JP2010180332A - Nonaqueous ink composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nonaqueous ink composition excellent in safety and health, and excellent in adhesion to a non-absorbing substrate and the like. <P>SOLUTION: The nonaqueous ink composition comprises at least an organic solvent, a pigment and a resin. The organic solvent contains β-alkoxypropionamides represented by formula (1): R<SP>1</SP>O-CH<SB>2</SB>CH<SB>2</SB>-CONR<SP>2</SP>R<SP>3</SP>, wherein R<SP>1</SP>is a 3-10C alkyl group; R<SP>2</SP>and R<SP>3</SP>are each independently a hydrogen atom, or a hydrocarbon group which may contain a 1-6C ether bond, and may be identical or different from each other, or may bond with each other to form a ring structure. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a printing ink, particularly an inkjet ink, which is excellent in safety and hygiene and has excellent adhesion to a non-absorbent substrate or the like.

  Conventionally, gravure printing for soft packaging materials, flexographic printing for sanitary, silk screen printing for metal plates, inkjet printing for indoor and outdoor advertising, etc. are generally known as printing methods for non-absorbent substrates. However, ink compositions used in these printing methods generally use solvents such as toluene, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc., which are classified as organic solvents of the second type. For example, it is difficult to handle such as the installation of a local exhaust system or an obligation such as a periodic health check, and inks with higher safety and hygiene have been demanded. In particular, ink jets are used in offices such as general offices, unlike gravure printing, flexo printing, and silk screen printing, which are printed at a dedicated factory. Therefore, safety, toxicity, and odor must be considered.

  In order to improve safety, non-toluene inks that do not use toluene, which has a low environmental concentration setting value, and water-based inks based on alcohol have been developed for soft packaging gravure printing and sanitary flexographic printing.

  On the other hand, an ink using a polyalkylene glycol solvent or a hydrocarbon solvent that is not applicable to the second type organic solvent has also been developed in ink jet printing. (Patent Document 1) However, since the surface of the printing substrate cannot be dissolved with an ink comprising a polyalkylene glycol solvent or a hydrocarbon solvent, there are problems such as poor fixability and weather resistance.

  Therefore, recently, nitrogen-containing heterocyclic compounds such as 2-pyrrolidone and N-methyl-2-pyrrolidone, which are not applicable to the second type organic solvent, as well as polyalkylene glycol solvents, or lactone compounds are used in combination as cosolvents. Thus, solvent-based inks having improved fixability and weather resistance have been developed. (Patent Literature 2, Patent Literature 3, Patent Literature 4, Patent Literature 5, Patent Literature 6). However, these inks have problems such as dissolution of pigments, corrosion of the printer head material, and strong odor due to their high solubility.

Japanese Patent No. 3590486 Japanese Patent Laid-Open No. 2005-60716 JP 2005-15672 A JP 2005-200469 A Japanese Patent No. 3692365 JP 2005-248006 A

An object of the present invention is to provide a non-aqueous ink composition and a non-aqueous inkjet ink excellent in safety and hygiene and adhesion to a non-absorbent substrate.

  The present invention relates to a non-aqueous ink composition comprising a β-alkoxypropionamide represented by the following general formula (1) as an organic solvent in a non-aqueous ink composition comprising at least an organic solvent, a pigment, and a resin. Related to things.

General formula (1)

（式中Ｒ^１は炭素数３〜１０のアルキル基、Ｒ^２およびＲ^３はそれぞれ独立に水素原子または炭素数１〜６のエーテル結合を有しても良い炭化水素基であり、互いに同一でも異なっていても良く、更に互いに結合して環構造を形成しても良い。）
更に本発明は、該有機溶剤の１気圧における沸点が１５０℃以上であることを特徴とする上記非水性インキ組成物に関する。

(In the formula, R ¹ is an alkyl group having 3 to 10 carbon atoms, and R ² and R ³ are each independently a hydrogen atom or a hydrocarbon group that may have an ether bond having 1 to 6 carbon atoms. They may be different from each other and may be further bonded to each other to form a ring structure.)
Furthermore, the present invention relates to the above non-aqueous ink composition, wherein the organic solvent has a boiling point at 1 atm of 150 ° C. or higher.

  Furthermore, the present invention relates to the non-aqueous ink composition described above, which contains an alkylene glycol solvent as the organic solvent.

  Furthermore, this invention relates to the non-aqueous inkjet ink in any one of the said description.

According to the present invention, by adding β-alkoxypropionamides to the ink composition, a non-aqueous ink composition excellent in adhesion to a non-absorbing substrate, particularly a non-aqueous inkjet ink is provided.

  As the organic solvent of the present invention, β-alkoxypropionamides represented by the general formula (1) are preferably used. These β-alkoxypropionamides have higher safety and hygiene compared to solvents such as N-methyl-2-pyrrolidone, but are very soluble in resins and the like. When used in printing inks, PVC, etc. It is possible to slightly dissolve the surface of the non-absorbent substrate and to exhibit very excellent adhesion. The amount of β-alkoxypropionamide added to the ink composition is preferably 1 to 50% by weight, preferably 3 to 30% by weight, more preferably 5 to 20% by weight. If the addition amount is 1% by weight or less, the effect of adhesion to the substrate due to its solubility cannot be obtained. Conversely, if it is 50% by weight or more, part of the printer or printer member is corroded, which is not preferable.

  Furthermore, as the organic solvent used in the present invention, various organic solvents can be mixed and used in addition to the β-alkoxypropionamides represented by the general formula (1). As an organic solvent that can be used, the boiling point at 1 atm is preferably 150 ° C. or higher, preferably 150 ° C. or higher and 280 ° C. or lower, more preferably 180 ° C. or higher and 280 ° C. It is as follows. When the boiling point is 150 ° C. or lower, the drying speed is high, the handling is poor with printing ink, and nozzle clogging is caused as inkjet ink. When the boiling point is 280 ° C. or higher, the drying speed is lowered, causing problems such as blocking of printed matter.

  As the kind of the organic solvent used by mixing with the β-alkoxypropionamide represented by the general formula (1), an alkylene glycol solvent is preferably selected from the viewpoint of odor and safety and health. Specific examples include glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol. Monobutyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, propylene glycol n-propyl ether, triethylene glycol monomethyl ether , Glycol ethers such as triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tetraethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol Monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether propionate, ethylene glycol Ethyl ether propionate, ethylene glycol monobutyl ether propionate, diethylene glycol monomethyl ether propionate, diethylene glycol monoethyl ether propionate, diethylene glycol monobutyl ether propionate, propylene glycol monomethyl ether propionate, dipropylene glycol monomethyl ether pro Pionate, ethylene glycol monomethyl ether butyrate, ethylene glycol monoethyl ether butyrate, ethylene glycol monobutyl ether butyrate, diethylene glycol monomethyl ether butyrate, diethylene glycol monoethyl ether butyrate, diethylene glycol monobutyl ether butyrate, propylene glycol Glycol monoacetates such as dimonomethyl ether butyrate and dipropylene glycol monomethyl ether butyrate, ethylene glycol diacetate, diethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, ethylene glycol acetate propionate, ethylene glycol acetate Butyrate, ethylene glycol propionate butyrate, ethylene glycol dipropionate, ethylene glycol acetate dibutyrate, diethylene glycol acetate propionate, diethylene glycol acetate butyrate, diethylene glycol propionate butyrate, diethylene glycol dipropionate, diethylene glycol acetate dibutyrate Propylene glycol acetate propionate, propylene glycol acetate butyrate, propylene glycol propionate butyrate, propylene glycol dipropionate, propylene glycol acetate dibutyrate, dipropylene glycol acetate propionate, dipropylene glycol acetate butyrate, Examples thereof include glycol diacetates such as dipropylene glycol propionate butyrate, dipropylene glycol dipropionate and dipropylene glycol acetate dibutyrate.

  As the pigment used in the present invention, various pigments used in printing inks, paints and the like can be used. When these pigments are represented by color index, Pigment Black 7, Pigment Blue 15, 15: 1, 15: 3, 15: 4, 15: 6, 60, Pigment Green 7, 36, Pigment Red 9, 48, 49 , 52, 53, 57, 97, 122, 149, 168, 177, 178, 179, 206, 207, 209, 242, 254, 255, pigment violet 19, 23, 29, 30, 37, 40, 50, pigment Yellow 12, 13, 14, 17, 20, 24, 74, 83, 86, 93, 94, 95, 109, 110, 117, 120, 125, 128, 137, 138, 139, 147, 148, 150, 151 , 154, 155, 166, 168, 180, 185, 213, Pigment Orange 36, 43, 51, 5 , Such as 59,61,71,74, and the like. As for carbon black, any carbon black such as neutral, acidic and basic can be used. The pigment is desirably contained in the ink composition in an amount of 0.1 to 10% by weight.

  The resin used in the present invention has an effect of further improving the adhesion to a non-absorbent substrate. Usable resins include acrylic resin, styrene-acrylic resin, styrene-maleic resin, rosin resin, rosin ester resin, ethylene-vinyl acetate resin, petroleum resin, coumarone indene resin, terpene phenol Resin, phenol resin, urethane resin, melamine resin, urea resin, epoxy resin, cellulose resin, vinyl acetate resin, xylene resin, alkyd resin, aliphatic hydrocarbon resin, butyral resin, maleic acid resin, fumaric acid Examples thereof include resins. Specific examples of the resin include Superester 75 manufactured by Arakawa Chemical Co., Ltd., Ester Gum HP, Malkid 33, YS Polystar T80 manufactured by Yasuhara, Hirtts HRT200X manufactured by Mitsui Chemicals, John Kuryl 586 manufactured by Johnson Polymer, Dow Chemicals Examples include Uker solution vinyl resins VYHD, VYHH, VMCA, VROH, VYLF-X, and solvin resins CL, CNL, C5R, and TA5R manufactured by Nissin Kagaku Kogyo. The resin is preferably contained in the ink composition in an amount of 0.1 to 10% by weight.

  In the present invention, a dispersant can be added in order to improve the dispersibility of the pigment and the storage stability of the ink composition. Examples of the dispersant include a hydroxyl group-containing carboxylic acid ester, a salt of a long-chain polyaminoamide and a high molecular weight acid ester, a salt of a high molecular weight polycarboxylic acid, a salt of a long chain polyaminoamide and a polar acid ester, a high molecular weight unsaturated acid ester, Molecular copolymer, modified polyurethane, modified polyacrylate, polyether ester type anionic activator, naphthalene sulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate salt, polyoxyethylene alkyl phosphate ester, polyoxyethylene nonyl Various acidic and basic dispersants such as phenyl ether and stearylamine acetate can be used.

  Specific examples of the dispersant include “Anti-Terra-U (polyaminoamide phosphate)”, “Anti-Terra-203 / 204 (high molecular weight polycarboxylate)”, “Disperbyk-101” (polyamino) manufactured by BYK Chemie. Amide phosphate and acid ester), 107 (hydroxyl group-containing carboxylic acid ester), 110, 111 (copolymer containing acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (high Molecular copolymer) ”,“ 400 ”,“ Bykumen ”(high molecular weight unsaturated acid ester),“ BYK-P104, P105 (high molecular weight unsaturated acid polycarboxylic acid) ”,“ P104S, 240S (high molecular weight unsaturated) Acid polycarboxylic acid and silicon) "," Lactimon (long-chain amine and unsaturated acid polycarbonate) Rubonic acid and silicon).

  Also, “Efka CHEMICALS” “Efka 44, 46, 47, 48, 49, 54, 63, 64, 65, 66, 71, 701, 764, 766”, “Efka Polymer 100 (modified polyacrylate), 150 (aliphatic) System modified polymer), 400, 401, 402, 403, 450, 451, 452, 453 (modified polyacrylate), 745 (copper phthalocyanine system) "," Floren TG-710 (urethane oligomer) "," Flownon "manufactured by Kyoeisha Chemical Co., Ltd. “SH-290, SP-1000”, “Polyflow No. 50E, No. 300 (acrylic copolymer)”, “Disparon KS-860, 873SN, 874 (polymer dispersing agent), # 2150 (manufactured by Enomoto Kasei Co., Ltd.) Aliphatic polyvalent carboxylic acid), # 7004 (polyether ester type) ” That.

Further, “Demol RN, N (Naphthalenesulfonic acid formalin condensate sodium salt), MS, C, SN-B (aromatic sulfonic acid formalin condensate sodium salt), EP”, “Homogenol L-18 (poly) Carboxylic acid type polymer), “Emulgen 920, 930, 931, 935, 950, 985 (polyoxyethylene nonyl phenyl ether)”, “Acetamine 24 (coconut amine acetate), 86 (stearyl amine acetate)”, manufactured by Lubrizol "Solspers 5000 (phthalocyanine ammonium salt type), 13940 (polyesteramine type), 17000 (fatty acid amine type), 32000, 24000", "Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IE, manufactured by Nikko Chemical Co., Ltd." X (polyoxyethylene monostearate), Hexagline 4-0 (hexaglyceryl tetraoleate) "," Ajisper PB821, PB822 (basic dispersant) "manufactured by Ajinomoto Fine Techno Co., and the like. The dispersant is preferably contained in the ink in an amount of 0.1 to 10% by weight.
The ink composition of the present invention can also use various additives such as a plasticizer, a surface conditioner, an ultraviolet light inhibitor, a light stabilizer, an antioxidant, and a hydrolysis inhibitor.

  Examples of the non-absorbable substrate whose effect can be confirmed in the present invention include a polyvinyl chloride resin (PVC) sheet, a polyolefin-based sheet, glass, metal, and the like, and a PVC sheet is particularly preferable.

[Example]
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not particularly limited to the examples. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”.

[Example 1]
[Production of Pigment Dispersion a]
Pigment dispersion a was prepared with the following composition. This pigment dispersion was prepared by putting a pigment and a dispersant in an organic solvent, stirring the mixture with a high speed mixer or the like until uniform, and then dispersing the obtained mill base with a horizontal sand mill for about 1 hour.

・ LIONOL BLUE FG-7400G (Toyo Ink phthalocyanine pigment)
35.0 parts Ajisper PB821 (basic pigment dispersant manufactured by Ajinomoto Fine Techno)
12.5 parts diethylene glycol diethyl ether
52.5 parts

[Production of Ink Composition A]
Using the pigment dispersion a, an ink composition A was prepared according to the following formulation. The β-alkoxypropionamides used are as shown in Table 1.

・ Pigment dispersion A 11.5 parts ・ Solvine CL (Nisshin Chemical's vinyl acetate resin) 4.5 parts ・ β-alkoxypropionamides 10.0 parts ・ Tetraethylene glycol dimethyl ether 10.0 parts ・ Diethylene glycol 64.0 parts diethyl ether

[Examples 2 to 8, Comparative Examples 1 and 2]
Ink compositions B to J were prepared as Examples 2 to 8 and Comparative Examples 1 and 2 in the same manner as in Example 1, using the raw materials and blending ratios described in Tables 1, 2, and 3.

The obtained ink compositions A to J were comparatively evaluated by the following method. The evaluation results are shown in Table 4.
[Printing stability]
In a 25 ° C environment, using Color Painter 64S (manufactured by Seiko I Infotech Co., Ltd., large-format inkjet printer), the surface is continuously printed on an untreated polyvinyl chloride resin sheet, and the frequency of occurrence of missing dots, flying bends or ink splattering is checked. Evaluate and show that dot missing, flying bent or ink splatter occurred less than 10 times in a 50-hour continuous test, ○ 10 times or more, less than 20 times, Δ, 20 times or more X was evaluated.
[Drying]
Under a 25 ° C. environment, a color printer 64S (manufactured by Seiko I Infotech Co., Ltd., large-format inkjet printer) was used to print solid on a non-treated polyvinyl chloride resin sheet and measure the time until drying at 40 ° C. Those that dried within 3 minutes were evaluated as ◯, those that were 3 minutes or more and less than 6 minutes were evaluated as Δ, and those that were dried for 6 minutes or more were evaluated as ×.
[Corrosive]
The parts of the printing press that are in contact with the ink composition are dipped in the ink compositions A to J, respectively, and the rate of change in dimensions and weight of the material before and after storage at 70 ° C. for 3 weeks is evaluated. A change rate of less than 3% was evaluated as ◎, 3% or more and less than 6% as ○, 6% or more and less than 9% as Δ, and 9% or more as ×.
[Adhesion]
Under an environment of 25 ° C., a color painter 64S (manufactured by Seiko I Infotech Co., Ltd., large-format inkjet printer) is used to print on a non-treated polyvinyl chloride resin sheet, and the printed surface is a rubbing tester (model AB301, manufactured by Tester Sangyo). To evaluate adhesion. As evaluation conditions, a test piece (gold width 3) was applied with a load of 200 g and 50 reciprocations. The case where the coated surface was not peeled off at all was indicated by ○, and the case where a part of the color was dropped was indicated by Δ. The case where the substrate was visible was evaluated as x.

  By using β-alkoxypropionamides as organic solvents in the ink composition, it can be applied to non-aqueous ink compositions with excellent adhesion to non-absorbent substrates, especially non-aqueous inkjet inks. It is.

Claims (4)

A non-aqueous ink composition comprising a β-alkoxypropionamide represented by the following general formula (1) as an organic solvent in a non-aqueous ink composition comprising at least an organic solvent, a pigment, and a resin. .
General formula (1)

(In the formula, R ¹ is an alkyl group having 3 to 10 carbon atoms, and R ² and R ³ are each independently a hydrogen atom or a hydrocarbon group that may have an ether bond having 1 to 6 carbon atoms. They may be different from each other and may be further bonded to each other to form a ring structure.)   The non-aqueous ink composition according to claim 1, wherein the organic solvent has a boiling point of 150 ° C or higher at 1 atm.   The non-aqueous ink composition according to claim 1, wherein the organic solvent contains an alkylene glycol solvent. The non-aqueous inkjet ink according to any one of claims 1 to 3.