invention ...
It is known to print textiles and other materials, particularly synthetic fabrics, by heat transfer dye printing using su~limable or vaporizable dyes which have been imprinted in a pattern or design upon a substrate such as paper. Heat transfer printing has been described in French Patent No~
1,223,330 and in Swiss Patent No, 476,893, Such printing techniques, however, are subject to limitations. Thus, it is particularly difficult, and in some cases impossible, to obtain certain complicated patterns or designs involving multicolored combinations of dyes.
In printing heat transfer dyes on a substrate to form a multicolored design to be transferred~ differently colored dyes are successively deposited on the substrate.
When these successive deposits overlap, stronger, darker prints are formed because, when dye is printed over dye, each dye reinforces the color developed by the other~ White is produced by printing no color where white is desired~ and when fine white lines are required~ a printing press must have printing stages exactly in register so that successive imprinting of differently colored dyes do not print in the fine white line area, Furtherr certain shading effects in which lighter and darker shades of the same color are sought can be difficult to obtain for some patterns.
These disadvantages are overcome by the present invention which utilizes a blocking agent capable of chemically reacting with the heat transfer dyes thereby binding -the same to the substrate. The dye thus immobiliæed cannot be heat transferred to the article to bc printed By the use of such bm ~;-:: . ,:
,, : , , , :.................. ,: :. , : ,:
,. . . .
blocking agents, complicated patterns and designs can beeconomically and efficiently produced in which the transfer of the dye is partially or completely blocked thereby allowing lighter shades or no color to be produced over darker shades.
It also allows for greater utilization of printing cylinders because from a given set of cylinders, a series of positive prints and a series of negative prints can be made without making additional engravin~s.
British Patent 1,391,012 describes the use of a physical barrier layer consisting of a proteinaceous coating, While a physical barrier is capable of preventing sublimed dye ~rom passing there through, the effectiveness of the barrier is dependent on the density and the heat stability o~ the barrier. Moreover, it must overlie the dye.
The blocking agent of the present invention is effective when deposited underneath as well as above the dye as it not only acts as a physical barrier but functions to chemically react with the dye and this will~ to an extent, bind dye lying immediately above it~ Further, in accordance with the present invention, heat transfer dyes can be selected so that one is reactive with the blocking agent while a second is non-reactive. This allows for a continuous overcoating o~ blocking agent which is capable of selectively allowing a dye to pass there through. ~till further, the present invention is heat stable as its chemical reactivity is increased wikh heat.
A still further feature of the present invention is that a blocking agent can be incorporated in an ink which contains a dye with which it is non-reactive. This ink is ~hen deposited over an ink con-taining a dye which is reactive with
It is known to print textiles and other materials, particularly synthetic fabrics, by heat transfer dye printing using su~limable or vaporizable dyes which have been imprinted in a pattern or design upon a substrate such as paper. Heat transfer printing has been described in French Patent No~
1,223,330 and in Swiss Patent No, 476,893, Such printing techniques, however, are subject to limitations. Thus, it is particularly difficult, and in some cases impossible, to obtain certain complicated patterns or designs involving multicolored combinations of dyes.
In printing heat transfer dyes on a substrate to form a multicolored design to be transferred~ differently colored dyes are successively deposited on the substrate.
When these successive deposits overlap, stronger, darker prints are formed because, when dye is printed over dye, each dye reinforces the color developed by the other~ White is produced by printing no color where white is desired~ and when fine white lines are required~ a printing press must have printing stages exactly in register so that successive imprinting of differently colored dyes do not print in the fine white line area, Furtherr certain shading effects in which lighter and darker shades of the same color are sought can be difficult to obtain for some patterns.
These disadvantages are overcome by the present invention which utilizes a blocking agent capable of chemically reacting with the heat transfer dyes thereby binding -the same to the substrate. The dye thus immobiliæed cannot be heat transferred to the article to bc printed By the use of such bm ~;-:: . ,:
,, : , , , :.................. ,: :. , : ,:
,. . . .
blocking agents, complicated patterns and designs can beeconomically and efficiently produced in which the transfer of the dye is partially or completely blocked thereby allowing lighter shades or no color to be produced over darker shades.
It also allows for greater utilization of printing cylinders because from a given set of cylinders, a series of positive prints and a series of negative prints can be made without making additional engravin~s.
British Patent 1,391,012 describes the use of a physical barrier layer consisting of a proteinaceous coating, While a physical barrier is capable of preventing sublimed dye ~rom passing there through, the effectiveness of the barrier is dependent on the density and the heat stability o~ the barrier. Moreover, it must overlie the dye.
The blocking agent of the present invention is effective when deposited underneath as well as above the dye as it not only acts as a physical barrier but functions to chemically react with the dye and this will~ to an extent, bind dye lying immediately above it~ Further, in accordance with the present invention, heat transfer dyes can be selected so that one is reactive with the blocking agent while a second is non-reactive. This allows for a continuous overcoating o~ blocking agent which is capable of selectively allowing a dye to pass there through. ~till further, the present invention is heat stable as its chemical reactivity is increased wikh heat.
A still further feature of the present invention is that a blocking agent can be incorporated in an ink which contains a dye with which it is non-reactive. This ink is ~hen deposited over an ink con-taining a dye which is reactive with
-2-bm:~
.: . . :
. . . ~. , the blocking a~ent. As a result, the dye incorporate~ in the blocking agent is transferred but the dye below the blocking agent is blocked.
Summar~ Of The Invention This invention provides a structure useful ~or heat transfer dye printing The structure comprises a substrate, such as a paper sheet, on one surface of which at least one -heat transferable dye has been imprinted or coated and a blocking agent has been deposited on or underneath at least a portion of said dye. ~he portion of the imprinted or coated dye in contact with the blocking agent is partially or completely blocked from being heat transferred.
In another embodiment, this invention provides a process for preparing the structure useful for heat transfer dye printing which comprises imprinting or coatiny at least one heat-transferable dye on one surface of a substrate and depositing a blocking agent in contact with at least a portion of said imprinted dye. In still another embodiment, this invention provides a process for heat transfer dye printing which comprises heating the structure, on which dye has been imprinted or coated and blocking a~ent deposited, together with a material to be printed. The sturcture and the material to be printed are placed adjacent to or in contact with one another and heated to a temperature at which the deposited dye sublimes or vaporizes or otherwise transfers so that the ~ye is transferred to the material to be printed with the dye in contact with the blocking agent being partially or completely prevente~
from transferring.
In still another embodiment, this invention provides bm~
. : . , printed materials prepared in accordance with the process described herein.
These and other embodiments of this invention will be understood more clearly by reference to the accompanying drawings and detailed description of the invention Brie~ Description Of The ~rawings Fig. 1 is a partial planar view o~ a dye transfer sheet in accordance with this invention which includes an imprinted dye upon a portion of which blocking agent has been ~posited;
Fig. 2 is a section taken substantially along the line 2-2 of Fig. l;
Fig. 3 is a partial planar view of a material ~hich has been printed using the transfer sheet of Fig 1, Detailed Description oE The Invention Specifically, this invention provides structures useful for heat -transfer dye printing of various materials, especially synthetic textile fabrics The structure of this invention comprises a substrate on one surface of which one or more heat transferable dyes have been imprinted or coated.
In addition, a blocking agent is dep~sited on or below at least a portion of the imprinted or coated dye or dyes~ Various substrates including plastic films and metal foils are usefully employed in the practices of this invention but paper is particularly preferred. The substrate may be in the form of continuous roll or sheet and may be rigid or ~lexible.
Paper transfer sheets, shown as 10 in Fig. 1, are particularly useful as substrates. After imprintiny with dye 14 and depositing blocking agent 12 on substrate 16, the sheets r bm:
, . . . , : :
,, . ::
.
can be rolled and stored for later use in the hea-t transfer dye printing of various materials. ~he blocking agent 12 and dye 14 of this invention, shown in cross sectional view in Fig. 2, can be printed by diverse printing techniques, such as, for example, ~ravure, flexographict letter press, rotary screen, etc. In addition, dye 14 and blocking a~ent 12 may be coated as well as printed b~ various diverse coating techniques, such as reverse roll, air knife, trailin~ blade, etc, While the ~lockin~ agent 12 is shown in Figure 2 overlying the dye 14, it is to be understood that the blocking a~ent 12 may be deposited directly on substrate 1~ with dye 14 overlyin~ the same~ In this instance, however, the blockin~
a~ent 12 will only partially block transfer of the dye.
The heat transferable dyes useful in this invention are dyes which sublime or vaporize or otherwise convert to a mobil phase in a range of 160 to ~40C. at or around atmospheric pressure. In vacuum transfer, dyes which convert to a mobil phase at a temperature lower than 160C can be used.
The heat transfer dyes used in the present invention are commonly referred to as disperse dyes but this terminology describes the way the dyes are used rather than a class or classes of dyes. Heat transfer dyes which are capable of bein~
heat activated to a mobil phase in the aforesaid -temperature ran~e can be selected from nitroso, nitro, monoazol disazo, trisazo, polyazo, stillbene, carotenoid, diphenylmethane, triarylmethane, xanthene, acridine, quinoline, methine, thiazolè, indamine, indophenol, azine, oxazine, thiazine, sulphur, lactone, aminoketone, hydroxyketone, anthraquinone, bm~
-' : .. : . : '' - :.... . : .
- .. .
., , ~
indigoia, and phthalocyanine dyes.
Dyes which include one or more polar functional ~roups such as -NH2 or -OH or-S02 NH2 are preferred, but the particular choice will depend on its chemical reactivity with the blocking agent employed~
The ollowing are examples of heat transferable dyes which have been found useful in the practice of this nventlon:
l-Amino - 4 ~ Hydroxyanthraquinones ~ ~ ~ Disp Red 60 O O}I
1l NH ~ CH3 C \ ~ ~ Disp Blue 72 0 0~
1, 4-Diaminoanthraquinone~s O NH~ OH NH
X~=X2=H Di~sp Viole-t 1 ~YJ~ X2 ~\~ Xl=X2--Cl Disp Violet 28 .~
bm:~
fl ,~H2 OH NH ~loilday's Subprin~
CN = ~ s~ue 11 Intr~- P-305 O HR OH NR
Azo Dyes - - CHg C~IsC NH ~) N No~ Disp Yellow 3 .
~ ~ CH 2 CH 3 NO~N = N ~ ~ Cii 2CH~OH
~N---- N~N--N~) OH DiSp Yellow 23 : bm :~i; . .
.
.
~g ,f -: : ~ ' ~' ` ` : .!, ', , :' , '::'. . ~,- . . : ~:
, " ~, :.` `' :`
~($8~
H2~
N = ~ ~ NH2 Solvent Brown 1 ~.
~1 ~H
\ N ~
TRIARYLME~HANE
~. .
. .. ~.~..-0}~
> N BASIC BLUE 1 BASE
.: . . :
. . . ~. , the blocking a~ent. As a result, the dye incorporate~ in the blocking agent is transferred but the dye below the blocking agent is blocked.
Summar~ Of The Invention This invention provides a structure useful ~or heat transfer dye printing The structure comprises a substrate, such as a paper sheet, on one surface of which at least one -heat transferable dye has been imprinted or coated and a blocking agent has been deposited on or underneath at least a portion of said dye. ~he portion of the imprinted or coated dye in contact with the blocking agent is partially or completely blocked from being heat transferred.
In another embodiment, this invention provides a process for preparing the structure useful for heat transfer dye printing which comprises imprinting or coatiny at least one heat-transferable dye on one surface of a substrate and depositing a blocking agent in contact with at least a portion of said imprinted dye. In still another embodiment, this invention provides a process for heat transfer dye printing which comprises heating the structure, on which dye has been imprinted or coated and blocking a~ent deposited, together with a material to be printed. The sturcture and the material to be printed are placed adjacent to or in contact with one another and heated to a temperature at which the deposited dye sublimes or vaporizes or otherwise transfers so that the ~ye is transferred to the material to be printed with the dye in contact with the blocking agent being partially or completely prevente~
from transferring.
In still another embodiment, this invention provides bm~
. : . , printed materials prepared in accordance with the process described herein.
These and other embodiments of this invention will be understood more clearly by reference to the accompanying drawings and detailed description of the invention Brie~ Description Of The ~rawings Fig. 1 is a partial planar view o~ a dye transfer sheet in accordance with this invention which includes an imprinted dye upon a portion of which blocking agent has been ~posited;
Fig. 2 is a section taken substantially along the line 2-2 of Fig. l;
Fig. 3 is a partial planar view of a material ~hich has been printed using the transfer sheet of Fig 1, Detailed Description oE The Invention Specifically, this invention provides structures useful for heat -transfer dye printing of various materials, especially synthetic textile fabrics The structure of this invention comprises a substrate on one surface of which one or more heat transferable dyes have been imprinted or coated.
In addition, a blocking agent is dep~sited on or below at least a portion of the imprinted or coated dye or dyes~ Various substrates including plastic films and metal foils are usefully employed in the practices of this invention but paper is particularly preferred. The substrate may be in the form of continuous roll or sheet and may be rigid or ~lexible.
Paper transfer sheets, shown as 10 in Fig. 1, are particularly useful as substrates. After imprintiny with dye 14 and depositing blocking agent 12 on substrate 16, the sheets r bm:
, . . . , : :
,, . ::
.
can be rolled and stored for later use in the hea-t transfer dye printing of various materials. ~he blocking agent 12 and dye 14 of this invention, shown in cross sectional view in Fig. 2, can be printed by diverse printing techniques, such as, for example, ~ravure, flexographict letter press, rotary screen, etc. In addition, dye 14 and blocking a~ent 12 may be coated as well as printed b~ various diverse coating techniques, such as reverse roll, air knife, trailin~ blade, etc, While the ~lockin~ agent 12 is shown in Figure 2 overlying the dye 14, it is to be understood that the blocking a~ent 12 may be deposited directly on substrate 1~ with dye 14 overlyin~ the same~ In this instance, however, the blockin~
a~ent 12 will only partially block transfer of the dye.
The heat transferable dyes useful in this invention are dyes which sublime or vaporize or otherwise convert to a mobil phase in a range of 160 to ~40C. at or around atmospheric pressure. In vacuum transfer, dyes which convert to a mobil phase at a temperature lower than 160C can be used.
The heat transfer dyes used in the present invention are commonly referred to as disperse dyes but this terminology describes the way the dyes are used rather than a class or classes of dyes. Heat transfer dyes which are capable of bein~
heat activated to a mobil phase in the aforesaid -temperature ran~e can be selected from nitroso, nitro, monoazol disazo, trisazo, polyazo, stillbene, carotenoid, diphenylmethane, triarylmethane, xanthene, acridine, quinoline, methine, thiazolè, indamine, indophenol, azine, oxazine, thiazine, sulphur, lactone, aminoketone, hydroxyketone, anthraquinone, bm~
-' : .. : . : '' - :.... . : .
- .. .
., , ~
indigoia, and phthalocyanine dyes.
Dyes which include one or more polar functional ~roups such as -NH2 or -OH or-S02 NH2 are preferred, but the particular choice will depend on its chemical reactivity with the blocking agent employed~
The ollowing are examples of heat transferable dyes which have been found useful in the practice of this nventlon:
l-Amino - 4 ~ Hydroxyanthraquinones ~ ~ ~ Disp Red 60 O O}I
1l NH ~ CH3 C \ ~ ~ Disp Blue 72 0 0~
1, 4-Diaminoanthraquinone~s O NH~ OH NH
X~=X2=H Di~sp Viole-t 1 ~YJ~ X2 ~\~ Xl=X2--Cl Disp Violet 28 .~
bm:~
fl ,~H2 OH NH ~loilday's Subprin~
CN = ~ s~ue 11 Intr~- P-305 O HR OH NR
Azo Dyes - - CHg C~IsC NH ~) N No~ Disp Yellow 3 .
~ ~ CH 2 CH 3 NO~N = N ~ ~ Cii 2CH~OH
~N---- N~N--N~) OH DiSp Yellow 23 : bm :~i; . .
.
.
~g ,f -: : ~ ' ~' ` ` : .!, ', , :' , '::'. . ~,- . . : ~:
, " ~, :.` `' :`
~($8~
H2~
N = ~ ~ NH2 Solvent Brown 1 ~.
~1 ~H
\ N ~
TRIARYLME~HANE
~. .
. .. ~.~..-0}~
> N BASIC BLUE 1 BASE
3.
., ~ .
DIPHEN~LAMINE OR "NITRO"
. .
NH _ ~ O ~ S~:N~I~ DISP YELLOW 33 hll, !...
.
.
. ~ ":
:~
g`~
.
QUI NOPHTH ALONE
PERINONE
.
<~ SOLVENT ORANGE 60 O
- _IOINDI~:OID
O
\=/~ VAT RED '11 O
METHINE
~Cll=CHNH~O~ 5)CN3 BASIC YELLOW 11 BASE
: 'OH C O
.'~ ' ClCH 2 CH 2\ fi~\ ~ COOc 2~-l 5 N~ ~ CH=C DISP YELI,OW 31 C4H~ CN
~m ~ g_ .
: , . ...
:~ . , .
The in~s containin~ the heat transferrable dyes will be formulated so as to be appropriate to the printing or coating ~ethod employed. Selection of binders, solvents, extenders are matters well ~ithin the skill o~ a chemist in the art.
For example, a gravure heat transfer ink could comprise a heat transfer dye dispersed in a vehicle composed o~ ethyl cellulose dissolved in ethyl~ alcohol vehicle. Likewise, a water-based flexographic heat transfer ink could be prepared by dispersing a heat transfer dye in a vehicle composed o~ an acrylic resin dissolved in a water and an isopropanol blend.
hot melt coating may be prepared by dispersing the dye in a hi~h melting wax mixture. A rotary screen ink could be prepared by using a dispersed dye paste compounded with a thickening agent and water.
The selection of the blocking agent is a matter within the skill of a chemist in the art as once the heat trans~er dye is selec-ted, a blocking agent can be selected from a wide range of compounds known to chemically react with the dye. The dye may be permanently bound by various mechanisms such as reactions which immobilize the dye, or other reactions which r destroy or convert the dyes to a non-colored form. For example, any dye chemist would know that many anthraquinone dyes may be reduced to a water-soluble, ionic, colorless Eorm by treatment with hydrosulphite. Accordingly, hydrosulphite could be used to bloc~ anthraquinone dyes. Reactive reagents such as isocyanates can be used as a blocking agent to block dyes containing hydroxyl functionality.
Since aminoplasts are capable oE chemically reacting with and immobilizing a broad range of dyes with ~unctional bm~
, . ~, . . .
:- . : . ... , -- ': ... .,: , , . :
., , - ~ , , . :
, ,~. - , - .::
, , ,~ ~
.
groups such as - NH2 or - OH or -SOzNH2~ this class is preferred.
The aminoplasts include, for example, urea formaldehyde, methylated urea formaldehyde, melamine formaldehyde, methylated melamine formaldehyde~ and glyoxal formaldehyde.
Epoxy resins have also been found to have a broad ~ange of application as a blocking agent particularly with dyes having amino functioned groups.
Melamine based compounds having a particularly large range of application as blocking agents are represented by the following formula:
N - R
/c~
R~ - C C ~- N - R5 \ N ~
Wherein R~, R2, R3, R4, R5, R6, may be the same or different, each of which may represe~t a hydrogen, a Cl-C6 alkyl, a methylol (-CH20CH2) a methoxymethyl (CH30CH2-), or a C2- C6 alko~ymethyl (n-butoxy methyl: CH9CH2CH2CH20CH2 for example) with the proviso that at least one of Rl, R2, R9, R~" R5, or R6 is a methylol (-CH2 OH), methoxyme-thyl (CH30CH2--? or a higher alkoxymethyl. Especially preferred as a blocking agent is hexamethoxymethylmelamine.
Urea based compounds may be of the following formulao . o Ill H2 - --11- ' ~ bm:~
..
.
:
Wherein Rl and R2 may be the same or diffexen-t, each of which m~y represent a hydrogen, a Cl-C6 ~lkyl, a methylol (-C~120H) and methoxymethyl ~CH3-OCH2-) or C2-c6 alkoxymethyl (n-butoxy methyl:
C~I3CH2CH2CH20CH2- for example) with the proviso that either R~ or R2 is a methylol (-CH20H~, a methoxymethyl (CH30CH2-) or a higher alkoxymethyl.
It is possible to replace Hl and Hz above with al];yls~ Dimethyl olethyleneurea indicated below is one possible modification.
1 0 ~0 HOH2C ~ C\ CH20H
H2~ ~2 Glyoxal basèd compounds may be of the following formula:
. Rl R2 ;.-~
I H 1 :
~~\ ~ ~
~N /~1\
~b R9 wherein R~, R2, R3, and R4 ~ may be the same or different, each o~ which may represent a hydrogen, a C1-C6 alkyl, a methylol (-C~I20H), methoxymethyl (CH30CH2-) or a C2-C6 alkoxymethyl (n-butoxy methyl: CH3CH2CH2CH2 OCE12 - for example) wlth the : ~roviso that at least one o:E Rl, R2, R3, or R~ is a methylol (-CH20H), methoxymethyl (CH30CH2-) or a higher alkoxymethyl~
The blocking agent is deposited as a layer using any conventional printing technique such as gravure, flexographic, letter press, etc Depending on the printin~
method employed, the blocking agent optionally has carrier, ~12-" ~ . . . .... .
- - : , , ' : ;
~31~
extender, and solvent added thereto.
In addition, catalysts may be added depending on the chemistry of the blocking agent to ~e employed. For example, an acidic catalyst will be added when an aminoplast is to be used.
The carrier or the components of the carriers, as well as the solvents and extenders are well known to chemists in the various printing fields. When, for example, gravure printing is employed to deposit the blocking agent and the bloc~in~ agent is one o~ the aminoplasts referred to above, cellulose ~erivatives are particularly useful as carriers:
Examples of such carriers include cellulose acetate butyrate, cellulose acetate propionate, ethyl cellulose~ and nitrocellulose.
Vinyl and vinyl copolymer resins~ acrylic and acrylic copolymer resins, alkyd resins (drying and non-drying), and chlorinated rubbers are also suitable.
Since the blocking agents of this invention are ordinarily colorless, it is oftentimes desirable to include in the layer a colored non-heat transferable dye as a marker to indicate the location of the blocking agent after it has heen deposited on the imprinted dye. A charged cationic dye, such as a Victoria Blue, and carbon black are useful in this regard.
The structures of this invention-as shown in Fig~ 1 can be prepared by imprinting or coating at least one heat transferable dye on one surface of a substrate and depositing a blocking agent on at least a portion of the imprinted dye.
In the alternative/ the blocking agent can be deposited first and the dye deposited thereover, but in this instance, -the dye will only be partially blocked.
bm~
: . , :
, ~ :
.
The structures can then be used in the printing of v~rious materials. For textiles, materials prepared from synthetic fibers such as polyesters, polyamides, and acrylics are particularly receptive to heat transfer dyes. When appropriate pretreatments are used, cellulosics and cellulosic containing blends may be used. Wood, films, and metals, provided with a dye-receptive coating are also suitable for printing.
Heat transfer printing is effected by heating the structure and the material to be printed, both oE which have been placed to~ether to a temperature of 160 and 2~0 C.
for a sufficient period of time to allow the heat transferable ;.
dye to convert to a mobil phase and then to move to the material which is being printed. The blocking agent undergoes a chemical reaction with at least`a portion of the dye upon which it has been deposited. This reaction takes place both or either at the time of deposit of the blocking agent in contact with the dye and/or during the heating process when the unreacted dye mobilized into the layer containing the blockin~ agent reacted dye is immibilized and therefore is not tranferred. The extent of this reaction depends upon the nature of the dye used and the concentration of the blocking agent in the layer deposited on or under the dye. By varying the concentration, complete blockage of dye transfer or partial blockage to produce shading effects can be obtained. Complete blockage occurs when there is sufficient concentration of blocking agent overlying the dye to completely react with all the dye attempting to pass there through.
A printed material such as a synthetic tex-tile fabric bm~
. ,' ., ~ ~ , ;
prepared in accordance with thi~ process is shown at 18 in Fig. 3.
The invention also has application to a heat transfer process commonly known as the dew print process described and illustrated on pages 71 and 72 o~ the October 1975 issue of "Textile Month's" published by Textile Business Press, Ltd , Staham House, Talbot Road, Stretford, Manchester, Great Britain wherein a water saturated fabric to be printed is brought in contact with a printed sheet containing dyestuff appropriate to the fabric. The dye dissolves in the water and migrates to the fabric.
The following examples are set forth hereinafter to illustrate the invention more fully but are not intended in any way to l mit the scope thereof. Parts and percentages are expressed by wei~ht unless an indication to the contary `
is ~iven.
Example 1.
An ink is prepared comprising about 16 percent Disp Yellow 23. The ink is imprinted on a paper sheet to completely cover its surface. A blocking agent is then deposited on a portion of the imprinted ink in the form of an organic layer havin~ the following composition:
Hexamethoxymethylmelamine 33O3%
Nitrocellulose (70% solid in ;
isopropanol) 16.7%
Solvent ~5.0%
(one part ester/one part alcohol/
one part toluol) Para-toluene sulphonic acid (50% 5.0%
solution in alcohol) ~ -15-. r. .~
bm~
,: :
.: -' : '. .~ .. ., ' ' ' ' -,.
.
, t3~
The sheet on which the dye has been imprinted and the blocking a~ent deposited is then used to heat transfer print a polyester fabric. Essentially complete blockage of d~e transfer is obtained from that portion of the sheet or dye on which the blocking agent had been deposited.
Example 2, An ink is prepared which contains 16 percent Disp Red 1 dye. This is imprinted on a paper sheet so as to cover its surface. Blocking agent is then deposited on a portion of the ink in the form of a layer having the following composition:
Hexamethyoxymethylmelamine 42.0~
Ethyl Cellulose - 4 C.P~S. 8.0%
Solvent (one part ester/one part 40,0%
- alcohol/one part toluol) Para-toluene sulphonic acid (50~ solution in alcohol) 10,0%
A fabric is then used to hea~ transfer print a nylon fabric. Essentially complete blockage of dye transfer is obtained.
Example 3~
The concentration of hexamethoxylmethylmelamine in Example is 2 is reduced to 6 percent by adding an ethyl cellulose solution (10 percent solids in the solvent blend of Example 2). About 65 percent of dye transfer is blocked.
Example 4.
NlN2 - Dimethoxymethylurea was substituted for the hexamethaxymethylmelamine of Example 1. Nearly complete blockage of the dye transfer was obtained.
bm: c,~
, .. .
~xample 5, The same as Example 1 except that the ink was deposited over the blocking agent~ About 50 percent of the dye was blocked.
E~ample 6.
An ink is prepared comprising 16 percent Holiday Subprint Blue 70032. The ink is imprinted on paper to con~pletely cover its surface. Blocking agent is then deposited on a por~ion of the imprinted ink in the form of a layer having the following composition:
Epon 1007 (epoxy resin) 30%
Solvent (one part Cellosolve~/ 6,%
one part toluol/one part methylethyl Ketone) Para-toluene sulphonic acid 3 (50% solution in alcohol) The sheet on which the dye has been imprinted and the blocking agent deposited is then used to heat transfer print a sheet of polyester film. A partial blockage of dye transfer is obtained from that portion of the sheet or d~e on which the blocking agent has been deposited, As t~ill be obvious to one skilled in the art, many modifications and variations are possible in this invention without departing from the scope and spirit thereof as set forth more fully in the claims which follo~
-~ bm~
;:, ~, :
: , . : , .
- ~ :: ~ ., : ;: ... .. .
..... . .....
: ;. "
: ,:. :: . :
., ~ .
DIPHEN~LAMINE OR "NITRO"
. .
NH _ ~ O ~ S~:N~I~ DISP YELLOW 33 hll, !...
.
.
. ~ ":
:~
g`~
.
QUI NOPHTH ALONE
PERINONE
.
<~ SOLVENT ORANGE 60 O
- _IOINDI~:OID
O
\=/~ VAT RED '11 O
METHINE
~Cll=CHNH~O~ 5)CN3 BASIC YELLOW 11 BASE
: 'OH C O
.'~ ' ClCH 2 CH 2\ fi~\ ~ COOc 2~-l 5 N~ ~ CH=C DISP YELI,OW 31 C4H~ CN
~m ~ g_ .
: , . ...
:~ . , .
The in~s containin~ the heat transferrable dyes will be formulated so as to be appropriate to the printing or coating ~ethod employed. Selection of binders, solvents, extenders are matters well ~ithin the skill o~ a chemist in the art.
For example, a gravure heat transfer ink could comprise a heat transfer dye dispersed in a vehicle composed o~ ethyl cellulose dissolved in ethyl~ alcohol vehicle. Likewise, a water-based flexographic heat transfer ink could be prepared by dispersing a heat transfer dye in a vehicle composed o~ an acrylic resin dissolved in a water and an isopropanol blend.
hot melt coating may be prepared by dispersing the dye in a hi~h melting wax mixture. A rotary screen ink could be prepared by using a dispersed dye paste compounded with a thickening agent and water.
The selection of the blocking agent is a matter within the skill of a chemist in the art as once the heat trans~er dye is selec-ted, a blocking agent can be selected from a wide range of compounds known to chemically react with the dye. The dye may be permanently bound by various mechanisms such as reactions which immobilize the dye, or other reactions which r destroy or convert the dyes to a non-colored form. For example, any dye chemist would know that many anthraquinone dyes may be reduced to a water-soluble, ionic, colorless Eorm by treatment with hydrosulphite. Accordingly, hydrosulphite could be used to bloc~ anthraquinone dyes. Reactive reagents such as isocyanates can be used as a blocking agent to block dyes containing hydroxyl functionality.
Since aminoplasts are capable oE chemically reacting with and immobilizing a broad range of dyes with ~unctional bm~
, . ~, . . .
:- . : . ... , -- ': ... .,: , , . :
., , - ~ , , . :
, ,~. - , - .::
, , ,~ ~
.
groups such as - NH2 or - OH or -SOzNH2~ this class is preferred.
The aminoplasts include, for example, urea formaldehyde, methylated urea formaldehyde, melamine formaldehyde, methylated melamine formaldehyde~ and glyoxal formaldehyde.
Epoxy resins have also been found to have a broad ~ange of application as a blocking agent particularly with dyes having amino functioned groups.
Melamine based compounds having a particularly large range of application as blocking agents are represented by the following formula:
N - R
/c~
R~ - C C ~- N - R5 \ N ~
Wherein R~, R2, R3, R4, R5, R6, may be the same or different, each of which may represe~t a hydrogen, a Cl-C6 alkyl, a methylol (-CH20CH2) a methoxymethyl (CH30CH2-), or a C2- C6 alko~ymethyl (n-butoxy methyl: CH9CH2CH2CH20CH2 for example) with the proviso that at least one of Rl, R2, R9, R~" R5, or R6 is a methylol (-CH2 OH), methoxyme-thyl (CH30CH2--? or a higher alkoxymethyl. Especially preferred as a blocking agent is hexamethoxymethylmelamine.
Urea based compounds may be of the following formulao . o Ill H2 - --11- ' ~ bm:~
..
.
:
Wherein Rl and R2 may be the same or diffexen-t, each of which m~y represent a hydrogen, a Cl-C6 ~lkyl, a methylol (-C~120H) and methoxymethyl ~CH3-OCH2-) or C2-c6 alkoxymethyl (n-butoxy methyl:
C~I3CH2CH2CH20CH2- for example) with the proviso that either R~ or R2 is a methylol (-CH20H~, a methoxymethyl (CH30CH2-) or a higher alkoxymethyl.
It is possible to replace Hl and Hz above with al];yls~ Dimethyl olethyleneurea indicated below is one possible modification.
1 0 ~0 HOH2C ~ C\ CH20H
H2~ ~2 Glyoxal basèd compounds may be of the following formula:
. Rl R2 ;.-~
I H 1 :
~~\ ~ ~
~N /~1\
~b R9 wherein R~, R2, R3, and R4 ~ may be the same or different, each o~ which may represent a hydrogen, a C1-C6 alkyl, a methylol (-C~I20H), methoxymethyl (CH30CH2-) or a C2-C6 alkoxymethyl (n-butoxy methyl: CH3CH2CH2CH2 OCE12 - for example) wlth the : ~roviso that at least one o:E Rl, R2, R3, or R~ is a methylol (-CH20H), methoxymethyl (CH30CH2-) or a higher alkoxymethyl~
The blocking agent is deposited as a layer using any conventional printing technique such as gravure, flexographic, letter press, etc Depending on the printin~
method employed, the blocking agent optionally has carrier, ~12-" ~ . . . .... .
- - : , , ' : ;
~31~
extender, and solvent added thereto.
In addition, catalysts may be added depending on the chemistry of the blocking agent to ~e employed. For example, an acidic catalyst will be added when an aminoplast is to be used.
The carrier or the components of the carriers, as well as the solvents and extenders are well known to chemists in the various printing fields. When, for example, gravure printing is employed to deposit the blocking agent and the bloc~in~ agent is one o~ the aminoplasts referred to above, cellulose ~erivatives are particularly useful as carriers:
Examples of such carriers include cellulose acetate butyrate, cellulose acetate propionate, ethyl cellulose~ and nitrocellulose.
Vinyl and vinyl copolymer resins~ acrylic and acrylic copolymer resins, alkyd resins (drying and non-drying), and chlorinated rubbers are also suitable.
Since the blocking agents of this invention are ordinarily colorless, it is oftentimes desirable to include in the layer a colored non-heat transferable dye as a marker to indicate the location of the blocking agent after it has heen deposited on the imprinted dye. A charged cationic dye, such as a Victoria Blue, and carbon black are useful in this regard.
The structures of this invention-as shown in Fig~ 1 can be prepared by imprinting or coating at least one heat transferable dye on one surface of a substrate and depositing a blocking agent on at least a portion of the imprinted dye.
In the alternative/ the blocking agent can be deposited first and the dye deposited thereover, but in this instance, -the dye will only be partially blocked.
bm~
: . , :
, ~ :
.
The structures can then be used in the printing of v~rious materials. For textiles, materials prepared from synthetic fibers such as polyesters, polyamides, and acrylics are particularly receptive to heat transfer dyes. When appropriate pretreatments are used, cellulosics and cellulosic containing blends may be used. Wood, films, and metals, provided with a dye-receptive coating are also suitable for printing.
Heat transfer printing is effected by heating the structure and the material to be printed, both oE which have been placed to~ether to a temperature of 160 and 2~0 C.
for a sufficient period of time to allow the heat transferable ;.
dye to convert to a mobil phase and then to move to the material which is being printed. The blocking agent undergoes a chemical reaction with at least`a portion of the dye upon which it has been deposited. This reaction takes place both or either at the time of deposit of the blocking agent in contact with the dye and/or during the heating process when the unreacted dye mobilized into the layer containing the blockin~ agent reacted dye is immibilized and therefore is not tranferred. The extent of this reaction depends upon the nature of the dye used and the concentration of the blocking agent in the layer deposited on or under the dye. By varying the concentration, complete blockage of dye transfer or partial blockage to produce shading effects can be obtained. Complete blockage occurs when there is sufficient concentration of blocking agent overlying the dye to completely react with all the dye attempting to pass there through.
A printed material such as a synthetic tex-tile fabric bm~
. ,' ., ~ ~ , ;
prepared in accordance with thi~ process is shown at 18 in Fig. 3.
The invention also has application to a heat transfer process commonly known as the dew print process described and illustrated on pages 71 and 72 o~ the October 1975 issue of "Textile Month's" published by Textile Business Press, Ltd , Staham House, Talbot Road, Stretford, Manchester, Great Britain wherein a water saturated fabric to be printed is brought in contact with a printed sheet containing dyestuff appropriate to the fabric. The dye dissolves in the water and migrates to the fabric.
The following examples are set forth hereinafter to illustrate the invention more fully but are not intended in any way to l mit the scope thereof. Parts and percentages are expressed by wei~ht unless an indication to the contary `
is ~iven.
Example 1.
An ink is prepared comprising about 16 percent Disp Yellow 23. The ink is imprinted on a paper sheet to completely cover its surface. A blocking agent is then deposited on a portion of the imprinted ink in the form of an organic layer havin~ the following composition:
Hexamethoxymethylmelamine 33O3%
Nitrocellulose (70% solid in ;
isopropanol) 16.7%
Solvent ~5.0%
(one part ester/one part alcohol/
one part toluol) Para-toluene sulphonic acid (50% 5.0%
solution in alcohol) ~ -15-. r. .~
bm~
,: :
.: -' : '. .~ .. ., ' ' ' ' -,.
.
, t3~
The sheet on which the dye has been imprinted and the blocking a~ent deposited is then used to heat transfer print a polyester fabric. Essentially complete blockage of d~e transfer is obtained from that portion of the sheet or dye on which the blocking agent had been deposited.
Example 2, An ink is prepared which contains 16 percent Disp Red 1 dye. This is imprinted on a paper sheet so as to cover its surface. Blocking agent is then deposited on a portion of the ink in the form of a layer having the following composition:
Hexamethyoxymethylmelamine 42.0~
Ethyl Cellulose - 4 C.P~S. 8.0%
Solvent (one part ester/one part 40,0%
- alcohol/one part toluol) Para-toluene sulphonic acid (50~ solution in alcohol) 10,0%
A fabric is then used to hea~ transfer print a nylon fabric. Essentially complete blockage of dye transfer is obtained.
Example 3~
The concentration of hexamethoxylmethylmelamine in Example is 2 is reduced to 6 percent by adding an ethyl cellulose solution (10 percent solids in the solvent blend of Example 2). About 65 percent of dye transfer is blocked.
Example 4.
NlN2 - Dimethoxymethylurea was substituted for the hexamethaxymethylmelamine of Example 1. Nearly complete blockage of the dye transfer was obtained.
bm: c,~
, .. .
~xample 5, The same as Example 1 except that the ink was deposited over the blocking agent~ About 50 percent of the dye was blocked.
E~ample 6.
An ink is prepared comprising 16 percent Holiday Subprint Blue 70032. The ink is imprinted on paper to con~pletely cover its surface. Blocking agent is then deposited on a por~ion of the imprinted ink in the form of a layer having the following composition:
Epon 1007 (epoxy resin) 30%
Solvent (one part Cellosolve~/ 6,%
one part toluol/one part methylethyl Ketone) Para-toluene sulphonic acid 3 (50% solution in alcohol) The sheet on which the dye has been imprinted and the blocking agent deposited is then used to heat transfer print a sheet of polyester film. A partial blockage of dye transfer is obtained from that portion of the sheet or d~e on which the blocking agent has been deposited, As t~ill be obvious to one skilled in the art, many modifications and variations are possible in this invention without departing from the scope and spirit thereof as set forth more fully in the claims which follo~
-~ bm~
;:, ~, :
: , . : , .
- ~ :: ~ ., : ;: ... .. .
..... . .....
: ;. "
: ,:. :: . :
Claims (18)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A structure useful for heat transfer dye printing which comprises a substrate, at least one heat transferable dye applied on one surface of said substrate and a heat activated chemically reactive blocking agent disposited on at least a portion of said imprinted dye.
2. A structure useful for heat transfer dye printing which comprises a substrate, a blocking agent deposited on a portion of said substrate, a heat transferable dye deposited on said substrate with a portion thereof overlying said blocking agent.
3. A structure in accordance with Claim 1 wherein said blocking agent is chemically reactive with said dye upon which said blocking agent is deposited.
4. A structure in accordance with Claim 1 wherein said blocking agent is chemically reactive with the dye upon which said blocking agent is deposited so that upon the application of heat to the structure containing said dye and blocking agent deposited thereon said blocking agent chemically reacts with said dye to prevent the heat transfer of that portion of the dye coated with said blocking agent from the surface of the substrate upon which dye is deposited.
5. The structure of Claim l wherein said heat transferable dye is a dye which sublimes or vaporizes at a temperature in the range about 160° - 240°C atmospheric pressure.
6. The structure of Claim 5 wherein said dye is an azo dye.
7. The structure of Claim 5 wherein said dye is an anthraquinone dye.
8. The structure of Claim 1 wherein said blocking agent is an aminoplast.
9. The structure of Claim 8 wherein said blocking agent is hexamethoxymethylmelamine.
10. The structure of Claim 1 wherein said blocking agent is deposited as a layer comprising the blocking agent, a carrier and a solvent.
11. The structure of Claim 10 wherein said layer further comprises a catalyst.
12. The structure of Claim 11 wherein said catalyst is acidic or acidic-acting and said blocking agent is an aminoplast.
13. The structure of Claim 12 wherein said catalyst is p- tolenesulfonic acid.
14. The structure of Claim 1 wherein said layer further comprises a colored non-heat transferable dye as a marker to indicate the location of said blocking agent,
15. A process for heat transfer dye printing which comprises placing a heat transfer dye in contact with a material to be printed, sandwiching a blocking agent between a portion of said dye and said material, heating said dye, blocking agent and material in a range between 160° to 240°C, for a sufficient period of time to allow the heat transferable dye to transfer and to penetrate into the material except that a lighter shade is produced in the material in the portion of the material in contact with said blocking agent.
16. The process of Claim 15 wherein said material to be printed is a synthetic fabric.
17. The process of Claim 16 wherein said material to be printed is wood, plastic or a metal with a dye receptive coating.
18. A structure of Claim 1, said blocking agent deposit includes a dye which is non reactive with said blocking agent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US861,422 | 1977-12-16 | ||
| US05/861,422 US4171202A (en) | 1977-12-16 | 1977-12-16 | Sheet containing sublimable dye and blocking reagent for heat transfer printing |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1108018A true CA1108018A (en) | 1981-09-01 |
Family
ID=25335750
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA314,436A Expired CA1108018A (en) | 1977-12-16 | 1978-10-26 | Sheet containing sublimable dye and blocking agent for heat transfer printing |
Country Status (16)
| Country | Link |
|---|---|
| US (1) | US4171202A (en) |
| JP (1) | JPS5834306B2 (en) |
| AU (1) | AU4259378A (en) |
| BE (1) | BE872806A (en) |
| BR (1) | BR7808274A (en) |
| CA (1) | CA1108018A (en) |
| DE (1) | DE2853894A1 (en) |
| DK (1) | DK522878A (en) |
| ES (1) | ES476020A1 (en) |
| FR (1) | FR2411713A1 (en) |
| GB (1) | GB2010339B (en) |
| IL (1) | IL56205A (en) |
| IT (1) | IT1111092B (en) |
| NL (1) | NL7812268A (en) |
| NO (1) | NO784222L (en) |
| ZA (1) | ZA787031B (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4238190A (en) * | 1975-07-21 | 1980-12-09 | Thomas Rejto | Simultaneous transfer printing and embossing or surface texturing method |
| US4265630A (en) * | 1978-11-17 | 1981-05-05 | Ciba-Geigy Ag | Thermotransfer process for printing synthetic fibre materials with multi-color effects, and carrier for performing the process |
| DE2930163A1 (en) * | 1979-07-25 | 1981-02-12 | Hoechst Ag | METHOD FOR THE PRODUCTION OF RESERVE PRINTING EFFECTS BY THE TRANSFER PRINTING PROCEDURE AND SUITABLE TRANSFER PRINT CARRIERS THEREFOR |
| JPS5885394U (en) * | 1981-12-04 | 1983-06-09 | 北川工業株式会社 | Fixture |
| US4619665A (en) * | 1985-03-11 | 1986-10-28 | Technographics Printworld, Inc. | Sheet containing heat transferable dye and selective blocking agent for heat transfer printing |
| US6186207B1 (en) | 1988-09-06 | 2001-02-13 | Donald C. Berghauser | Press for transferring video prints to ceramic mugs and other surfaces |
| GB8900747D0 (en) * | 1989-01-13 | 1989-03-08 | Payne J M Innovators | Improved printing process |
| DE59712026D1 (en) * | 1996-09-12 | 2004-11-25 | Saurer Gmbh & Co Kg | Texturing machine with height adjustable thread guide |
| US5904738A (en) * | 1998-01-28 | 1999-05-18 | Crompton & Knowles Corporation | Gas-fade inhibition |
| US8337006B2 (en) * | 1998-05-06 | 2012-12-25 | Sawgrass Technologies, Inc. | Energy activated printing process |
| US6964722B2 (en) * | 2002-08-07 | 2005-11-15 | Trio Industries Holdings, L.L.C. | Method for producing a wood substrate having an image on at least one surface |
| US9399362B1 (en) | 2015-03-31 | 2016-07-26 | Vivid Transfers, LLC | Method of selectively transferring an image and heat-transfer assembly |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA999192A (en) | 1971-03-10 | 1976-11-02 | Sublistatic Holding Sa | Temporary supports, their preparation and their use in dry dyeing and in dry printing by hot transfer |
| US3940246A (en) * | 1971-04-26 | 1976-02-24 | Ciba-Geigy Ag | Sublimation transfer and isocyanate fixation of amino- or hydroxy-containing dyestuffs and transfer sheets therefor |
| JPS4983508A (en) * | 1972-12-20 | 1974-08-12 | ||
| JPS5743519B2 (en) * | 1974-06-24 | 1982-09-14 |
-
1977
- 1977-12-16 US US05/861,422 patent/US4171202A/en not_active Expired - Lifetime
-
1978
- 1978-10-26 CA CA314,436A patent/CA1108018A/en not_active Expired
- 1978-11-23 DK DK522878A patent/DK522878A/en not_active Application Discontinuation
- 1978-12-14 IT IT52299/78A patent/IT1111092B/en active
- 1978-12-14 IL IL56205A patent/IL56205A/en unknown
- 1978-12-14 ES ES476020A patent/ES476020A1/en not_active Expired
- 1978-12-14 GB GB7848497A patent/GB2010339B/en not_active Expired
- 1978-12-14 DE DE19782853894 patent/DE2853894A1/en not_active Withdrawn
- 1978-12-15 AU AU42593/78A patent/AU4259378A/en active Pending
- 1978-12-15 JP JP53154309A patent/JPS5834306B2/en not_active Expired
- 1978-12-15 FR FR7835388A patent/FR2411713A1/en not_active Withdrawn
- 1978-12-15 NO NO784222A patent/NO784222L/en unknown
- 1978-12-15 BR BR7808274A patent/BR7808274A/en unknown
- 1978-12-15 ZA ZA787031A patent/ZA787031B/en unknown
- 1978-12-15 BE BE192355A patent/BE872806A/en unknown
- 1978-12-18 NL NL7812268A patent/NL7812268A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| US4171202A (en) | 1979-10-16 |
| GB2010339B (en) | 1982-11-10 |
| IT1111092B (en) | 1986-01-13 |
| IL56205A (en) | 1982-09-30 |
| NL7812268A (en) | 1979-06-19 |
| IT7852299A0 (en) | 1978-12-14 |
| BE872806A (en) | 1979-03-30 |
| JPS5488407A (en) | 1979-07-13 |
| ZA787031B (en) | 1980-07-30 |
| GB2010339A (en) | 1979-06-27 |
| BR7808274A (en) | 1979-08-14 |
| FR2411713A1 (en) | 1979-07-13 |
| AU4259378A (en) | 1979-06-21 |
| NO784222L (en) | 1979-06-19 |
| DE2853894A1 (en) | 1979-06-21 |
| DK522878A (en) | 1978-06-17 |
| JPS5834306B2 (en) | 1983-07-26 |
| IL56205A0 (en) | 1979-03-12 |
| ES476020A1 (en) | 1979-06-16 |
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