JPS609066B2 - Labeling liquid composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to the use of multi-component marking liquids (marki
nglioujd).

This labeling liquid is highly reactive and can absorb part or substantially all of the visible spectrum with a wavelength of 400 to 500 millimicrons, and reacts with a recording material made sensitive by an acidic substance, for example, to produce a clear label. It forms the Various labeling liquids are known.

For example, Bamett K.
US Pat. No. 2,850,395, issued September 2, 1958, by M. Green, describes a printing fluid containing crystalline violet lactone and a red dye. According to the present invention, a usually colorless labeling liquid consisting of multiple components that absorbs a portion or substantially all of the visible spectrum of 400 to 500 millimicrons in wavelength is reacted with a suitable sensitive recording material to produce an extremely sharp, generally blue color. sign (recorded image)
In addition to being able to form a blue marker, a blue marker formed in this manner has an advantage in that it has excellent copying performance by xerography or xerox processing. The blue signs referred to here are colors ranging from deep blue to purple-blue.
It also includes pure tone color or steel blue color.

There are at least two types of colorless reactants used in the labeling liquid of the present invention.

Each of them develops color by reacting independently with a recording material sensitized with an appropriate acidic substance. The labeling liquid contains a liquid oil solvent and a colorless reactant dissolved in this solvent in a few percent as necessary, and develops a color when it comes into contact with a sensitive recording material, but the color is visible to the naked eye or to a photoconductor.
exhibits a blue color to electromagnetic photosensitive devices such as Furthermore, this color recording material has excellent copying properties when subjected to xerographic processing. *The labeling solution of the present invention is a colorless reactant, namely (A) crystalline violet lactone represented by the structural formula (i.e., 3,3-bis(4-dimethylaminophenyl)-6-dimethylaminophthalide).
Alone or in combination with penzoylleucomethylene blue (i.e., 3,7-bis(dimethylamino)-10-penzoinphenothiazine) represented by the structural formula (C),
and (B) 3,3-bis(1-ethyl-2-methyl-indol-3-yl) phthalide represented by the structural formula and 3,3-bis(1-benzyl-2-
It consists of at least one member selected from the group consisting of methyl-indol-3-yl) phthalide.

The amount of crystalline violet lactone (hereinafter referred to as CVL) is up to 2% by weight in the labeling solution of the present invention.

The amount of penzoyl leucomethylene blue (hereinafter referred to as BLMB), if present, is up to 1.5% by weight in the labeling liquid. The amount of colorless reactant remaining in the labeling solution is CV
The amount of L plus BLM old is generally up to 1.5% by weight of the marking fluid. In a preferred embodiment of the invention, the marking liquid is encapsulated in fine capsules and these capsules are applied onto the base sheet recording material.

The sensitive lower layer sheet (dish d) is in close contact with the base sheet recording material.
ersheet).

Such a capsule-bearing sheet is described in U.S. Pat.
ingsheet), when printing pressure is applied to the base sheet, label droplets corresponding to the printed image are eluted onto the sensitive undersheet and colored. US Pat. No. 2,712,507 also discloses a preferred method of forming capsules. Another preferred method of making oil-containing microcapsules is described by Palette Kay Green and Lowell Schleicher.
July 2, 1957 by El I Schleicher
U.S. Patent No. 2,800,457, issued on June 3, 1962, and U.S. Pat.
It is written on the instrument number. Application of printing pressure causes the capsule to rupture, releasing a small droplet of marking liquid within the capsule.

At least one substance that is an acid reactant is coated or impregnated on the surface of the lower sheet, and the base sheet is provided with a component that develops color when it comes into contact with the reactant. Typical acidic substances are oil-insoluble minerals or particulate inorganic solid materials,
For example, caolitho, attapulgite
te), silica gels, zeolites, etc., and organic polymeric acidic substances, such as oil-soluble acid-reactive phenolic resins.Such polymeric materials will be further described herein.The present invention One of the main features of is to provide a multi-component labeling liquid, which forms a bright blue color that absorbs the incident white light component, especially light between 400 and 500 millimicrons. The blue print has excellent copying performance in xerography.It has not been possible to form a blue print with such characteristics until now.The recording material has a fibrous structure such as paper or an organic polymer. A base sheet or web material having a continuous film-like structure of material.
r) on which a coloring reactant is supported.

When the acid reactants are in particulate form, they are arranged in close apposition to form a surface that is apparently receptive to the following liquid, yet each particle is arranged in such a way that it is in substantial contact with the color forming liquid.

When using an acidic material of a phenolic polymer, the acidic particles can be dispersed in a coating solution and applied to the recording material. This recording material is coated with a pre-colored or colored marking liquid, but in the present invention, a novel oil-based marking liquid containing a normally colorless coloring reactant is used. It has characteristics. All suitable particles are substantially insoluble in water, but at least one type of particles is soluble in oil-based inks and at least another type is insoluble in oil-based inks. The color-forming reactant material contained in the novel labeling liquid of the present invention performs an acid-base reaction with an acid reactant to form a clear color-forming mark on a recording material. The coloring mechanism is such that a coloring reactant, such as penzoylleucomethylene blue, comes into contact with acidic particles on the recording material, is hydrolyzed, and further undergoes oxidation/reduction reactions, thereby producing color. When several color-forming reactants are applied through a common solvent, it is natural that the color will be a mixture of the individual colors. In its simplest form, the present invention comprises an acidic reactant (as shown later in specific examples, represented by a powdered oil-soluble phenolic polymer that reacts as an acid and an acidic mineral, either alone or in combination). This can be carried out using a combination of the above-mentioned colorless color-forming liquids, but it is also possible to use reactants with different properties if desired.

These various properties are physical or chemical properties. Color reactant recording systems are called color reactant recording systems because the components of the color reactant materials used in such systems are essentially colorless and, when applied to a particularly sensitive recording material surface, may readily become colored or This is because it is possible to develop color after contacting the material for a long time.

Even if the recording sheet is sensitive, it can also be printed in some areas with conventional colored printing inks and in other areas with the novel colorless liquid of the present invention. Unlike pigment liquids, the color forming material in the novel colorless liquid of the present invention is a combination of various colorless reactants that chemically react with the acidic reactants on the sheet to produce a visible, vivid color. emits.

For recording purposes, the colorless reactant is applied to the recording surface and immediately develops a vivid color so that any recorded content can be clearly displayed (i.e., the color is clear and the color intensity is high); It is also desirable that the markers remain colored for a long time and serve the purpose of permanent records.

Colored dyes have various drawbacks such as photobleaching, thermal bleaching, and various molecular rearrangements and decompositions, which may cause the coloring to disappear partially or completely. Polymeric materials are well suited for use in the present invention because they are sufficiently acid-active and oil-soluble; patents for these materials include Robert E. Miller and Paul S. Phillips Giunier. (PauISrhillips.
No. 744,601, filed June 17, 196 Yoo, which is based on U.S. Patent Application No. 392,404 filed August 27, 1964 by John Jr.

Suitable solvents and oil-soluble organic polymeric materials suitable for use in the present invention include acid-reactive phenolic aldehyde polymers, phenol-acetylene polymers, and styrene-maleic anhydride copolymers. Polymers and ethylene
Maleic acid-rosin resin obtained by partially or totally hydrolyzing maleic anhydride copolymer, carboxypolymethylene (trade name: carbopoi934), and vinyl methyl ether-maleic anhydride copolymer completely or partially hydrolyzed. Polymers can be cited as a representative example of highly reactive acid copolymer materials.

Among the phenolic aldehyde polymers that have been found to be useful are those commonly referred to as novolacs, which are soluble in common organic solvents and permanently cured in the absence of crosslinking agents. It is characterized by being soluble.

Another example of a useful phenolic polymeric material is an alkylphenol-acetylene resin, which is also soluble in common organic solvents and is permanently soluble when not treated with a crosslinking agent. Phenolic polymeric materials useful in the practice of this invention generally have free hydroxyl groups and are free of groups that tend to unmelt or crosslink the polymer, such as methylol, are soluble in organic solvents and are aqueous. She has the characteristic of being relatively intolerant. A useful experimental method for selecting a suitable phenolic resin involves measuring the infrared absorption pattern of candidate materials.

Suitable phenolic resin is 3200~3500cm-1
It shows absorption in the region (indicating the presence of free hydroxyl groups), but 16
It was found that the sample had no absorption in the 00-1700 cm-1 region. The latter absorption region represents a reduced activity of the hydroxyl groups, so that such groups are not available for reaction with the color-forming materials mentioned above. For the preparation of phenol-formaldehyde polymeric materials suitable for the practice of the present invention, see Industrial and Engineering Chemistry (Industrial and Engineering Chemistry).
43, pp. 134-141 (January 1951 issue), ``Special polymers among these are described in 193 by Herbert Hennel (Herbert Honet).
The production of phenol-acetylene polymers is described in Example 1 of U.S. Pat.
Engineering Chemistry” Volume 41, No. 73~
It is written on page 7 (194g King January issue).

The preparation of copolymers of maleic anhydride is described, for example, by Calvin E. Schildk.
``Vinyl and Related Polymers'' by
PoMme Dai) 2nd edition, published April 1859, John
Willie & Sons (John Wmey & So
The production of maleic anhydride-vinyl copolymers is described in the literature, such as the preparation of maleic anhydride-vinyl copolymers described by Co., Ltd.

This document includes pages 65-68 (styrene-maleic anhydride copolymer), pages 628-630 (pinyl methyl ether-maleic anhydride copolymer), and pages 530-53.
You can refer to page 1 (ethylene-monohydric maleic acid copolymer). The solvent portion of the labeling liquid can dissolve the coloring component.

Solvents can be volatile or nonvolatile and can be single component or multicomponent solvents that are all or partially volatile.
Examples of volatile solvents useful with basic chromogens and acidic polymeric label-forming components include toluene,
Mention may be made of petroleum distillates, perchloroethylene and xylene. Examples of non-volatile solvents include high-boiling petroleum fractions and chlorinated diphenyls. In general, a broad range of vehicle solvents will be capable of dissolving at least 1% by weight, preferably 2% or more, of the basic color forming material, and will be capable of dissolving large amounts of polymeric material (say up to 15% or more). ) must be selected so that the reaction can be carried out sufficiently.

However, in a preferred system, a solvent must be chosen that will dissolve the excess polymeric material to maximize the reaction effect of the color-forming substance and thus maximize the color development at the site of the reaction. Another criterion for choosing a solvent is that it does not interfere with the label formation reaction. In some cases, the presence of a solvent can interfere with the label-forming reaction or reduce the strength of the label; in these cases, a sufficiently volatile solvent should be chosen to remove the label-forming components. After bringing into intimate admixture in the form of a solution, the solvent must separate from the solution and disappear from the reaction sites, so that the label-forming reaction can proceed. In the above-mentioned base-acid coloring system, the selected polymeric label-forming component (single or multiple) is more acidic than the basic coloring compound, and is reactive with the coloring material, resulting in a clear color. One must choose one that can develop color or change color.

Kaolin, as it is commonly known and used in the paper industry as a "chemist", is a non-porous and water-resistant oil that has the acidic properties necessary to produce the color penzoylleucomethylene blue, one of the key color-forming ingredients. It is particularly preferred as a non-combustible particulate mineral material.

White china clay is used because it is white and has a plate-like particle system, so it has unparalleled coverage in aqueous slurry, and its supply is abundant worldwide. Industrial and paper processing industries have historically commonly used this;
White china clay is an ideal material because of its low cost and low cost.

Another type of particulate, virtually colorless, oil- and water-insoluble mineral material that requires acidic properties are those that appear to be equivalent to kaolin, some of which are pentonites. . Atabarugide can be used as an effective colorless reactant in the present invention, which upon contact with the novel liquid colorless chromogenic compounds of the present invention undergoes an electron donating and accepting reaction to develop color.

Also, because of its high oil-absorbing capacity, attapulgite is doubly useful as an absorbing reactant for coating on paper, and for coloring oil-soluble color-forming compounds that can be applied thereto.
By selecting the materials as described above, a wide variety of specific compositions can be prepared on a dry basis, and these compositions can optionally be made into aqueous slurries which are then applied to the finished paper sheet. , may also be applied in a preferred manner to a wet paper sheet as a constituent thereof;
Alternatively, it may be a paper finishing part for producing a paper sheet, or on the other hand, a continuous film-like web such as a recording sheet, recording band or recording stripe of synthetic organic polymeric material or other recording support. It may also be applied as a dispersion to the surface of the material. Generally, and without being limited in any way, an aqueous dispersion of particulate material may consist of 40-75% by weight water, with the remaining 60-25% being particulate reactants, which are generally divided. The oil-soluble component is divided into 5% by weight of the oil-insoluble component and 1% by weight of the oil-soluble component, but this is just a guideline and is not limiting.

Adhesive paper coating binders are added to adhere the particles to the base web, but of course should not be used in amounts that physically mask the particles or render them chemically inert. Also, of course, an excessive amount of adhesive should not be used than is actually required.

The binder can be selected from paper coating latexes such as styrene-butadiene and acrylic latexes.

If desired, an amount of silica gel can be used up to an amount equal to the amount of acid polymeric material.

This silica gel is insoluble in oil but absorbs oil, can be finely ground, is colorless, easily disperses in water, and can also be treated to increase its porosity and effectiveness as an acid. The particle size of the reactants is preferably from 1 micron up to 3 microns, but is not necessarily limited to this range for reasons of efficiency and economy.

For example, if it is expensive to grind the material to the most effective size, it may be possible to use larger particles as long as a sufficient color reaction per unit area of the recording material is observed. One of the considerations for the preferred embodiment of the invention relates to the manufacture of the recording sheet, and the best way to make the sheet sensitive is to apply a coating in the paper machine to the rolled paper web. step is to apply an aqueous slurry of the composition of the present invention.

Such coating compositions contain a binder and may also contain the same foam inhibitors and dispersants as in the paper coating. The present invention will be further illustrated in accordance with the following examples.

The reactants, proportions, and other specific conditions are representative and are not intended to limit the invention. Example 1 Violet lactone crystals 1.5% by weight and 3.3% by weight
-pis(1-ethyl-2-methyl-indol-3-yl)phthalide 0. $% by weight is dissolved in an oil consisting of a 2:1 mixture by weight of chlorinated biphenyls and saturated hydrocarbons to produce a homogeneous solution.

This solution had a purple-blue tint on the sensitive recording material. Example 2 Another solution was prepared according to Example 1 and served as a control.

This solution contains 0.3-bis(1-ethyl-2-methyl-indol-3-yl)phthalide. 0.9% by weight of penzoyl leucomethylene flue is used instead of % by weight of base. This solution had a steel blue tint on the sensitive recording material. Example 3 Crystalline violet lactone 1.7% by weight
and 0.55% by weight of 3,3-bis(1-ethyl-2-methyl-indol-3-yl)phthalide, and 3,3-
A mixture of 0.55% by weight of bis(1-benzyl-2-methyl-indol-3-yl)phthalide, 64.8 parts by weight of monoisopropylbiphenyl and 3 parts by weight of saturated hydrocarbon
A homogeneous solution is prepared by dissolving in oil consisting of 2.4 parts by weight.

All weight percentages are based on the total weight of the solution. This solution had a purple-blue tint on the sensitive recording material. Example 4 The colorless labeling solutions prepared in Examples 1-3 are encapsulated by the following steps.

A solution of 11% by weight made by dissolving pork skin gelatin in water and adding 71 grams of water.
200 mg of any of the above labeling solutions are suspended in 0.0 mL of water.

This emulsion has a pH of 6.5 at 5500. Gelatin sol is 11% Gelatin 996 per Elside 75 (
Contains E1side75)4. The emulsion 500
10.5 kg of a 5% solution of polyvinyl methyl ether-maleic anhydride copolymer, 87 kg of 11% by weight gum arabic dissolved in water, and a further 590 kg of water, about 70 q0.
Coacervation is caused by mixing the mixture with water. The resulting mixture is kept under gentle continuous stirring at 5500 ℃. The pH of the mixture is adjusted to 9 using 20% sodium hydroxide. Then slowly at first, 14%
of acetic acid is added dropwise. The internal phase of the ink thus produced, the droplets, is supported by the walls of a liquid capsule consisting of a composite of gelatin, gum arabic, and polyvinyl methyl ether monohydric maleic acid copolymer, which increases the coacervating power. (Coacelvateゎce
), the material is supported in a dense manner around the oil drop. Next, the produced capsules are cooled to a temperature of about 10 qo and solidified while being continuously stirred.

The capsules are then cooled and then 7.5' of a 25% by weight aqueous solution of glitaraldehyde is added as the walls of the capsules solidify. The glutaraldehyde on the wall of the polymeric material serves to harden and solidify the wall. After 1 hour, an additional 15' of a 5% by weight aqueous solution of polyvinyl methyl ether-maleic anhydride copolymer is added to prevent the capsules from agglomerating.

Next, add 20% sodium hydroxide dropwise to adjust the pH to about 10.
Adjust slowly to The capsules can then be handled as solids dispersed in the remaining aqueous medium or dried and processed as finely divided solids. Example 5 Capsules made according to the process of Example 4 are used to form prints on various sensitive sheets.

Table 1 lists character 1 of the xerographic copy of each print obtained from the Xerox Model 2400.
l) for the Siemens densitometer (Sieme
It is the reflection intensity measured using r) for nsDensitome.

Each of the four different types of sensitive recording materials exhibits excellent copying properties when using the labeling liquid of the present invention.

The present invention includes the following embodiments.

[1--A composition according to claim 1 or 2, wherein the amount of component (B) is in the range up to 1.5% by weight.

'21 (a) Support web or sheet material and (
b) a pressure-sensitive recording unit supported by the sheet material and comprising a label-forming component and a releasable liquid solvent for the label-forming component juxtaposed adjacent to each other; Paragraph 1 or 2
The labeling liquid composition according to any one of paragraphs 1 and 2, and a Lewis acid-type electron-accepting material that reacts with the labeling liquid composition to produce a label, such that the label-forming component reacts with this labeling liquid composition upon pressurized release of the liquid solvent. A pressure-sensitive recording unit characterized by being catalytically reactive in the released solvent.

[3' Innerohase of solvent vehicle]
A transfer coating having as a finely dispersed layer a large number of microscopic pressure-rupturable capsules containing
a first web or sheet having a coating on one surface thereof; a second web or sheet having an adhesive coating dispersed on or in its surface; claims 1 or 2; and a second coating component in the form of an electron-accepting substance of the Lewis acid type;
and a second web or sheet are held in a mutually facing arrangement such that the transfer coating and the adhesive coating are in face-to-face relationship, and one of said coating components is attached to the first web or sheet. or dissolved in a solvent liquid vehicle present as an inner layer of a number of microscopic pressure-rupturable capsules in a transfer coating on or within the sheet, the other one of said coating components being a second in the adhesive coating on the web of the parentheses, coupled with a second web to receive another substance for contact with a portion of the adhesive coating of the parentheses, thus locally impacting said capsule. and rupture to release a liquid vehicle containing one coating component from at least some of the capsules on adjacent adhesive coatings, a contact reaction occurs between the two coating components. , characterized in that a blue substance is produced when the labeling liquid composition acts on a Lewis acid type electron-accepting substance that causes a color change in this composition and makes it a blue-colored substance. Label-forming unit.

Claims (1)

[Scope of Claims] 1. A color-forming component containing (A) up to 2% by weight of 3,3-bis(4-dimethylaminophenyl)-6-dimethylaminophthalide, and (B) a lesser amount of (a )3・3
-bis(1-ethyl-2-methyl-indol-3-yl)phthalide and (b) at least one selected from the group consisting of 3,3-bis(1-benzyl-2-methyl-indol-3-yl)phthalide. 1. A labeling liquid composition comprising an organic oily solution of a color-forming component. 2 The oily solution further contains up to 1.5% by weight of (C) 3,7-bis(dimethylamino)-10-benzoylphenothiazine, and component (B) is combined with component (A) and component (C). ) in an amount less than the total amount of the composition according to claim 1.