JP4952010B2 - Oil-based liquid ink - Google Patents

Description

  The present invention relates to an oil-based liquid ink excellent in suitability for use, in particular, fluidity and dispersion stability, gloss, and bleeding properties.

In general, when fine particles of pigment are dispersed in an oily vehicle, it is difficult to obtain a stable dispersion, which is known to cause various problems in the manufacturing operation and the value of the resulting product.
For example, dispersions containing pigments consisting of fine particles often exhibit high viscosity, making the product difficult to remove and transport from the disperser, and if worse, cause gelation during storage. It may be difficult to use. Furthermore, with respect to the color-extended product, there may be a state failure such as a decrease in gloss and a leveling failure. In addition, when different types of pigments are used in combination, color unevenness and a marked decrease in coloring power may appear in the developed product due to phenomena such as color separation and sedimentation due to aggregation.

  In order to solve the various problems as described above, a method in which an organic pigment is used as a base skeleton and a pigment derivative having an acidic group or a basic group as a substituent in a side chain is mixed as a dispersant is disclosed in Patent Document 1 and Patent Document 2, Patent Document 3, Patent Document 4, Patent Document 5, and the like. In these methods, the mechanism in which the pigment derivative and the resin component in the varnish interact to contribute to the stabilization of dispersion is considered, but since there are a large number of varnish systems in oil-based liquid ink, the pigment derivative In fact, the resin in the varnish does not always work effectively, and a satisfactory effect is not obtained except for some varnishes.

In addition, since these pigment derivatives have properties similar to dyes, they may be inferior in resistance to pigments. When a pigment composition containing these pigment derivatives is used in inks or paints, the pigment derivatives may deteriorate over time. The hue may fade and the coating film hue may change. In particular, oil-based liquid inks for food packaging have a problem (bleed) in which these pigment derivatives are raised and hue shifts due to high-temperature treatment such as boiling and baking and pressure bonding after the coating film is formed.
Japanese Patent Publication No.41-2466 US Pat. No. 2,855,403 JP-A-63-305173 JP-A-1-247468 JP-A-3-26767

  Accordingly, an object of the present invention is to provide an oil-based liquid ink excellent in fluidity, dispersion stability, gloss of printed matter, bleeding property by boiling in water, and the like.

（式中、ＸはＳＯ₂ 、ＹはＮＨ（ＣＨ₂）ｎを表し、Ｒ₁、Ｒ₂はそれぞれ独立に、水素 原子、炭素数１〜６の置換基を有してもよいアルキル基を表すか、またはＲ₁、Ｒ₂で 窒素原子または酸素原子を含んでも良い複素環を形成し、ｎは１〜６の整数を表す。）
The oil-based liquid ink of the present invention is represented by a resin solution, a pigment, a phthalocyanine derivative (D1) having one substituent represented by the following general formula (1) for the phthalocyanine residue, and the following general formula (1). And a phthalocyanine derivative (D2) having two substituents for the phthalocyanine residue, wherein the weight ratio of the phthalocyanine derivative (D1) to the phthalocyanine derivative (D2) is 85:15 to 56. : 44.
General formula (1)

(Wherein X represents SO ₂ , Y represents NH (CH ₂ ) n, and R ₁ and R ₂ each independently represents a hydrogen atom or an alkyl group which may have a substituent having 1 to 6 carbon atoms. Or R ₁ and R ₂ form a heterocyclic ring that may contain a nitrogen atom or an oxygen atom, and n represents an integer of 1 to 6.)

  The oil-based liquid ink of the present invention uses a specific ratio of a phthalocyanine derivative (D1) having one specific basic substituent to a phthalocyanine residue and a phthalocyanine derivative (D2) having two specific basic substituents to disperse the pigment. Therefore, the secondary particles of the pigment are very few, the particle diameter of the pigment is uniform, the pigment can be highly dispersed, and the non-aggregation property, the non-crystallinity and the fluidity are excellent. For this reason, by using the oil-based liquid ink of the present invention, it is possible to obtain a printed matter excellent in gloss, bleeding property by boiling in water, and the like.

（式中、ＸはＳＯ₂ 、ＹはＮＨ（ＣＨ₂）ｎを表し、Ｒ₁、Ｒ₂はそれぞれ独立に、水素原子、炭素数１〜６の置換基を有してもよいアルキル基を表すか、またはＲ₁、Ｒ₂で窒素原子または酸素原子を含んでも良い複素環を形成し、ｎは１〜６の整数を表す。）
First, the oil-based liquid ink of the present invention will be described in detail by giving preferred embodiments.
The oil-based liquid ink of the present invention is represented by a resin solution, a pigment, a phthalocyanine derivative (D1) having one substituent represented by the following general formula (1) for the phthalocyanine residue, and the following general formula (1). And a phthalocyanine derivative (D2) having two substituents for the phthalocyanine residue, wherein the weight ratio of the phthalocyanine derivative (D1) to the phthalocyanine derivative (D2) is 85:15 to 56. : 44, preferably 80:20 to 65:35.
General formula (1)

(Wherein X represents SO ₂ , Y represents NH (CH ₂ ) n, and R ₁ and R ₂ each independently represents a hydrogen atom or an alkyl group which may have a substituent having 1 to 6 carbon atoms. Or a heterocyclic ring that may contain a nitrogen atom or an oxygen atom is formed by R ₁ and R ₂ , and n represents an integer of 1 to 6.)

Even when both the phthalocyanine derivative (D1) and the phthalocyanine derivative (D2) are used, if the ratio of the phthalocyanine derivative (D1) is larger than the above range, the pigment aggregates after dispersion, resulting in poor fluidity. In addition, since the dispersion stability is also deteriorated, thickening with time and generation of coarse particles occur, which causes a decrease in gloss and the like. In addition, when the ratio of the phthalocyanine derivative (D1) is less than the above range, a bleocyanine derivative is dissolved in water due to boiling treatment of the printed matter in water. Become. Furthermore, even if three or more phthalocyanine derivatives (D3) with respect to the phthalocyanine residue are mixed in the oil-based liquid ink of the present invention, the bleedability deteriorates because the solubility in hot water is increased.
The total amount of the phthalocyanine derivative (D1) and the phthalocyanine derivative (D2) is 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight with respect to 100 parts by weight of the pigment contained in the oil-based liquid ink. Can be used.

The phthalocyanine derivatives (D1) and (D2) having the substituent of the general formula (1) can be synthesized by various synthetic routes. For example, after introducing a substituent represented by phthalocyanine compound of the following general formula (2) can be reacted with the amine component is synthesized by forming a substituent of the general formula (1).
Formula ₍₂₎ -SO 2 C l

The weight ratio of the phthalocyanine derivative (D1) and the phthalocyanine derivative (D2) can be controlled as follows.
For example, when the substituent represented by the general formula (2) is introduced, the phthalocyanine compound is dissolved in chlorosulfonic acid and reacted with a chlorinating agent such as thionyl chloride. The reaction temperature and reaction time at this time The number of substituents represented by the general formula (2) to be introduced into the phthalocyanine compound can be controlled by the above conditions, and as a result, the weight ratio of the phthalocyanine derivative (D1) and the phthalocyanine derivative (D2) can be controlled.

Examples of the phthalocyanine compound constituting the phthalocyanine residue include metal phthalocyanines having a central metal such as copper, nickel, cobalt, aluminum, iron, zinc, manganese, and metal-free phthalocyanines. When the central metal is a metal having a valence of 3 or more, a chlorine atom, a bromine atom, and in some cases, a sulfonic acid group or a carboxylic acid group may be bonded to the central metal as desired.
In the phthalocyanine compound, the hydrogen atom of the phthalimide skeleton may be optionally substituted with a chlorine atom, a bromine atom, or in some cases, a sulfonic acid group or a carboxyl group.

Examples of the amine component used to form the substituents of the general formula (2) is reacted with a substituted group represented the general formula (1), for example, dimethylamine, diethylamine, N, N-ethyl-isopropylamine, N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N- sec-butylpropylamine, dibutylamine, disec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, di (2-ethylhexyl) amine, dioctylamine, N , N-methyloctadecylamine, didecyla , Diallylamine, N, N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N -Diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N- Tyl-laurylaminopropylamine, N, N-ethylhexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecoline, 3 -Pipecoline, 4-Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-Piperidinemethanol, Pipecolic acid, Isonipecotic acid, Methyl isonicopetinate, Ethyl isonicopetinate, 2-Piperidinethanol, Pyrrolidine 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N-aminopropyl-4 -Pipecoline, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine and the like.

During the reaction between the substituents and the amine component represented by the general formula (2), part of a substituent group represented by the general formula (2) is hydrolyzed, may chlorine is substituted with a hydroxyl group. In that case, the substituent represented by the general formula (2) ing and a sulfonic acid group, both may be left free acid, also form a monovalent to trivalent metal or the monoamine salt Good.

As the pigment contained in the oil-based liquid ink of the present invention, organic or inorganic pigments can be used alone or in admixture of two or more. Specific examples of organic pigments include C.I. I. Pigment Green 7, 36, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 60, C.I. I. Pigment Violet 23 and the like. Examples of the inorganic pigment include carbon black.
In the oil-based liquid ink of the present invention, white pigments and color pigments other than the above specific examples can be mixed and used.

The resin solution contained in the oil-based liquid ink of the present invention is obtained by dissolving a resin in an organic solvent. As the resin, any of those used in ordinary oil-based liquid inks can be used. For example, nitrocellulose, cellulose acetate, ethyl cellulose, urethane resin, polyamide resin, polyvinyl butyral resin, acrylic resin, polyester resin, alkyd resin , Vinyl resin, cyclized rubber, chlorinated rubber, chlorinated polypropylene resin, ethylene-vinyl acetate resin, epoxy resin, vinyl chloride, silicon resin and the like.
As the resin, one or more of the above resins can be used, and a high-concentration pigment dispersion dispersed using one or more resins may be diluted with another resin. .

  Examples of the organic solvent used in the oil-based liquid ink of the present invention include aromatic hydrocarbons such as toluene, petroleum hydrocarbons such as mineral spirits, halogen hydrocarbons such as chlorobenzene, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. , Esters such as ethyl acetate, butyl acetate, amyl acetate and 2-ethoxyethyl acetate, alcohols such as methanol, ethanol, propanol and butanol, cellosolves such as ethyl cellosolve and butyl cellosolve, and the like. Particularly preferred are highly polar organic solvents such as aromatic hydrocarbons, ketones, alcohols, cellosolves and esters. Of course, the organic solvent may be a mixture of two or more.

If necessary, the oil-based liquid ink of the present invention may be used by mixing various additives, dispersants and the like.
As additives, antifoaming agents, leveling agents, anti-blocking agents, surfactants, viscosity modifiers, waxes and the like can be used.
Examples of the dispersant include Solsperse 24000 (manufactured by Abyssia), Disperbyk-160, Disperbyk-161, Disperbyk-162, Disperbyk-163, Disperbyk-170 (manufactured by Big Chemie), Adisper PB711, Adisper PB1 Tech. Company-made).

  The oil-based liquid ink of the present invention can be produced by dispersing a pigment and a phthalocyanine derivative in a resin solution using a horizontal sand mill, vertical sand mill, annular bead mill, attritor or the like. In addition, before dispersing with a horizontal sand mill, vertical sand mill, annular bead mill, attritor or the like, pre-dispersion may be performed using a kneader mixer such as a kneader, three-roll mill, or two-roll mill. In addition, any disperser or mixer such as a high speed mixer, a homomixer, a ball mill, a roll mill, a stone mill, or an ultrasonic disperser can be used for producing the oil-based liquid ink of the present invention.

The oil-based liquid ink of the present invention exhibits good fluidity such as a decrease in viscosity and a decrease in structural viscosity, and at the same time, there are no problems such as color separation and crystal change, and the printed matter has a good gloss. In addition, since a phthalocyanine derivative that is hardly soluble in hot water is used, it is possible to obtain a beautiful product excellent in bleeding property by boiling in water by using the oil-based liquid ink of the present invention. .
The oil-based liquid ink of the present invention can be used as oil-based gravure ink, oil-based flexo ink, and oil-based inkjet ink.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In Examples and Comparative Examples, “part” means “part by weight”, and “%” means “% by weight”.

(Preparation of phthalocyanine derivative composition)
After adding 30 parts of copper phthalocyanine to 300 parts of chlorosulfonic acid and completely dissolving it, 24 parts of thionyl chloride was added, and the temperature was gradually raised and reacted at 101 ° C. for 3 hours. The reaction solution was poured into 9000 parts of ice water, stirred, filtered and washed with water. The obtained press cake was made into a slurry with 300 parts of water, then 15 parts of N, N-dimethylaminopropylamine was added, and the mixture was stirred at room temperature for 3 hours, then at 60 ° C. for 2 hours, filtered, washed with water and dried. 36 parts of a phthalocyanine derivative composition were obtained. The obtained phthalocyanine derivative composition was subjected to a composition analysis using a liquid chromatograph mass spectrometer platform LCZ manufactured by Waters, and those having three or more substituents were not included. The weight ratio of one phthalocyanine derivative (D1) and one phthalocyanine derivative (D2) having a substituent of the following formula (6) was 85:15.

Further, after adding 24 parts of the above thionyl chloride, the reaction temperature is set to 105 ° C., 106 ° C., 100 ° C., and 110 ° C., whereby a phthalocyanine derivative (D1) having one substituent of the following formula (6): A phthalocyanine derivative composition having a weight ratio of 65:35, 60:40, 90:10, and 41:59 of the phthalocyanine derivative (D2) having one substituent of formula (6) was obtained.
Formula (6)

[Examples 1-5, Comparative Examples 1-3]
A pigment composition obtained by adding the phthalocyanine derivative composition shown in Table 1 to a copper phthalocyanine pigment (CI Pigment Blue 15: 3, “Lionol Blue FG-7351” manufactured by Toyo Ink Co., Ltd.) in an amount shown in Table 1. 10 parts, varnish for oil-based liquid ink (nitrocellulose resin 12%, ethyl acetate 33%, toluene 30%, isopropyl alcohol 15%, methanol 10%) 90 parts and 3 mm glass beads 100 parts are mixed, and paint conditioner is used for 60 minutes. An oily liquid ink was prepared by dispersing. The viscosity of the prepared ink was measured with a B-type viscometer (6 rpm). In addition, the gloss value (60 °) of the printed product obtained by spreading the prepared ink on a nylon film with a bar coater, and further, this printed product is adhered to the white ink printed product with the printing surface overlapped and immersed in water. The bleeding property after boiling for a minute (transition coloring of the colored ink onto the white ink printing surface) was evaluated in three stages. The results are shown in Table 1.
The inks of the present invention using the phthalocyanine derivative (D1) and the phthalocyanine derivative (D2) in a specific ratio all have low viscosity, excellent fluidity, high gloss, and no bleeding. Excellent quality that met.

Claims (1)

A resin solution, a pigment, a phthalocyanine derivative (D1) having one substituent represented by the following general formula (1) with respect to the phthalocyanine residue, and a substituent represented by the following general formula (1) as a phthalocyanine residue An oil-based liquid ink containing two phthalocyanine derivatives (D2), wherein the weight ratio of the phthalocyanine derivative (D1) to the phthalocyanine derivative (D2) is 85:15 to 56:44. An oil-based liquid ink that is used for food packaging .
General formula (1)

(Wherein X represents SO ₂ , Y represents NH (CH ₂ ) n, and R ₁ and R ₂ each independently represents a hydrogen atom or an alkyl group which may have a substituent having 1 to 6 carbon atoms. Or a heterocyclic ring that may contain a nitrogen atom or an oxygen atom is formed by R ₁ and R ₂ , and n represents an integer of 1 to 6.)