DE1669263A1 - Instant drying, non-evaporating ink - Google Patents

Description

FATKKfANWiIt ₁ TI -Ϊ D Ω Q ^ R

DR. ING. KARL »OIKMltT · DIPL-INO, AUlRT IOIHMlRf

28 BREMEN, FEMSSTRASSE 24 - FERNRUF (0421) 491700

File number: NeUanmeldUng Posf «fi« <* kOBtQ: Homfeure U6O89

lenbkontoi Iransar Bank, Iranian, Account 1001449

Nam. d. Ann ·., THE PAHKBR PEN GOMPAT / My character: P 166 28 Bremen, 11 October 1966 _#

THE PAEKSR PM GOMPANY ₉ Janeeville, Wisconsin, Y.St.A.

Instant drying, non-evaporating ink

The present invention relates to a non-aqueous Ink with improved writing properties

In particular, is it for? Inks desired that they dry quickly, but do not evaporate too quickly before applying to the paper, and furthermore not "

leak and not penetrate the paper. Sine ink of low viscosity and large surface tension _s has the Eigensehaften this high degree. exists according to dei ^; Invention from a major part of a

009831/3042

non-aqueous, molecule-associated carrier liquid, which contains molecules capable of polyfunctional hydrogen bonds, and a smaller one Proportion of a coloring substance

The carrier liquid can consist of a single substance or a mixture, or of a solution ^ a substance which has at least one point for hydrogen bonding and which in a solvent, that itself for the formation of hydrogen bonds is capable of being dissolved by molecule association between solvent and dissolved molecules

A molecule-associated liquid is understood to mean one that contains molecules in which a hydrogen atom by strong forces of two Atoms rather than being attracted to just one, so it can be viewed as a bond between these atoms can. This hydrogen bond is largely electrical and can only be between the most electronegative Form atoms. Their occurrence was confirmed by conventional spectroscopic and crystal structure studies as well as proven by the evaluation of physico-chemical data * Form fluorine, oxygen and nitrogen strong hydrogen bonds, the strength of the

009839/2042

Bonding increases the electronegativity of the atoms bridged by water off. For example, the phenols form stronger Waseerstoffbrückenblndungen as aliphatiBche alcohols, n because of the increased electrical "gativit t of oxygen atoms by BesonanSt examples ■ pi *! · AsBOaiierten for Vasseratoffbrückenbindungen in Kolekül- liquids are following!

F-H. ..F Q-H, ,.O Ν-Η · ..N H-H. . “F K-H. ..0

In certain cases where the carbon atom is attached to a strongly electronegative group, form hydrogen bonds between carbon and oxygen (C-H. *. Ο) and between carbon and Nitrogen (C-H .. * N). In the same way can chlorine

and sulfur form weak hydrogen bonds, ™ when the other atoms are strongly electronegative, e.g.

0-Η 01 and N-H ... S.

Molecule-associated liquids are accordingly those that are relatively complex, by connecting a relatively large but not exactly determinable number

009839/2042

6AD

• «4 -

individual molecules through hydrogen bonds resulting molecular structures contain

In molecule-associated substances, the hydrogen bond can occur consist of different molecules of the same substance between two identical atoms, as it is with the alcohols of the pail · you bond can consist of different molecules of the same substance between two different atoms, as in the case of formamides, or the bond can be formed between atoms of molecules of different substances be·

The organic carrier liquid preferably consists of small molecules which are di- or poly-functional with respect to hydrogen bonds to such an extent that the carrier liquid has quasi-crystalline properties even in the liquid state. The hydrogen bonds cause the organic molecules to join together or clump together to form groups in a three-dimensional network. The molecule clumps are too large to pass through between the forming molecules of a web or a surface and are therefore of one

009839/2042

- ORIGINAL INSPECTED

Penetration of the web excluded

Examples of suitable di-functional imprinting liquids are hydrazine, sormamide, hydroxy alcohols, amides, esters, diamines, symmetrical bifluorotetraobloroethanes and the like. Suitable polyfunctional carrier liquids are polyhydroxy alcohols, · Β · oleo-glycerol »! , Polyamines, e.g. Triethylenetetramine, hydrazine polymeric fluorinated hydrocarbons, see “Trifluor-trichloroethane unö. Dargl "Examples of liquids that are monofunctional in relation to hydrogen bonds are aliphatic alcohols, ss« B * methyl-r, ethy! -alcohol, simple amines, s «B * n-butyla3! in _s tert * butyl-amine, ketones * z # E * acetone and the like *

MäSe Molskül- * apao2: iated organic Ink can be any © commonly available

fllrbeijue fabrics are used »Bsr coloring fabric '

Can be an organic dye or an inorganic pigment, but organic dyes are obviously organic dyes which are used for non-aqueous saksite, both in a 3-carrier and also in water. arb3tc-.fx verwends-'j W ^ x = S ₅ AEAT -It ^ ⁵ dye, the fen ™ Denss a "43 of the ^I:.; -3 .-: i; '? "- and the fareupw - * Jltissigte I' ^-: ^ * f if5.2.1 euo5 ¹ ^ ^ .is; ■: ■ ': ■ & μΓ: \ ,,,...."_; - \ n.ä «5% ·."'." * ια; _{; ί} | ρλ ·; _; , ": ^; / Oe ü J (; OS / ™ ν) i» ±.

Dye can cause clogging and poor starting performance of the spring.

For a non-aqueous ink according to the invention, in particular the following typical organic dyes are used, which are present in both water and are also soluble in molecule-associated liquids such as formamide

National Alphazorine FG Cone. $ 200 CI. 42090

National Fast light Yellow 2 G O.I. 18965

Victoria Pure Blue BO CI. 42595

Brilliant Scarlet 3 R CI. 16255 -

Erie Black G.A.C Cone. CI. 30235

Diphenyl Dark Blue H C1, 30205

Ink Blue PP Pye U.S. Pat. 2,489

Me first five of the above dyes are from The Allied Chemical and Dye Corporation, New York, while Diphenyl Dark Blue R dye is manufactured by The Geigy Company, New York, and the Ink Blue PP dye is described in XJ * 3, Patent 2,439,463.

In the new class τοη inks is the MoIek ^: .L "l ~ associated ^ 03839/2042

1 S £ ° 2 6 3

- v> WW t - W w

The main liquid carrier Plüsaigkeit and makes the use of any other material, since "ale solvent are referred to for dl.e ink kbnnte _e nioht required" Though various additives in the ink may be contained to the extent of Papierdurchdringung that Trooknungsgeeohwindigkeit and Depending on the surface tension and viscosity, these substances are used in small amounts so that the molecular-associated liquid makes up the largest proportion of the total concentration of the additives, i.e. more than 50 mol percent.

The upper limit of the water-soluble dyes used in water-soluble dyes used on the basis of molecular-associated liquids is about 35%. With this composition, the ink solutions are generally too viscous for use in instruments intended for real liquids, although it is It is possible to use such a line for ball springs.

For a simple plush-ear bucket like the 0 CS 8 3 9/2 C 4 2

ORIGINAL INSPECTED

The usual pen of a draftsman is that preferred composition range of the feint Molecule-associated liquid base 1-25 percent by weight Dye · For conventional fountain pens with pointed nibs and various reservoirs and supply systems, the optimal viscosities are around 4 percent by weight of dye, but it can down to 1 percent by weight in some cases.

Although the molecule-associated liquids formed If webs do not penetrate appreciably, it has been found that the paper penetration properties of such liquids even further by the additional use of clumping agents that bind the level of hydrogen bonding Increase in the solution, and the effect that other substances with a low tendency to form Hydrogen bonds such as those with the clumping agent can be reduced · Suitable Lumping agents are organic substances that contain amino, hydroxyl, and fluorine groups, such as Cane sugar, cane sugar dioleate, arabitol, guar gum, Raffinose and trimethylol propane «These substances reduce the paper penetration properties of the ink carrier fluid if they are molecule-associated,

009839/2042

OR!

1369263

to a small extent in Besag for the urgent training of Hydrogen-bridging binary di-functional. Carrier fluids to be added «

Ea \ nirä ?, furthermore gsf under *, d & 3 the evaporation or soccion rate behind it, on the basis of a molecular association with liquidity, without the use of small amounts of non-evaporating additives, substances that interfere with the formation of waterborne substances

are capable of external bonds like liquid polyethylene glycol or monofluoroperhalo-mono-alcohols, reduce the evaporation of the ink carrier liquid essential·

The monofluoroperhalo-mono-alcohols are of the following general structure?

FCH ₉ - (C oil «) -0-H ₀ OH

C. Cr X C,.

Compounds of this class have two sites capable of forming hydrogen bonds, 3? and Ghj on "The fact that these at the ends of the molecule sit _f cause they icnerhelb 3 liquid quasicrystalline Strukturenj the, especially if χ a small number, dio property en ο: vortäusciisn α water piping *

CCS83S / 2042

- ίο -

sites capable of forming hydrogen bonds also cause a polarity to dissolve Dyes, and cause these molecules to convert to multi-hydroxy additives, such as drill sugar dioleate » hang around and associate with them.

Because of their polar arrangement, the monofluoro-perhalo-mono-alcohols have dye-dissolving power and low viscosity, so that the release of ink from the end of a pen is mainly determined by the surface tension compared to lines with flat cross-sectional shapes. The halogen substitution creates heavy molecules that are difficult to get into the atmosphere by thermal energy, thereby reducing volatility. The viscosity is low and the surface tension is generally greater than normally in quaai-crystalline liquids. ψ An example of a suitable, non-evaporating additive is 2,3 £ etrachloro-4-monofluorobutyl alcohol

The importance of non-evaporating additives lies in the relationship found between surface tension and viscosity of the carrier liquid. If the The surface tension is greater than the viscosity, so that

009839/2042

mainly the surface tension the fluid properties Depending on the carrier liquid, less ink is drawn from the tip to the tip while writing Paper dispensed and the small amount of ink dispensed when drawing a line approximates Instantly dry and not step or bleed through the paper. In order to do this, the viscosity must be used low compared to the surface tension of the liquid · Therefore, at larger surface areas- ^ tensions, a higher viscosity may exist, although the flow rate of a liquid is made up of a pipe will be decreased as its viscosity increases, an increase in viscosity increases a Liquid in the form of a drop that can be pulled out by a fountain pen or a nib tip It is only necessary, therefore, that the surface tension regulates the flow rate predominantly determined and sufficiently large, the liquid at the Pederepitze against the influence of viscosity which tends to draw the liquid from the tip of the peddler, which is drawn along a surface, to hold on »

If it becomes necessary to dilute the ink composition, e.g. to reduce the viscosity, it is desirable, the surface tension as little as 009839/2042

ORIGINAL INSPECTED

possible to change. Suitable non-aqueous diluents are the halogen-substituted hydrocarbons, because these usually have low viscosities and can be obtained in pure form · In the following are examples of halogen-substituted, non-aqueous Given diluent »Trifluor-trichloroethane, Trichlorethylene, perchlorethylene, monobromo-difluoro- ^ trichloroethane and mono-broa-difluor-mono-iodo-dichloroethane.

Hydrazine is also an excellent diluent for reducing the viscosity of non-aqueous inks, although inks made using hydrazine require special handling because of the toxicity and risk of explosion W allow molecule-associated liquid without lowering its surface tension and, in principle, hydrazine would be a preferred diluent «

Although the primary objective of the non-aqueous inks of the present invention is to provide a new, convenient notation enable and achieve this goal by using largely non-volatile liquids that are not so

009839/2042

evaporate as quickly as water and thus do not dry out in fountain pens, the result is "dry them down quickly on paper". The halogenated compounds offer advantages: "The halogen atoms are all heavy atoms" and increase the weight of a molecule when they replace a hydrogen atom. Because these molecules are much heavier, more kinetic energy is required "to get them out of their liquid surface into the atmosphere * In other words, they don't usually evaporate quickly from fountain pens or other containers." ₈ different chemical principles can be applied to written lines, and because of their strongly negative properties they evaporate much faster

To help prevent ™ skin drying

Ink at the tip of a pen, which can cause constipation or poor starting performance, was found "that it is desirable ₉ to add a hygroscopic material of the ink solution _β Although 3? Räger" llüssigkeiteiij as formamide itself hygroscopic are _s this property can by adding small amounts of Substances such as anhydrous lithium chloride, anhydrous calcium chloride, potassium acetate »glycerine or 0 093 39/2 04 2

like. Be reinforced. By using such Substances, the tip of a pen remains moist and ready to write at any time, even if they are used over long periods of time Time remains uncovered.

The concentration of additive or ingredients in the final molecule-associated liquid-based ink is not critical. Depending on the desired properties of the ink w and the intended use of various concentrations of Klumpungsmittel, evaporation-reducing substances and / or hygroscopic substances may be used. In general, small but certain amounts of any of these substances can be used to improve the properties of the ink. The particular concentrations can vary in the range of about 1 to 34 weight percent.

The maximum additive concentration in inks Molecule-associated liquid base is 50 mole percent additive. Would this focus exceeded, more additive molecules than Carrier-liquid molecules are present. The practical one applied range is therefore not greater than 33 mole percent. This is the case when the additive

009839/2042

- 15 -

«Knows about the formation of water-metal bridge bonds has capable sites per molecule and therefore two difunctional carrier liquid molecules be able to associate with an additive

Ia "The following are examples of the various in the substances contained in the ink according to the invention}

Execution example 1

Example of a basic mixture of a dye in a pormamide carrier liquid. The new, formamide-based inks according to the invention are produced by first making sure, by heating and stirring, that formamide is ammonia-free * Sarauf becomes the dye added »in some cases the other additives, and dissolved · After filtering the solution is ready for use · If desired, the |

Additive before the addition of the dye in the formamide solved·

Dye \ Formamide 100 grams (Natl. Alphasorine F.G. Cons., 200 ^) 5 grams

From example 2

A second example of a Pormamid Ink Master Mix " 009839/2042

Formamide 100 grams Dye (diphenyl Dark blue R) 1.30 grams Embodiment 5

An example of a Formamich ink with an anhydrous, hydrophilic substance

Formamide 100 grams Dye 5 grams Lithium chloride (anhydrous) 1.05 grams Embodiment 4

An example of a formamide ink with a non-evaporating additive.

Formamide 100 grams

Dye 5 grams of polyethylene glycol No.

200 5.25 gram

Execution example ü>

A second example of formamide Tiiite with a non-evaporating additive "hydroxyethyl formamide is particularly so of Voi * in part because it heavier

0 0 9 8 3 3/2 0 ^; ; i:

«. 17 -

MoIeMiIe contains j to increase the ax viscosity dsr Jjoswng ,, without affecting their surface tension *

Formamide 100 fe-aram

Hydroxyäthyl-IoriHamid 11 «1 G-ranmi Dye (Blue PI- Inks) 5 * 55 grams

Example .6

An example of a jj'or-m & iaid sirite with a non-vaporizing one and a wasaaraasieiien & Gn additive

Formamide 100 grams

Dye 5 grams.

Polyethylene GlySol Jf ο * 200 5c 23 grams LithiuoiChlüriä (v; asss3? Free) 3? 15 ßraisa

sl 7

äβmnαlwKίιt ^ t

An example of a jormamid ink with a niclat evaporating and a water-attracting additive with the addition of water β

Formamide 100 Crraam

Dye 5 grams

Polyethylene glycol Hp * 200 5.25 grams Solution (see below) a 3c15 grams

a = 2 Graiam lithium chloride (vja

in 73 © ramm Wg, saer

009339/2042

Embodiment 8

An example of a formamide ink that contains additional clumping agents to help keep things from sticking out To support solvent molecules of the formamide and to improve their paper performance.

Formamide 10.17 grams of Ar-aMtol (a sugar derivative) 4 * 20 grams of dye o _e ol & ramm

33x11 Example of an i'drmamid-ink with pure cane sugar as an anti-inflammatory agent. "The cane sugar is soluble in its pure, non-esterified ore-in and is effective as an anti-inflammatory agent. The existing _f öi-f unct ioneil u V / aöserstoffbräcken effect: the formamide iDrager liquid makes this a good solvent for cane sugar.

formamid 17cc

Cane sugar (pure) O "57 grams of coloring 0.01 grams

009839/2042

Execution 8example 10

An example of a formamide ink with monofluoroperhalomono alcohol as an evaporation reducing agent.

Formamide 9 grams

2,3, tetrachloro-4-monofluorobutyl alcohol 1 gram of dye (inks blue PP) 0.5 grams

Execution example 11

In this example the effect of molecule association through the use of a monofunctional ink carrier liquid (n-Butyl-amine) together with a poly-functional additive (trimethylolpropane

'Ai-C- (CHpOH),). The effective reduction the paper penetration is determined by the length of the lines created with higher consistency inks I.

Eusatsstoff that forms hydrogen bonds “The tip of a conventional fountain pen was placed inside a microscope and thereupon was <Her ^ darspitze with equal amounts Ink loaded with different contents of additives * The following are the results:

0 0 9 8 3 9/2042

viscosity Mole percent Length of (Centipoise) Additive preserved line
(cm) _ O 5.59 1.56 12.1 8o38 2.27 16.49 9.65 6.59 23.89 12.70

In a similar experiment, an addition of 5 percent eaffinose to tertiary butyl amine as the carrier liquid increased the length of the ink line from 6.86 cm in the control experiment to over 76.2 cm and shows the effectiveness of a hydrogen-bonding additive that works with a In a comparative experiment, an ink composed of 10 grams of tetrachlorethylene (Cl ₂ C = C Cl ₂ ), 1.4 grams of cane sugar dioleate and traces of an alcoholic sol from Past Blue R penetrated a writing paper so quickly that it was impossible to draw a well-defined line, whereas the same ink, using 10 grams of trifluorotriehlorathane instead of the tetrachloro-ethylene, did not penetrate and formed a well-defined line.

The ones given in the preceding exemplary embodiments Compositions limit the present

009839/2042

Invention is not one, much is only served by the limited to the following patent claims »

0 0 3 8 3 "■ I? 0 h 2

Claims (2)

Claims 1. Instant drying, non-evaporating ink with a viscosity not exceeding lOGO centipoise, characterized by a major proportion of a non-aqueous, molecule-associated carrier liquid, those for polyfunctional hydrogen bonds contains capable molecules, and a smaller proportion of a coloring substance. 2. Ink according to claim 1, characterized in that formamide is used as the molecule-associated liquid and an organic dye is used as the coloring substance. 3 ο Ink according to claim 1 or 2, characterized in that a soluble additive having at least one hydrogen bridge bond per molecule is contained as a further component. 4o ink according to any one of claims 1 to 3, characterized marked that as an additional Besfendteil 0 0 9 3 8> ^1/2 0 Λ 2 Klurapmittel that the exhaustion of the '.'asnerstoffbruckentinden increased in the molecule-associated fluid, contain eats. 5 # ink according to any one of claims 1 "bin 4, characterized indicated that the ink additionally contains a substance that reduces evaporation « b <t Ink according to one of Claims 1 to 5 »characterized in that the ink additionally contains a hygroscopic substance. Q Q 9 8 3 9> 2 Q <· 2