JPS5876473A - Improved printing ink composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION An improved printing ink, more particularly an irises, is directed to a printing ink adapted for high speed printing operations. This improved ink uses a novel sterile clay complex that is dispersible in the right-wall vehicle and forms a gel within the medium.

Recently, as the circulation of newspapers has rapidly increased to the level of VC, the development and use of ShoSokuyo@- has become popular in the printing industry. This required printing inks that dried (set) quickly. In addition, such a multi-speed printing machine can set the size, tack (adhesion, task), permeability, and body thickness in less than one second.
Requires ink to maintain proper balance of control.

j) Ink with too strong tackiness may cause paper to tear or ink to blur, ie, misting, during high-speed printing.

Also, inks with insufficient tack properties do not transfer properly during printing operations. If the penetrating nature of the ink is too high, the printed characters may be visible from the back side of the paper or may be blurred. If you are concerned about the degree of penetration, even if the ink appears to be set, it will stain (smud).
ging) may occur. The ink must have a body that prevents it from flying out due to centrifugal force when used at high speeds. In contrast, thick, viscous ink does not ride properly on the stamp roller yc due to ink retention.

Because of these numerous properties and conditions, it is necessary for the ink industry to use multiple formulations of inks. An example is Japanese Patent No. 2,750,2
No. 96 contains a colorant dispersed in a vehicle containing an oil-soluble resin binder that is bath-soluble in mineral oil, and is treated with an aliphatic amine having a 64-carbon aliphatic chain association. A printing ink containing bentonite is shown. In contrast, U.S. Patent No. 2,754,219 discloses that montmorillonite is added to an ink vehicle whose main vehicle component is a hydrocarbon containing an aromatic component by adding a specific compound having a long chain group t of 12 or more carbon atoms. The production of an anti-missing Inkuri ink prepared by adding imitative particles of an organic derivative of montmorillonite obtained by processing is shown.

This tree is 18! ! 1, as well as U.S. Patent No. 2,73
No. 9.067 discloses a printing ink formulated with an improved clay that forms a gel in one vehicle and exhibits substantial gel consistency in one vehicle. However, these conventional printing inks have a number of disadvantages. For example, some inks require the use of undesirably polar dispersants. This polar dispersant reacts with other ink formulation components and detracts from the desired properties of the ink. 1 In addition, other types of ink need to be passed through roller mills many times to apply shearing action many times, and only then can a printing ink with a stable viscosity that does not increase in viscosity even during storage be produced. or can be obtained. Accordingly, this increases labor costs and requires interruption of ink manufacturing operations.

Unlike these conventional inks, U.S. Patent No. 4.193
．． No. 806 describes a methyl benzyl dialkyl ammonium compound or a dibenzyl dialkyl ammonium compound containing an alkyl group having 14 to 22 carbon atoms,
Organophilic clay gel-forming agents (GS
The production of a storage-stable printing ink comprising a gelling agent and an organic vehicle for the ink is disclosed. Unlike conventional printing inks containing gel-forming agents whose viscosity continues to increase, ζO U.S. Patented O Printing 1 ink is an ink that can achieve the desired viscosity level just by passing it through an S-roll mill once. has been done. This U.S. patented printing ink was a major advance in this technology, but
In addition, there are some items that require separate improvements. This is because the printing ink book of this US patent still requires the same high shearing effect as before to obtain a viscosity level suitable for use.

The present inventor unexpectedly discovered that organic cations, organic anions, and smectite clays are
It is a φ reaction product obtained by reacting 00 with a smectite clay having a cation exchange capacity of 75 bar equivalent or more, in which the organic cation-organic anion complex of 7 is intercalated with the smectite clay. t(int@r
calate) Shioshi and smectite clay cation exchange site (Sai), 1111t@s
) is substituted with said organic cation, the novel organophilic clay exhibits high dispersibility in non-aqueous fluid systems and is a gel-forming agent (g @ 1 l).
ant). (Patent Application No. 1983 filed by the present applicant on the same day: “Organophilic clay gel-forming agent”)
reference). Unexpectedly, a printing ink made by using this new organophilic clay gel-forming agent and blending it as a thickener into an organic vehicle for ink containing dispersed ink colorants is excellent. The present inventor has discovered that it has various properties.

The tenth aspect of the present invention is that an organic cation,
organic anions and at least 75 per 100 f of clay.
The organic kanone-organic anion complex is intercalated into the smectite clay as a reaction product with a smectite clay having a milliequivalent cation exchange capacity, and the kanone exchange site of the smectite clay is the organic kanone-organic anion complex. An organophilic clay gel-forming agent or gelling agent (2) consisting of a reaction product substituted with a cation and an ink color viscosity (b) are dispersed in an organic vehicle for ink. Printing ink with percentage characteristics.

In addition, in the above, "the organic cation-organic anion complex intercalates into the smectite clay" means that it penetrates into the intermediate layer of the complex t1 clay.

The printing ink of the present invention comprises an organic vehicle for the ink in which an ink color additive and an organophilic clay negative gel former are dispersed. The organic vehicle for the ink consists of a solvent and a binder. The solvent is a high boiling point hydrocarbon, preferably a high boiling point aliphatic solvent or a mixture thereof. Binders are synthetic or natural resins with film-forming properties and are used as carriers for the pigments. The type of binder used will vary depending on the intended use of the printing ink.

Binders that can be used include drying oil faces, alkyd resins, polyester vehicles, urethane alkyds, and the like. Ink colorants are applied to pigments or pre-dispersed bases. This pre-dispersed paste contains pigment, vehicle and solvent. By incorporating other additives into the printing ink, the ink properties can be modified for special applications. These additives include wax compounds, driers, dispersants, pigment extenders,
Antioxidants etc.

The organophilic clay used in the present invention can be prepared by the usual method 9 and t.
tf rice ffi! It can be produced by the method described in No. 11K 4,105,578. It is preferable to manufacture it by the following method. That is, an aqueous slurry of smectite clay is prepared by dispersing 1 to 80 parts by weight of smectite clay in water (a), and this slurry is heated, preferably to a temperature between 20 and 100°C. ),
Adding 5 to 100 millimeters of organic anion per 100 f of smectite clay (based on 100% active clay), and increasing both the cation exchange capacity of the smectite clay and the cationic reaction activity of the added organic anion. A sufficient amount of organic kanone is also added to satisfy the reaction condition, and the reaction solution is stirred in the meantime.
I=b, the intercalation is 9 ψφ, and the reaction is continued for a sufficient time to form a reaction product in which the smectite-type clay is substituted with an organic cation at the canonic exchange site (d).

Furthermore, it is preferable to use a method for producing an organophilic clay gel-forming agent, which is characterized in that the reaction product is collected as an organophilic clay-negative gel-forming agent.

The organic cationic compound and organic anionic compound used in the present invention can be selected from a wide range of substances.

The organic cationic compound that can be used in the present invention is one that can form an organophilic clay through a cation exchange reaction with a smectite clay, and can be selected from a wide range of substances.

However, this organic cationic compound must have a positive charge localized on one atom or small atomic group within the compound. The organic cation line selected from quaternary ammonium salts, phosphonium salts, sulfonium salts, or mixtures thereof may be A or L. The organic cation may be a linear or branched saturated or unsaturated alkyl having 8 to 600 carbon atoms. Preferably, at least 1111 of the groups are included. More preferably, ari-kanaon 扛α,
It is preferable to include a β, r-unsaturated alkyl group, a hydroxyalkyl group having 2 to 6 carbon atoms, or a mixture thereof.

Representative examples of the organic cation of the present invention include those of the following formula.

and [wherein, X is nitrogen or phosphorus, Y is sulfur, R1 is an alkyl group having 8 to 60 carbon atoms, R2, R1, and R1 are (
a) hydrogen, (b) saturated and unsaturated alkyl groups having 1 to 22 carbon atoms, (C) aryl group, (d)
Aralkyl groups containing 1 to 22 carbon atoms on the alkyl group.

(.) A hydroxyalkyl group having 2 to 6 carbon atoms, and a mixture thereof].

The above long-chain alkyl group (Cl-110) may be a branched or unbranched saturated or unsaturated and substituted or unsubstituted alkyl group, or may have 8 to 60 alkyl groups in the straight chain portion of the alkyl group. must have carbon atoms. Desirably, R3 is an alkyl group having 12 to 22 carbon atoms.

The long chain alkyl groups mentioned above can be extracted from natural fats and oils such as various vegetable oils, such as corn oil, coconut oil, soybean oil, cottonseed oil, castor oil, and various animal fats, such as tallow oil (beef tallow). Demeru. This alkyl group may be synthesized from raw materials such as α-olefins.

Alternative examples of branched saturated alkyl groups that can be used include:
12-methylstearyl and 12-ethylstearyl. Representative examples of branched unsaturated alkyl groups that can be used include 12-methyloleyl and 12-ethyloleyl. Representative examples of unbranched saturated alkyl groups include lauryl, stearyl, tridecyl, myristal (tetradecyl), pentadecyl, hexadecyl, hydrogenated tallow,
(Hydrogenated beef tallow) alkyl group, Dokonyl Kameru. A typical example of an unbranched saturated alkyl group is diuryl.

Stearyl, tridecyl, baristyl (tetradecyl)
, pentadecyl, hexadecyl, the alkyl group of hydrogenated tallow, and doconyl. Unbranched and unsubstituted unsaturated combined alkyl groups include oleyl, lylyl, lylunyl, soybean and! -There is one alkyl group.

! 1R1, R4ti, each of hydrogen, a saturated and unsaturated alkyl group having 1 to 22 carbon atoms, an aryl group, an aralkyl group containing 1 to 22 carbon atoms in the alkyl chain of the aralkyl group; , a hydroxyalkyl group having 2 to 6 carbon atoms, and mixtures thereof.

Saturated and unsaturated alkyl groups having 1 to 22 carbon atoms may be flocculent or branched, cyclic or unbroken, saturated or unsaturated. Representative examples of alkyl groups that can be used include methyl, ethyl, propyl, 2-propyl, intravenal, cyclopentyl, cyclohexyl, and the like.

The β,r-unsaturated alkyl group can be selected from a wide range of materials. These groups may be substituted with cyclic or acyclic compounds, or may be substituted with aliphatic groups containing up to 5 carbon atoms. The total number of carbon atoms in the aliphatic group in this β, γ-unsaturated alkyl group is 6
or less is better. The β, r-unsaturated argyl group can also be substituted with an aromatic group, and this aromatic ring can also be in a position conjugated with the unsaturated bond of the β, r portion. Furthermore, it may have both a β, γ-unsaturated alkyl-based aliphatic group and an aromatic group as substituents.

Representative examples of cyclic β, r-unsaturated alkyl groups include 2-cyclohexenyl and 2-cyclopentenyl. Representative examples of acyclic β, γ-unsaturated alkyl groups having 6 or less carbon atoms include propargyl, 2-propenyl, 2-butenyl,
2-pentenyl, 2-hexanyl, 6-methyl-2-butenyl, 3-methyl-'2-pentenyl, 2.3-dimethyl-2-butenyl, 1.1-dumenal-2-propenyl, 1.2- Dimethyl propenyl, 2,4-pentagenyl, 2,4-hexagenyl, etc.

Representative examples of aromatic-substituted acyclic groups include 3-phenyl-2-propenyl, 2-phenyl-2-propenyl, and 5-(4-methoxy-phenyl)-2-propenyl. Representative examples of aromatic and aliphatic substituted groups include 3-phenyl-2-cyclohexenyl, 3-phenyl-2-cyclopentenyl. The alkyl group can have an aromatic ring as a substituent.

Each alkyl base line can be derived from the same raw materials as in the case of the long chain alkyl group (R1) above.

Examples of the above-mentioned aryl group include phenyl group, and N-alkyl group containing an alkyl group having 1 to 22 carbon atoms or t! Substituted phenyl groups such as those present in N,N-dialkyl anilines are included. S') K, o
-m- or t; j-p-nitrophenyl group; sulfur-, m- or p-furkylphenyl group containing aro- or alkyl group having 1 to 22 carbon atoms; halo group including chlor-p, bromo- or 2-15-or 4-halophenyl group containing iodine; 2-, 5- or 4-carboxyphenyl group; the carboxy moiety of these carboxydiphenyl groups has 1 to 2 carbon atoms;
An ester-type carboxyphenyl group that is often esterified with an alkyl alcohol, phenol to v! An ester-type carboxyphenyl group esterified with an aryl group such as the one described above or an aralkyl group derived from benzyl alcohol; an aryl group containing a condensed ring such as naphthalene or anthracene can also be substituted with the above-mentioned substituted aryl group. This is a basic example.

Representative examples of aralkyl groups may be benzyl groups or substituted benzyl groups, but other examples of aralkyl groups include, for example, benzyl halides, benzhydryl halides, trityl halides, and those containing 1 to 22 carbon atoms in the alkyl moiety. α-halo α-ph: t, nyl 7 , A, f) a, e.g. Examples of substituted benzyl groups include O-e m- or u-chlorobenzyl halides.

halides of p-methoxybenzyl, o-, m- or p
- Nitrilobenzyl halides, 1 to alkyl moiety
Other examples of substituted benzyl groups include those derived from 0-9 m- or p-alkylbenzyl halides having 22 carbon atoms, and 2-halomethylnaphthalene, 9
There are benzyl group-type radicals with fused rings, such as those derived from -halomethylanthracene or 9-halomethylphenanthrene. The halo substituent placed on this benzyl type group having a fused ring is chloro.

However, when this benzyl group-type group is subjected to a nucleophilic attack, the dissociative group (!
・A group of another type (other than halo) can be used, such as acting as an avtag group. Moreover, the dissociative group present on the benzyl group type group of Mayuki is
When a nucleophile is attacked, a type of substance that can replace the nucleophile is released.

The hydroxyalkyl group is selected from hydroxyl-substituted aliphatic alkyl groups in which the hydroxyl is not located at a carbon adjacent to a positively charged atom in the hydroxyalkyl group and the aliphatic moiety has 2 to 6 carbons. Ru. Among these, the alkyl group portion can have an aromatic ring as a substituent, separate from the 2 to 61m aliphatic carbon atoms therein.

Representative examples of hydroxylalkyl groups include 2-hydroxyethyl (ethanol residue), 3-hydroxyfurohyl, 4
-Hydroxypentyl, 6-hydroxyhexyl, 2-
Hydroxypropyl (impropatol residue), 2-hydroxydibutyl, 2-hydroxybentel, 2-hydroxyhexyl, 2-hydroxycyclohexyl, 3-hydroxycyclohexyl, 4-hydroxycyclohexyl, 2-hydroxycyclopentyl, 3-hydroxy Cyclopentyl, 2-methyl-2-hydroxyethyl A/
, 1 + 1 * 2-trimenthyl-2-hydroxypropyl, 2-7enyl-2-hydroxyethyl, 6-
Methyl-2-hydroxyethyl, 5-hydroxy-2-
Pentenyl etc.

Organic kanaone salts that can be used in the present invention are described in U.S. Pat.
No. 555,556, No. 2,775.61 'y, No. 3
．． No. 156,819. The anion associated with the organic cationic compound is selected from among the anions of chloride or bromide and mixtures thereof. Other anions, such as iodide, acetate, hydroxyl, nitrite, etc., may be present in the organic cationic compound to neutralize the cation, but chlorine is most preferred.

The organic anion used in the present invention can react with the +Sakura cation, and in addition, the generated cation-organic anion complex is an intercalation type compound (intercalmtions) in the smectate type clay.
) can be selected from a wide range of materials, as long as they can produce Molecular weight of organic anion with (Durham molecular weight)
is preferably 3,000 or less, preferably 100
Preferably, the number is zero or less, and the organic anion molecule contains at least one moiety per molecule of the organic anion. About 11.
Ijll! with a pK value less than 0! Those obtained from acids are preferred. The source of this organic anion is
must not contain at least one ionizable hydrogen atom with the preferred pKA value mentioned above to enable the formation of the Nanki cation-organic anion complex and subsequent clay intercalation reaction.

In addition to the above, compounds that yield desired organic anions when hydrolyzed can also be used as organic anions. Examples of such compounds include:

1) Hot acid hydrates 9 examples include acetic anhydride, maleic anhydride, succinic anhydride, phthalic anhydride 9, etc.

2) Acid halides, such as acenal chloride.

Octanoyl chloride, lauroyl chloride,
lauroyl bromide and benzoyl bromide, etc.

! l) 1.1.1-) Rehalides 1 e.g. 1°1.1
-trichloroethane; 1,1.1-tribromooctane, etc. ' 4) Nine examples of orthoesters include ethyl orthoformate and ethyl orthostearate.

Organic anions can be in acid or salt form. The salt can be selected from alkali metal salts, alkaline earth metal salts, ammonia or organic amines. Typical examples of such salts are hydrogen, lithium, and sodium.

Potassium, magnesium, calcium, barium.

Ammonium and organic amines such as ethanolamine, reethanolamine, triethanolamine, methyl diethanolamine, butyl diethanolamine,
diethylamine, dimethylamine, triethylamine,
Salts with dibutylamine, etc. or combinations thereof.

The most preferred salt is the sodium salt as the alkali metal salt.

As mentioned above, the organic anion may be in the form of a liquid,
Examples of suitable organic compounds that act as such surface acids and can be used in the present invention include the following #i.

1) Carboxylic acids (,) Benzene carboxylic acids, such as benzoic acid,
o-, m-1 or p-phthalic acid, 1,2.3-betricarboxylic acid, 1.3.5-benzene tricarboxylic acid, 1.2.4.5-benzene tetracarboxylic acid, 1
, 2,5,4,5.6- is hexacarboxylic acid (
mellitic acid).

(b) Alkyl carboxylic acids, especially of the formula H-(CH
t) carboxylic acids of n-COOH (on an integer from 1 to 20), such as acetic acid, propionic acid, butyric acid, hanthanic acid,
Hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid.

Hexadecanoic acid, heptadecane rII1. Octadecanoic acid (stearic acid), nonadecanoic acid, eicosonic acid.

(c) Alkyl dicarboxylic acids, especially 2HOOC
-(CHt)n -COOH (in the formula n tri 1~
B) dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, superric acid.

azelanic acid, sebacic acid.

(d) Hydrokylalkyl carboxylic acids, Example 12
-Hydroxystearic acid.

(・) Unsaturated alkyl carboxylic acids, such as maleic acid, fumaric acid, and cinnamic acid.

(f) Clamp ring aromatic carboxylic acids, such as naphthalene acid and anthracene carboxylic acid.

(g) Alicyclic carboxylic acids, such as cyclohexane.
Carboxylic acid, cyclo is tanthane carboxylic acid.

Furan carboxylic acid.

2) Organic sulfur acids tl) Sulfonic acids (1) Benzene sulfonic acids, such as benzene sulfonic acid, phenol sulfonic acid, dodecylbenzene
Sulfonic acid, benzene disulfonic acid, benzene trisulfonic acid, p-)luene sulfonic acid.

(2) Full? sulfonic acids such as evamethane sulfonic acid, ethane sulfonic acid, butane sulfonic acid, butane disulfonic acid, sulfosuccinate alkyl esters such as dioctyl succil sulfonic acid and alkyl polyethoxy-succinyl sulfonic acid.

(b) Alkyl heptaates, such as lauryl half ester of sulfuric acid, octadecyl half ester of sulfuric acid.

5) Organophosphoric acids (,) Phosphonic acids (b) of the following formula % formula % (3 (Riot aryl group or alkyl group having 1 to 22 carbon atoms in the formula)) -22 alkyl groups), such as dicyclohexyl phosphinic acid, diptylphosphinic acid.

Dilauryl phosphinic acid.

(c) Thiophosphinic acids of the following formula (wherein R is an aryl group or an alkyl group having 1 to 22 carbon atoms) 9 For example, di-isobutyl dithiophosphinic acid, :) butyl dithiophosphinic acid, dioctadecyl dithiophosphinic acid .

(d) Phosphites, ie, phosphoric acid glue esters represented by the following formula % (in which R1f is an alkyl group having 1 to 220 carbon atoms), such as diotadecyl phosphite.

(,) Phosphates, ie, phosphoric acid glue esters represented by the following formula % () (where Rij is an alkyl group having 1 to 22 carbon atoms), such as diotadecyl phosphate.

4) Phenols, such as phenol, hydroquinone, t-butylcatechol, p-methquinphenol,
Naphthols.

5) Thioacids, especially thioacids of the following formula % (wherein RH aryl group or alkyl group having 1 to 22 carbon atoms), such as thiosalicylic acid, thiobenzoic acid,
Thioacetic acid, thiolauric acid, thiostearic acid.

6) Amino acids, such as natural amino acids and derivatives thereof, such as 6-aminohexanoic acid, 12-aminododecanoic acid, N-phenylglycine, 3-aminocrotonic acid.

7) Polymeric acids, q! Polymeric acids containing residual acid groups in polymers made from acidic monomers, such as low molecular weight acrylic acid polymers or copolymers, styrene-maleic anhydride copolymers.

8) Special acids and acid salts, such as ferrocyanide, sodium tetraphenylborate, phosphotungstic acid, phosphosilicate, or other anions that form tight ions with organic cations, i.e., organic cations. Anion that produces a water-insoluble precipitate when acting on it.

Next, a method for producing the organophilic clay used in the present invention will be described.

This organophilic clay can be produced by mixing a smectite clay, an organic cation, an organic anion and water, and the mixture Fi20-100℃, I/I
The mixing time, which is preferably carried out at a temperature between 37°C and 77°C, is such that the complex formed between organic cations and organic anions undergoes intercalation (% n
t@rcalatioa). After reaction, filter.

Washing, drying and pulverization may be carried out. The addition of organic cations, organic anions and p may be carried out separately, or may be added as a complex of both. When using the produced organophilic clay for emulsion neutralization, drying The process of crushing can be omitted.

Furthermore, when mixing clay, organic cations, organic anions, and water, the steps of Ku, filtration, and washing can be omitted if their concentrations are set to such a level that they do not form a slurry.

The raw material clay is preferably dispersed in water, and the concentration in the water is about 1 to 80 grams, preferably 2 to 7 grams. The aqueous clay slurry can be centrifuged, if desired, to remove about 10-5 otst of non-clay impurities in the raw clay. Prior to adding the organic reactant, the clay slurry is preferably stirred and preheated to a temperature in the range of 35°C to 77°C.

As another manufacturing method, the organophilic clay used in the present invention can be manufactured by the following method. That is, the organic anion is mixed with the raw material clay and water, and the temperature at the time of mixing is preferably 20 to 100°C, the mixing time is sufficient to make a homogeneous mixture, and then the raw material clay is mixed with the raw material clay. Sufficient surface organic cation is added to satisfy both the cation exchange capacity of the organic anion used and the cation reactivity capacity of the organic anion used.

When these mixtures are reacted with stirring at a temperature of 20 to 100°C for 0 reaction time, an organic cation-organic anion complex is formed, and the raw material clay is intercalated inside this complex. Sufficient time is allowed to saturate the exchange sites to be replaced by organic cations. The reaction temperature was set to 20
It is possible, but not preferred, to be lower than 100°C or higher than 100°C.

For purposes of this invention, the amount of organic anion added to the smectite clay must be sufficient to impart the desired high dispersion properties to the organophilic clay produced. The amount added is defined by the milliequivalent ratio;
The equivalent ratio of clay is 1 [) [), ? (Activated clay is 10
(based on the coefficient 0), it is the number of building equivalents (M, 1.) of organic anion in the organoclay. Preferably, the organophilic clay of the present invention has an anion milliequivalent ratio of 5 to 100, preferably 10 to 500. Lower or higher onion milliequivalent ratios have a negative effect on the dispersibility and performance of the organophilic clay.

/ The organic anion is preferably added as a solid or an aqueous solution to the other reactants in a proportion corresponding to its desired milliequivalent ratio, with stirring, so as to obtain a mixture that appears macroscopically homogeneous.

The organic cation is used in an amount at least slightly sufficient to satisfy both the cation exchange capacity of the raw clay and the cation reaction capacity (activity) of the organic anion used. Total value J of cation exchange capacity between raw material clay and anion:
9 Extra cations can be used if desired. When erythmectite clay is used in the present invention, using 90 milliequivalents or more of organic cations is sufficient to satisfy at least a portion of O out of the total cation exchange capacity between raw material clay and organic anions. May it be discovered.

For ease of handling, the total organic content in the organophilic clay of the present invention is preferably less than about 50% by weight of the organoclay. Although the total organic matter content can be increased to more than son, the organophilic clay as a reaction product obtained in this case is difficult to heat, dry, and grind.

For producing the organophilic clay gel forming agent of the present invention, m
- Chireru clay is a smectite clay that has a cation exchange capacity of 75 milliequivalents or more per 100 g of clay. Particularly desirable types of clays are the naturally occurring swellable bentonite and similar clays from Wyoden, as well as hectorite, a swellable magnesium-lithium silicate clay.

Both naturally occurring smectite-type clays and synthetic smectite-type clays, such as those synthesized by pneumatolytie or hydrothermal processes, can be used to prepare the organophilic clays of the invention. An example of this is KFi,
Montmorillona (,,), bentonite.

There are idellite, hectorite, sabonite, and steppensite.

When the clay used, especially the bantonite type clay, is not in the sodium form, it is preferable to use the sodium form instead. Conversion to the sodium form is conveniently accomplished by making an aqueous slurry of the clay and passing it through a bed of cation exchange resin in the sodium form. Alternatively, clay can be added to water and soluble compounds (e.g. carbonate).
Mix with IJum, sodium hydroxide, etc., and make the mixture /
It may be kneaded while applying shearing force using a zogumill or an extruder.

The cation exchange capacity of smectite clay can be measured by the ammonium acetate method.

The printing ink of the present invention can be produced economically and practically by simply mixing an organophilic clay gelling agent into a basic ink stock solution containing an ink colorant and an organic vehicle for the ink.

The printing ink composition manufactured to have the composition of the present invention can be put to practical use as a printing ink by simply stirring it into an ink stock solution11□ and has a high viscosity level9, and in order to increase the viscosity, There is no need for scouring using corrugated roll sills or other similar equipment systems.

The printing ink composition of the present invention is easily dispersed as a rheology agent, and the maximum viscosity can be increased simply by applying it to a conventional dispersion device without applying it to a three-roll mill. The ink compositions made using the organophilic clays of the present invention have sufficiently fine particle sizes that, as long as they are properly dispersed, no pass or double processing is required to obtain a practical printing ink. An ink composition is provided.

A three-roll mill can be used for this purpose to facilitate the dispersion of the ink coloring pigment colorants in order to condition the ink for satisfactory printing performance on the printing press. Although this milling was conventionally necessary, in the ink compositions of the present invention, passing through a roll mill is not necessary for the purpose of increasing viscosity.

However, in the case of ink systems that are prone to oxidation, in order to prevent the air trapped in the ink from forming hardened small particles in the ink during the dispersion process, the ink should be gently rolled in a three-stage roller. It may also pass through the composition.

The present invention can also be practiced by adding the organophilic clay gel formers of the present invention into pre-manufactured printing ink products. These manufactured ink products can be manufactured by conventional methods using colloid mills, roller mills, ball mills, etc., in which the high shear forces generated ensure that the ink pigments are well dispersed across the organic ink vehicle width. However, when the pigment is dispersed in the vehicle in this way,
A conventional ink is obtained, which conventionally exhibits the drawback of printing blur (misting).

In the present invention, the organophilic clay gelling agent is used in an amount sufficient to impart the desired viscosity and tack to the ink. If necessary, the viscosity can be further adjusted by adding viscosity reducing agents such as naphthalene oil or solvents.

Generally, the use of organophilic clays in amounts of 0.1 to 15% by weight of the printing ink is sufficient to greatly reduce the tendency of the ink to blur (misty jig) in high speed printing operations. The amount of clay used is preferably 5-4% by weight of the skin.
, most preferably 1 to 3% by weight. It's a little more than 0.1% by weight of printing ink! Use of organophilic clay gel formers at concentrations greater than 10% by weight significantly impairs physical properties that affect consistency, flow, and other critical properties of the ink.

That is, the desired increase in viscosity and tack cannot be obtained.

The printing ink of the present invention can contain ink additives commonly used in inks. For example, oil-soluble toners (ton@r 3
Also, carbon black pigments can be added together with small amounts of waxes or greases to impart special properties to the printing ink.

The printing ink of the present invention can be used as, but not limited to, a thermosetting or newsprint ink, a water or steam curing ink, or a lithography printing ink.

Although newsprint inks dry primarily by penetration and absorption, some heat is used to accelerate drying and prevent hand smearing. In the case of the above-mentioned printing ink, by appropriately adjusting the viscosity, tack, yield point, etc., it is possible to prevent the organophilic clay used from separating due to centrifugal force or causing print blurring. Enables effective and proper penetration.

When the organophilic clay gel-forming agent according to the present invention is incorporated into other thermosetting letterpress printing inks containing additives such as binders and solvents, such as high-grade release inks, those inks can: It becomes extremely flexible, does not smudge, prints well, and sets quickly when heated to high temperatures.

When the present invention is applied to an ink that can be set with steam or water, the shortness characteristic of the ink (5-hour
ess), which greatly influences viscosity and tack.

Lithographic Ink Company, on the other hand, has a composition very similar to letterpress printing inks, except that the body of the ink is somewhat larger or the pigment concentration is higher. Konori,
Even when the present invention is applied to 5-Tography printing ink, the above-mentioned advantages can be obtained.

The present invention will now be illustrated by way of examples, in which "-" as used herein is by weight unless otherwise specified.

In the examples, the following test method was used.

The ink sample for the dispersion test was measured using a Grade 1 Grandmeter (Griado) from NPIRI (Printing Ink Research Institute).
met@r) in two channels (dr
awn doten), grinding fineness (fineness o
f grind) (small particles) and scratchability (5c
ratches). Gauge scale readings range from 10 to 0. A reading of 10 corresponds to a depth of 1 mil, and a reading of 0 corresponds to a depth of zero. The ink sample was run down so that the gauge readings were taken four separate times, the minimum reading being taken and the minimum readings averaged out. A reading on an ink sample of zero for both grind fineness and scratchability would be considered perfect.

Viscosity Test Viscosity f is Thwing-
The measurement was carried out using an Albvrt falling bar type falling bar. Remove air from the ink sample using a spatula and then completely cover the drop bar with the ink sample. To measure the fall time of the bar, three types of weights are used: 700. L 5
A weight of 00 g and 200.9 was used. Measurements are repeated using these weights, and the obtained data is
ett-Paekard computer, 100
The predicted Bingham viscosity expressed as a Boyes value of 0 aee-''1 unit was obtained. The viscosity values chosen to appear in each table were calculated from the Bingham equation below. This was obtained using data including the minimum mean square deviation value compared to the reference straight line.

fB=T-DBMB In this equation, is the intercept (1ntercept) on the display axis of the shear stress when the shear rate is 0.

here, fBFi breakdown value TFi shear stress DB is shear rate M is viscosity It is.

The performance of the organophilic clay gel former was evaluated by infusion when incorporated into a thermosetting red ink base for web offset. This ink base material is made using the ink components listed in the m1 table below, and is
It has been passed through a corrugated roll mill once. In the case of rheology, the organophilic clay as a rheology modifier was gradually added to the ink base with stirring, but the stirring was kept as low as possible to prevent spillage. Then diameter 1
．． 500O with a 0.5 HP pre-mini-rule (Pr5mler) type disperser using a 75 inch C0WI@I impeller.
r, p, nt.

Dispersion was performed by rotation. Appropriate blade rotation speed was maintained for the specified mixing time. Viscosity measurements were performed following the dispersion operation.

Separate ink samples were treated with various organophilic clay gel formers or comparative gel formers at a concentration of 2 wt.

In Comparative Example 1 described later, no rheology agent was used, but in Comparative Example 2, Aerosil R-972 (Degutsa) was used.
Particulate silica commercially available as a rheology agent was used as a rheology agent. Comparative Example 314 uses Wyoming bentonite as a quaternary ammonium salt, i.e. benzyl.
Trihydrogenated tallow long chain alkyl ammonium tritetralide (BAIT) or methyl trihydrogenated tallow long chain alkyl ammonium chloride (M3HT),! :
The reaction product obtained by the reaction was used as a rheology agent in the indicated milliequivalent ratio of 10. Examples of the invention used reaction products of bentonite reacted with various organic cations and organic anions shown in the table. Unless otherwise specified, the organophilic clay gel formers used in the Examples contained 122.5 mequivalents of organic cations and 22.5 mequivalents of organic anions.

The test results are listed in Table ■. As is clear from the test results, the rheology agent used for comparative purposes has a higher grinding fineness (fln・■of grlnd) than that of the present invention.
) or Fi gelling performance is poor, or both.

Table Comparative Example 1 Blank test 2゜2 Fused silica 153
B3HT (114MB) 20
4 M3HT (115MB)
201 example (invention) I AM 2 HT /N a benzoate (11) 202 8
M 2 HT /N a benzoate (spicy 21
203 B M 2 HT /
Na benzoate (13) 20
4 2 M 2 HT /N a benzoate (Mine 4) 205 AM
2HT/Na salicylate
206 B M 2 HT /N a Salicylate 207 2 M 2 HT /N a
Salicylate 208
BM2HT/Na phthalate
20 Dispersion test Viscosity test 0 0 43 10 0 5B 0 0 62 0 0 58 0 0 66 0 0 780
1 640 1
64 0 0 64 0 0 65 0 1 93 0 2 65 (continued) Test example Rheology agent used (organo sample) Example (invention) 9 AM2HT/Na octoate 10
8M2HT/Na Laurate 11 A
M2HT/Na stearate 12 BM2H
T/Na stearate L5 AM2HT/12
-H3A(5)14 BM2HT/12-H3
A (6) 15 AM2HT (115MFri/P
P8 (15MI!t)16 AM2HT/PP
8 17 AM2HT (130M) iri/PP8(
130MFi) 18 BM2HT (115MB
)/PP8 (15MB) 19 BM2HT/P
P8 20 8M2HT (130MB)/PP8 (50
MB) Dispersion test Viscosity test 20 0 1 6220
0 1 6720 0 1
9520 0 1 6
820 0 1 6720
0 2 6420 0
0 6120 0 0
7120 0 0 6920
0 0 6520 0
1 6020 0 0
68 Notes to Table 1 (Tochini (1) λM2H'r = allyl methyl dihydrogenated long chain alkyl group (2) 8M21 (te = benzyl methyl dihydrogenated long chain alkyl group) (3) 1M2HT - ethanol methyl dihydrogenated tallow long chain alkyl group (4) 2M2HT = dimethyl dihydrogenated tallow long chain alkyl group (5) 12-H8A = 12-hydroxystearin i sodium salt (6) PP8=P-phenolsulfonic acid, meaning sodium 1) salt.

Having thus described the invention, it will be clear that the invention may include a variety of implementation motives in many respects.

Claims (1)

[Scope of Claims] 1. A printing ink comprising an organic vehicle for ink containing a coloring agent dispersed therein, and an organophilic clay gel forming agent or gelling agent dispersed in the vehicle; The organic clay gel-forming agent or gelling agent combines organic cations and organic anions into one type of smectite clay.
Cation exchange of at least 75 meq per 002: #
The invention is characterized in that it consists of a reaction product with a smectite-type clay having t, in which the kanaone exchange site of the Miao-Shin-tite clay is replaced with the organic cation. printing ink, 2. The organic kanone in the organophilic clay has 8 to 2 carbon atoms.
20. The printing ink according to claim 1, further comprising at least one of 20 linear or branched alkyl groups and an ammonium salt, phosphonium salt or sulfonium salt or a mixture thereof. 6. The organic anion in the organophilic clay is less than about 11 J], which is the book from Ikki acid with ρKA clay%*#
Scope of Restrictions Item 1 6 Self-published printing ink. 4 The smectite type clay in Oyinan Shinsei clay is made with hectorite or sodium bentonite.
The ink described in item 1 of the M pot range. 5. The ink according to claim 1, wherein the amount of organic anion in the organophilic clay is from 5 to 100 bur equivalents per 100r (based on 100% active clay) of the heptemectite clay. 6. The t of the organic cation in the parent MD clay is sufficient to satisfy the canon exchange bar of the smectite clay and the canon exchange cap of the organic anion as set forth in claim 1. ink. Z 41 in the pro-self-reliance clay (the enemy of the smectite type clay is 1t) Of (based on 100% active clay) 60 to 200<! The ink according to claim 1, which can be packed in a J cover. 8. 1. The ink of claim 1 Ii [2-], wherein the particle size in the organophilic clay is 100 to 160 particles per 10 of the smectite-type clay (based on 100% active clay). 9. The ink according to claim 1, wherein the organophilic clay shell forming agent accounts for 0.1 to 15% by weight of the printing ink. 10. 1.0 of the ink to the organophilic clay gel forming agent
The ink according to claim 7i11 having a weight of ~'5.0. 11. The reaction product U forming the organophilic clay gel-forming agent (a) an organic anion from an organic acid having a p K A value of less than about 11.0; and (b) the following formula or the following formula [ In the formula, XUM is cumulative/deme9, Y is iota demeri,
R+H with an alkyl group having 8 to 22 carbon atoms, R1+ R
1 and R1 are hydrogen, a saturated or unsaturated alkyl group having 1 to 22 carbon atoms, an aryl group, or a carbon alkyl group, respectively.
JI & aralkyl group with 1 to 22 atoms or carbon $62
an organic cationic compound represented by 6 hydroxyalkyl groups or a combination of these; and (C)
The reaction product produced by the reaction with a smectite clay having a cation exchange capacity of at least 75 meq per 1100f of the clay is an organic cation-organic anion complex intercalated with the smectite clay to form a kalate 4-6. -C and wherein the cation exchange site of the smectite clay is replaced with the organic canone. 12. In a method for manufacturing printing ink. (a) A dispersion of the colorant for the ink dispersed in an organic vehicle for the ink is prepared, and (b) an organic cation ti) and an anion (11) are prepared.
) and a smectite-type clay (110) having a cation exchange rate of at least 75 iat per 100 of the smectite-type clay. (c) preparing an organophilic clay gel-forming agent consisting of a reaction product in which the exchange site is substituted with an organic kanone; (c) dispersing this organophilic clay gel-forming agent in the above-mentioned ink colorant dispersion; A method for producing a printing ink, the aim of which is to produce a viscous printing ink.