JP2885780B1 - Ink composition for inkjet printing - Google Patents

Abstract

Abstract: PROBLEM TO BE SOLVED: To form a printed film having excellent adhesion, heat resistance, abrasion resistance, water resistance and light resistance on a base material surface such as metal, glass and plastic; Even if a substrate is superimposed on the printed film, a printed film that is not transferred to the superposed substrate surface can be formed, and ink jet printing excellent in anti-bleeding properties, anti-fogging properties and storage stability. The present invention provides an ink composition. SOLUTION: As components, (1) a solvent mainly composed of ethanol, (2) at least one binder selected from a polyamide resin, a toluenesulfonic acid formaldehyde resin and an amine-modified silicone acrylic resin, and (3) a polyalkylene oxide. It contains carbon black grafted with a polymer containing a group as a side chain, and (4) a dye having an imino group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to metal, glass,
Adhesion, heat resistance,
A printed film that can form a printed film excellent in wear resistance, water resistance and light resistance, and is not transferred to the surface of the superposed substrate even when the substrate is overlaid on the printed film. The present invention relates to an ink composition for ink jet printing, which is capable of forming an ink and has excellent anti-bleeding property, anti-fogging property and storage stability.

[0002]

2. Description of the Related Art In recent years, metals, glass, plastics,
It is widely practiced to apply dot printing, pattern printing, and the like to the surface of a substrate such as paper by an inkjet printing method. There is a method in which dot printing or pattern printing is performed by this inkjet printing method, and a film formed by this printing is tested by a cross-cut tape method, but a film that is considered to have sufficient adhesion in the evaluation by this test method Has not been obtained so far. In addition, the above-mentioned base material surface is subjected to inkjet printing, and after drying, when a base material is superimposed on the printed film and a load is applied, the printed film is transferred to the superposed base material surface. was there. Furthermore, in order to improve the durability of a product having a pattern coating formed by an inkjet printing method, it is required to further improve the heat resistance, abrasion resistance, water resistance and light resistance of the print coating, and In order to improve the quality of printing, it is required to further improve the bleeding preventing property, the bleeding preventing property and the storage stability of the ink composition for jet printing.

[0003] However, at present, a print film that sufficiently satisfies all of the above conditions has not been obtained with the ink composition for ink jet printing used in the conventional ink jet printing method.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above-mentioned problems of the conventional ink composition for ink jet printing, and to improve the adhesiveness, heat resistance, abrasion resistance and the like.
It is possible to form a print film excellent in water resistance and light resistance, and to form a print film that is not transferred to the surface of the superimposed substrate even when a substrate is superimposed on the print film. An object of the present invention is to provide an ink composition for ink jet printing which is capable of preventing bleeding, preventing bleeding and having excellent storage stability.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, using a polyamide resin, a toluenesulfonic acid formaldehyde resin or a silicone acrylic resin amine-modified product as a binder, A carbon black grafted with a polymer such as a vinyl polymer containing a polyalkylene oxide group as a side chain (hereinafter also referred to simply as "grafted carbon black"), and a dye having an imino group as a dye. Adhesion, heat resistance,
A print film with excellent abrasion resistance, water resistance, light resistance, etc. can be formed, and even if a base material is overlaid on the print film, a print film that is not transferred to the surface of the superposed base material is formed. The present invention has been found that an ink composition for inkjet printing which can be obtained and has excellent anti-bleeding property, anti-fogging property and storage stability can be obtained.

That is, the present invention provides the following components: (1) a solvent mainly composed of ethanol, (2) at least one binder selected from a polyamide resin, a toluenesulfonic acid formaldehyde resin and an amine-modified silicone acrylic resin, The present invention relates to an ink composition for inkjet printing containing (3) carbon black grafted with a polymer having a polyalkylene oxide group as a side chain, and (4) a dye having an imino group.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the ink composition for ink jet printing of the present invention will be described in detail. The solvent (1) used in the present invention is used for appropriately adjusting the viscosity of the ink composition for inkjet printing. The solvent used in the present invention is a solvent mainly composed of ethanol. That is, the solvent used in the present invention is a solvent consisting of ethanol alone or a mixed solvent of ethanol and an additional solvent other than ethanol.

The additional solvent used in the present invention includes:
For example, ketones such as acetone, methyl ethyl ketone and cyclohexanone, other alcohols such as methanol and isopropanol, and ethers such as cellosolve and butyl cellosolve can be preferably mentioned. These additional solvents may be used alone or in combination as a mixture. Suitably, such additional solvents are formulated in small amounts with respect to ethanol. For example, the additional solvent is usually 0.01 to 3%, preferably 0.1 to 1%.
It is appropriate to use%. The solvent is determined in consideration of the viscosity, surface tension, and the like of the ink composition for inkjet printing of the present invention, but is usually 60 to 95% by weight of the ink composition for inkjet printing, preferably 70 to 9%.
A suitable amount is 0% by weight.

[0009] The binder used in the present invention is selected from polyamide resins, toluenesulfonic acid formaldehyde resins and amine-modified silicone acrylic resins. A polyamide resin is a polymer containing amino acids, lactams or diamines, and dicarboxylic acids as main components. As the amino acid, for example, an aliphatic amino acid such as 12-aminododecanoic acid is preferably exemplified. As a lactam,
For example, ε-caprolactam, enantholactam, ω
-Lactams such as laurolactam are preferred.

Examples of the diamine include tetramethylenediamine, hexamethylenediamine, undecamethyleneamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, and 5-methylnonamethylene. Diamine, m-xylylenediamine, p-xylylenediamine, 1,3-bisaminomethylcyclohexane, bis-p-aminocyclohexylmethane, bis-p-aminocyclohexylpropane,
Isophoronediamine and the like. Examples of the dicarboxylic acid include adipic acid, alicyclic acids such as suberic acid, azelaic acid, sebacic acid, and dodecane diacid; alicyclic acids such as 1,4-cyclohexanedicarboxylic acid and 1,3-cyclohexanedicarboxylic acid. Examples include aromatic dicarboxylic acids such as dicarboxylic acid, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid, and dimer acids.

These constituents are subjected to polymerization alone or in the form of a mixture of two or more kinds, and any of the polyamide homopolymers and copolymers thus obtained can be used in the present invention. Particularly useful polyamides useful in the present invention include nylon 6, nylon 66, nylon 610, nylon 11, nylon 12, and polyamide copolymers and mixtures thereof. There is no particular limitation on the degree of polymerization of the polyamide resin used here. As the toluenesulfonic acid formaldehyde resin used in the present invention, a resin having a structure represented by the following general formula is suitable, and either an ortho type or a para type may be used.

[0012]

Embedded image (In the formula, n is 2-3.)

The amine-modified silicone acrylic resin (also referred to as "amine-modified product") used in the present invention is obtained by reacting an acrylic acid or an acrylate-based polymer with an organopolysiloxane to give, for example, a molecular weight of 10,000.
0 to 150,000, preferably 10,000 to 5
It is obtained by preparing a silicone acrylic resin composed of 000 block polymer or graft polymer, and then substituting some or all of the functional groups of the silicone acrylic resin with a secondary amine. The acrylic acid or acrylic ester polymer is obtained by polymerizing a monomer such as an α, β-unsaturated acid or an ester thereof. Usually, it is a polymer or copolymer having a molecular weight of 500 to 8,000, preferably 1,000 to 15,000. Examples of the α, β-unsaturated acid or its ester include acrylic acid, methacrylic acid, their methyl ester, ethyl ester, butyl ester, stearyl ester, 2-ethylhexyl ester, 2-hydroxyethyl ester, 3-hydroxypropyl Examples include alkyl esters such as esters. Α, β
-Comonomers that can be copolymerized with unsaturated acids or their esters include maleic acid, itaconic acid, fumaric acid, styrene, α-methylstyrene, vinyl acetate, vinyl propionate and the like. In the case of the above-mentioned acrylic acid or acrylate ester-based polymer or copolymer, the ratio of acrylic acid, methacrylic acid or its ester in the total copolymer is usually 10 to 75 mol%, preferably 25 to 75 mol%. 60 mol% is suitable. As the organopolysiloxane used for producing the amine-modified silicone acrylic resin, a linear polymer having a hydroxyl group is preferably used, and examples thereof include compounds represented by the following formula.

HO-Si (CH_Three)_Two-O- (Si (C
H_Three)_Two-O) n-Si (CH_Three) _Two—OH (in the formula, n is 10 to 5000) In addition, up to 80 mol% of the methyl groups in the above formula is ethyl.
Group, a vinyl group or a phenyl group.
In particular, the methyl group is 50 mol% or more, preferably 60 mol%.
% Or more is preferred. Ami
Used to produce modified silicone acrylic resin
Examples of the secondary amine include dimethylamine and diamine.
Ethylamine, dipropylamine, diisopropylamido
Has an NH group such as dibutylamine, dibutylamine and diamylamine
Preferred are aliphatic secondary amines.

The binder (2) used in the present invention can be obtained by using the above-mentioned polyamide resin, toluenesulfonic acid formaldehyde resin and silicone acrylic resin amine modified product alone or in the form of a mixture of two or more. Good. The binder (2) is suitably used in an amount of usually 1 to 50% by weight, preferably 1 to 20% by weight, based on the weight of the ink composition for inkjet printing. The pigment (3) used in the present invention is a grafted carbon black obtained by grafting a polymer containing a polyalkylene oxide group as a side chain. Grafting a polymer containing such a polyalkylene oxide group in the side chain onto carbon black is very useful for achieving the object of the present invention.

The grafted carbon black is obtained, for example, by reacting a grafted polymer having a reactive group capable of reacting with a functional group on the surface of the carbon black and containing a polyalkylene oxide group as a side chain with the carbon black. Can be easily prepared. On the surface of the carbon black, as a functional group, for example,-
OH, -COOH, = C = O and the like exist. Therefore, as the reactive group of the grafted polymer, a reactive group that reacts with these functional groups is used. Examples of such a reactive group include an oxazoline group, an aziridine group,
Examples include an N-hydroxyalkylamide group, an epoxy group, a thioepoxy group, an isocyanate group, a vinyl group, a silicon-based hydrolyzable group (for example, a hydrolyzable silyl group), and an amino group. Among them, particularly, an oxazoline group, an aziridine group and the like can be preferably used.
Preferred examples of the polyalkylene oxide group include those having a structure represented by the following formula.

-(A-O) _n -wherein A represents an alkylene group. As the alkylene group, a linear or branched alkylene group is exemplified, and for example, the number of carbon atoms is preferably 1 to 5, preferably 2 to 4, particularly preferably 2 to 3. is there. As such an alkylene group, for example, a methylene group,
Examples include an ethylene group, a propylene group, and a butylene group. It is appropriate that n indicating the number of moles to be added is usually 25 to 40, preferably 27 to 38, and particularly preferably 28 to 35. Therefore, the molecular weight of the polyalkylene oxide group is usually 1,000 to 2,000, preferably 1,100 to 1,80.
0, particularly preferably 1,200 to 1,600, is within this range, since the dispersibility in ethanol is improved, which is preferable.

The grafted polymer used in the present invention is
For example, it can be obtained by copolymerizing a vinyl polymerizable monomer having a polyalkylene oxide group and a vinyl polymerizable monomer having a reactive group that reacts with a functional group present on the surface of carbon black. As the vinyl polymerizable monomer having a polyalkylene oxide group, for example, a vinyl polymerizable monomer represented by the following structure can be preferably mentioned.

[0019]

Embedded image In the formula, R ₁ represents a hydrogen atom or a methyl group, and X is a protecting group for a hydroxyl group derived from an alkylene glycol group, for example, an alkyl group such as a methyl group or an ethyl group. n
Is a number from 25 to 40. When n is less than 25, problems occur in the water resistance and dispersibility of the obtained grafted polymer. Conversely, when n exceeds 40, problems in solubility in a solvent and synthesis occur easily, which is not preferable. . When this monomer is polymerized, a vinyl polymer having a polyalkylene oxide group in a side chain is obtained. Further, as the vinyl polymerizable monomer having a reactive group that reacts with the surface functional group of carbon black, for example, the following monomers are preferably exemplified.

[0020]

Embedded image

[0021]

Embedded image

[0022]

Embedded image

[0023]

Embedded image

[0024]

Embedded image

[0025]

Embedded image

[0026]

Embedded image

[0027]

Embedded image

[0028]

Embedded image

[0029]

Embedded image

N-hydroxymethylacrylamide, N-hydroxyethylacrylamide, N-hydroxybutylacrylamide, N-hydroxyisobutylacrylamide, N-hydroxy-2-ethylhexylacrylamide, N-hydroxycyclohexylacrylamide , N
N-hydroxyalkyl amides such as -hydroxymethyl methacrylamide, N-hydroxyethyl methacrylamide, N-hydroxybutyl methacrylamide, N-hydroxyisobutyl methacrylamide, N-hydroxy-2-ethylhexyl methacrylamide, N-hydroxycyclohexyl methacrylamide Group-containing monomers; 2-vinyl-2-oxazoline, 2-vinyl-4-
Methyl-2-oxazoline, 2-vinyl-5-methyl-
2-oxazoline, 2-vinyl-4-ethyl-2-oxazoline, 2-vinyl-5-ethyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, Oxazoline group-containing monomers such as 2-isopropenyl-5-methyl-2-oxazoline, 2-isopropenyl-4, and 5-dimethyl-2-oxazoline can be exemplified. Particularly, isopropenyl oxazoline and the like can be mentioned as suitable monomers. These monomers are
It can be used alone or as a mixture of these monomers.

The amount of the monomer having a polyalkylene oxide group is preferably from 65 to 85, based on the total amount of the monomer and the monomer having a reactive group which reacts with the functional group present on the surface of the carbon black. Suitably, it is in an amount of from 68% to 83% by weight. If the content of the monomer having a polyalkylene oxide group is less than 65% by weight, even if the obtained polymer reacts with carbon black, the dispersibility of the polymer will be impaired, which is not preferable. On the other hand, when the amount of the monomer containing a polyalkylene oxide group is 85%
If the content is more than the weight%, it is difficult to synthesize the composition, which is not preferable. In producing the grafted polymer, an additional monomer may be copolymerized with the above monomer in order to improve other properties and the like of the grafted polymer. Examples of such additional monomers include those that do not adversely affect the grafting reaction.
Various monomers can be used. Such additional monomers include, for example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-methoxystyrene, p-methoxystyrene.
Styrene monomers such as tert-butylstyrene, p-phenylstyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene; acrylic acid, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate , Dodecyl acrylate, stearyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, Acrylic or methacrylic monomers such as 2-ethylhexyl methacrylate and stearyl methacrylate; ethylene, propylene, butylene, vinyl chloride, vinyl acetate, acrylonitrile, acrylamide, methacrylamide , N-vinylpyrrolidone and the like, and these can be used alone or as a mixture of these other monomers.

The reactive group must have at least one reactive group in one molecule of the grafted polymer on average. However, as the number of reactive groups increases, the dispersibility of the grafted carbon black in other constituent components increases. Therefore, it is appropriate that the average number is 1 to 5, preferably 1 to 2, and particularly preferably 1 in one molecule. The molecular weight of the grafted polymer is not particularly limited as long as the molecular weight of the polyalkylene oxide group is within the above range,
In terms of a remarkable treatment effect on carbon black and workability at the time of reaction with carbon black, for example, the number average molecular weight is 500 to 1,000,000, preferably 1,000 to 500,000,
Particularly preferably, it is suitable to be 2,000 to 100,000. In the grafted polymer, the proportion occupied by the polyalkylene oxide group is usually 65 to 85% by weight, preferably 68 to 85% by weight, based on the weight of the grafted polymer.
Suitably, it is 重量 83% by weight. This ratio is 6
If the amount is less than 5% by weight, a problem occurs in the dispersibility of the grafted polymer.

The amount of carbon black in the grafted carbon black is usually 30 to 50% by weight, preferably 35 to 45% by weight. Also, the grafted carbon black is based on 100 parts by weight of the binder.
Usually, it is appropriate to use it in an amount of 5 to 1,000 parts by weight, preferably 50 to 250 parts by weight. As the dye used in the present invention, a dye having an imino group (NH group) in a molecular structure or a dye having an imino group added to a molecule can be suitably used. Examples of such dyes include C.I. I. Solvent Black 28, C.I.
I. Solvent Blue 70, C.I. I. Basi
c Blue 5, C.I. I. Basic Blue 7,
C. I. Basic Violet 1, C.I. I. Bas
ic Violet 3, C.I. I. Basic Red
1, C.I. I. Basic Red 8, C.I. I. Acid
Black 2 and the like.

The amount of the dye having an imino group is usually 50 to 400 parts by weight, preferably 80 to 250 parts by weight, per 100 parts by weight of the binder. The ink composition for ink-jet printing of the present invention comprises the solvent
Contains (1) and, if necessary, further includes additives such as a coloring agent other than a dye having an imino group, a conductivity adjuster, a surfactant, an ultraviolet absorber, a quencher, a dispersant, and a preservative. can do. The other colorant that can be used in the present invention is compatible with other ink components,
Further, those having good solubility in a solvent are preferable. Representative examples include C.I. I. Solvent Black 22,
C. I. Solvent Black 27, C.I. I. S
solvent Black 29, C.I. I. Solven
t Red83 1, C.I. I. Solvent Red
125, C.I. I. Solvent Red 132, C.I.
I. Solvent Blue 47, C.I. I. Solv
ent Blue 48, C.I. I. SolventY e
low 88, C.I. I. Solvent Yellow
89, basic dye, titanium oxide, carbon black,
Zinc sulfide, oil smoke, graphite, red bengal, phthalocyanine blue, phthalocyanine green, brilliant carmine 6
B, Lake Red C, and other inorganic or organic pigments. However, when an insoluble dye or pigment is used, the particle size is usually 3 μm to prevent nozzle clogging.
m or less, particularly preferably 0.5 μm or less.

Such a colorant is usually used in an amount of 50 to 400 parts by weight, preferably 80 to 400 parts by weight, per 100 parts by weight of the binder.
A suitable amount is 250 parts by weight. Examples of the conductivity adjuster that can be used in the present invention, for example, lithium nitrate, lithium nitrite, ammonium sulfite,
Examples thereof include ammonium formate, ammonium acetate, lithium halide, and sodium thiocyanate. Further, the above-mentioned surfactants, ultraviolet absorbers, quenchers, preservatives and the like which can be used in the present invention are those usually used in ink compositions for ink jet printing. The ink composition for ink jet printing of the present invention may contain these additives in an amount of, for example, 0.1 to 5% by weight of the ink composition. The ink composition for ink-jet printing of the present invention needs to have properties suitable for an ink-jet printing method, and therefore, the ink composition for ink-jet printing usually has a viscosity of 1 to 1.
0 centipoise (20 ° C), surface tension is usually 20 to
60 dynes / cm, specific resistance is usually 200 to 3,000 Ω
It is generally desirable that the specific gravity and the specific gravity be in the range of 0.8 to 1.2.

When preparing the ink composition for ink jet printing of the present invention, after mixing and stirring each component, for example, about 1/10 of the nozzle diameter of the jet printer to be used.
The mixture is filtered and purified using a filter having the following pore size. The ink composition for inkjet printing of the present invention can be used in a conventionally known inkjet printer. Examples of such an ink-jet printer include a load control system, an ink-on-demand system, and a system in which ink is ejected by a thermal head. The ink-jet printed ink forms a dry film by drying at room temperature to several hundred degrees Celsius. During this drying, the imino group in the dye having an imino group forms a hydrogen bond and forms a reaction film on the surface of the coating film in a dense structure in which water molecules are hardly mixed. Can be suppressed.

The object to be printed using the ink composition for ink jet printing of the present invention is not particularly limited as long as it is not deformed or deteriorated under the conditions for drying the printed ink composition. For example, metal, glass,
Examples include the surface of a base material such as plastic, paper whose surface is coated with a resin, and a transparent sheet for an overhead project. The ink composition for ink-jet printing of the present invention can form a print film excellent in adhesion, heat resistance, abrasion resistance, water resistance and light resistance as compared with conventional ink compositions for ink-jet printing. In addition, even when a substrate is overlaid on the printed film, a printed film that is not transferred to the surface of the overlaid substrate can be formed, and furthermore, bleeding prevention, bleeding prevention and storage during printing can be achieved. Excellent stability.

[0038]

The present invention will be described below in more detail with reference to Examples and Comparative Examples. <Preparation of grafted carbon black>Methanol; 32 parts, sodium hydroxide; 0.35 in an autoclave equipped with a stirrer, a thermometer, and an ethylene oxide supply device.
264 parts of ethylene oxide were added dropwise while maintaining the pressure at 5 to 8 kg / cm ² while stirring, and the mixture was aged for 1 hour.
The temperature was further raised to 150 ° C., and ethylene oxide: 1
056 parts was added dropwise over 5 hours and then aged for 2 hours to obtain an adduct of 30 mol methoxylated ethylene oxide at one end. A flask equipped with a Dean Stark equipped with a stirrer, a thermometer, and a condenser was charged with 1352 parts of methoxylated ethylene oxide adduct (1352 parts) at one end, melted at 50 ° C., and then melted with methacrylic acid (MA
A); 172.2 parts, as a catalyst, p-toluenesulfonic acid (PTS); 15.24 parts, as a polymerization inhibitor, phenothiazine; 0.3 parts, as a dehydrating solvent, cyclohexane;
22 parts were charged.

Thereafter, the temperature was raised, the internal temperature was raised to 105 ° C., and the esterification reaction was terminated while removing generated water and the like. Hydroquinone as a polymerization inhibitor; 50 ppm
The mixture was added, and the remaining MAA and PTS were neutralized to obtain a macromonomer of ethylene oxide 30 mol adduct having a methoxy group at one end and a methacryloyl group at the other end. The above macromonomer; 75 parts, styrene; 20
Part, isopropenyl oxazoline; 5 parts, 2,2'-azobis (2,4-dimethylvaleronitrile) as an initiator; 5 parts dissolved in 100 parts of toluene; and charged in a dropping funnel in advance to prepare a monomer composition. did. Stirrer,
A flask equipped with a reflux condenser, a dropping funnel, and an N ₂ inlet was charged with 50 parts of toluene, and the temperature was raised to 80 ° C. The monomer composition was dropped from the dropping funnel over 3 hours. Thereafter, polymerization was performed for 2 hours, the temperature was raised to 110 ° C., and polymerization and aging were further performed for 2 hours. The solvent was removed by an evaporator, and toluene was completely removed using a reduced-pressure drier to obtain a vinyl polymer having an oxazoline group and a polyalkylene oxide group as a reactive group in the side chain (molecular weight: 15,000). .

10 parts of carbon black and 8 parts of the above vinyl polymer were subjected to a kneading reaction at 100 ° C. and 100 rpm for 1 hour with a Labo Plastomill (manufactured by Toyo Purification Co., Ltd.) to obtain grafted carbon black (GCB). I took it out. The GCB was dissolved and dispersed in 82 parts of ethanol to obtain an ethanol dispersion.

Examples 1 to 5 and Comparative Examples 1 to 4 As polyamide resins, the following formulas were used:-[RCONH] _n- and-[ORCONHRRN
H] _n − (R is an alkyl group, and n is the degree of polymerization.) A copolymer having a constitutional unit (molecular weight: about 9,000) is used as a toluenesulfonic acid formaldehyde resin.
The following formula:

[0042]

Embedded image (Where n is the degree of polymerization)
Amine modified product prepared by using a copolymer of methyl methacrylate and dimethylpolysiloxane as a silicone acrylic resin amine modified product and using Nn-butoxymethylacrylamide as a secondary amine (molecular weight: about 2000
0), a copolymer of methyl methacrylate and dimethylpolysiloxane (molecular weight: about 2000) was used as a silicone acrylic resin as a control, and an acrylic resin (molecular weight: about 2000) was used as a control.
0; acid value: 599), and the above GCB ethanol dispersion (carbon black: polymer: ethanol = 1) as an imino group-containing dye and grafted carbon black.
0: 8: 82), using the materials shown in Table 1 below as a colorant, a solvent and a conductivity adjuster, respectively, blending them in the amounts (parts by weight) shown in Table 1 and mixing them uniformly. Thereafter, the mixture was purified by filtration through a membrane filter having a pore size of 1.0 μm to prepare ink compositions for inkjet printing corresponding to each Example and each Comparative Example.

Each of the obtained ink compositions is jetted in a predetermined image by an ink jet printer,
Glass plate and polyethylene terephthalate film (P
ET) to form a print film on each, and the adhesion, transfer resistance, heat resistance, bleeding / repelling of dots, abrasion resistance, water resistance, light resistance, and storage stability of the print film as described below. evaluated. <Adhesion>: 1 mm square according to JIS K5400
A cross-cut test of 00 pieces was carried out, the peeled state was confirmed with a cellophane tape, and the number of adhesions out of 100 pieces (the number of cross-cuts remaining without being peeled) was evaluated. <Transfer resistance>: The same substrate is superimposed on the printed film,
Press down with a force of 10 kgf / cm ² ,
After standing for a time, the presence or absence of transfer to the stacked substrates was examined and evaluated according to the following criteria. ：: no transfer ×: transfer was partially observed <heat resistance>: After standing in a thermostat at 120 ° C. for 50 hours, a ΔE value with the sample before the test was obtained and evaluated according to the following criteria. . ：: ΔE ≦ 1 ×: ΔE> 1 <Dot bleeding / repelling>: The dot bleeding / repelling immediately after dot printing was visually examined and evaluated according to the following criteria. ：: No abnormality ×: Bleeding or bleeding <Abrasion resistance>: The printed coating was rubbed 100 times with a rubbing tester with a load of 750 kg / cm ² , and the presence or absence of peeling of the printed coating was examined. Was evaluated. ：: No abnormality ×: Printing film peeling was observed in part

<Water resistance>: After immersion in water at room temperature for 24 hours, the above-mentioned abrasion resistance test was carried out and evaluated according to the following criteria. ：: No abnormality x: Printed film peeling was partially observed. <Light resistance>: UV intensity was 23 mw in 360 nm spectrum.
After exposure to a fade meter of / cm ² for 300 hours, the OD value ratio with the duplicate sample is determined. ：: OD value ≦ 6 ×: OD value> 6 <Storage stability>: Each was left at 60 ° C., 20 ° C., or −5 ° C. for one month to confirm precipitation and to measure the viscosity with an Ostwald viscometer. The evaluation was based on the following criteria. ：: Difference from initial viscosity is within 0.5 centipoise, no precipitate ×: Difference from initial viscosity is 0.6 centipoise or more or precipitate is present

[0045]

[Table 1] Example Comparative example1 2 3 4 5 1 2 3 4 Binder : Polyamide resin 100 50 50 50 Toluenesulfonic acid form 100 50 Aldehyde resin Amine-modified silicone 100 50 Acrylic resin Silicone acrylic resin 100 50 50 Acrylic resin 100 50 Imino group-containing dye : C.I.Basic Violet 1 150 100 150CIAcid Black 2 150 100 150 Pigment : Grafted carbon 30 80 30 30 80 BlackCarbon black 30 30 Colorant :CISolvent Black 29 100 100 150 150 150 solvent : Ethanol 1230 1000 1230 1000 1230 1000 1230 1000 1000 Methyl ethyl ketone 230 230 230 230 230 Lithium nitrate 3.0 3.0 3.0 3.0 3.0 3.0

[0046]

[Table 2] Table 2 例 Example 1 1 1 2 2 2 3 3 3 Substrate Metal glass PET Metal glass PET Metal glass PET Adhesion 100/100/100/100/100/100/100/100/100/100 100 100 100 100 100 100 100 100 Transfer resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ Heat resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ Dot bleeding and splashing ○ ○ ○ ○ ○ ○ ○ ○ ○ Abrasion resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ Water resistance ○ ○ ○ ○ ○ ○ ○ ○ ○ Light fastness ○ ○ ○ Storage stability 60 ℃ ○ ○ ○ 20 ℃ ○ ○ ○ -5 ℃ ○ ○ ○

[0047]

[Table 3] Table 2 (continued) 実 施 Example 4 4 4 5 5 5 Substrate Metal glass PET Metal glass PET Adhesion 100/100/100/100/100/100/100 100 100 100 100 100 Transfer resistance ○ ○ ○ ○ ○ ○ Heat resistance ○ ○ ○ ○ ○ ○ Dot bleed・ Repelling ○ ○ ○ ○ ○ ○ Abrasion resistance ○ ○ ○ ○ ○ ○ Water resistance ○ ○ ○ ○ ○ ○ Light resistance ○ ○ Storage stability 60 ℃ ○ ○ 20 ℃ ○ ○ -5 ℃ ○ ○

[0048]

Table 3 Table 3 Comparative Example 1 1 1 2 2 2 Material Metal glass PET Metal glass PET Adhesion 80/50/30/80/80/90/100 100 100 100 100 100 Transfer resistance ○ ○ × ○ ○ ○ Heat resistance ○ ○ ○ ○ ○ ○ Repelling ○ ○ ○ ○ ○ × Abrasion resistance × × × ○ × × Water resistance × × × ○ × × Light resistance ○ × Storage stability 60 ℃ × ○ 20 ℃ × ○ -5 ℃ × ○

[0049]

[Table 5] Table 3 (continued) 比較 Comparative Example 3 3 3 4 4 4 Base metal glass PET Metal glass PET Adhesion 80/80/80/90/80/80/100 100 100 100 100 100 Transfer resistance ○ ○ ○ ○ ○ ○ Heat resistance ○ ○ ○ ○ ○ ○ Dot Bleeding / Repelling ○ ○ ○ ○ ○ ○ Abrasion resistance ○ × × ○ ○ × Water resistance ○ × × ○ ○ × Light resistance ○ × Storage stability 60 ℃ × ○ 20 ℃ × ○ -5 ℃ × ○

[0050]

As is clear from the data of the examples, the jet printing ink composition of the present invention has excellent bleeding-prevention and bleeding-prevention properties during printing. Heat resistance, abrasion resistance, water resistance,
It is excellent in light resistance and storage stability, and is not transferred to the surface of the base material even when the material is stacked on the printed film.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Tetsuo Sugawa 2-22-10 Shibuya, Yamato-shi, Kanagawa Prefecture Grand Deal Yamato 401 (72) Inventor Tsuneo Shirota 1-18-3 Nakazato, Minato-ku, Yokohama-shi, Kanagawa Pref. 31 102 No. 72 (72) Inventor Hayato Ikeda 5-8 Nishiobari-cho, Suita-shi, Osaka Japan Catalyst Inside Tsukuba Research Laboratories Co., Ltd. In-house (56) References JP-A-9-272831 (JP, A) JP-A-10-251573 (JP, A) JP-A-10-195356 (JP, A) JP-A 8-333535 (JP, A) JP-A-10-30073 (JP, A) JP-A-6-214385 (JP, A) JP-A-9-324133 (JP, A) JP-A-10-87768 (JP, A) JP-A 9-39381 (JP, A) JP-A-10-6 0299 (JP, A) JP-A-6-128517 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C09D 11/00-11/20 C09C 1/56 C09C 3/10

Claims (1)

(57) [Claims] 1. The following components: (1) a solvent mainly composed of ethanol; (2) at least one binder selected from a polyamide resin, a toluenesulfonic acid formaldehyde resin and an amine-modified silicone acrylic resin; An ink composition for ink-jet printing, comprising: carbon black grafted with a polymer having an alkylene oxide group as a side chain; and (4) a dye having an imino group.