JPH10251573A - Ink composition for jet printing - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ink composition for jet printing, capable of forming a printed film excellent in adhesion, heat, abrasion and water resistances and further forming the printed film without being transferred to a superposed substrate surface even when the substrate is superposed on the printed film and excellent in bleeding preventing and cissing preventing properties. SOLUTION: This ink composition for jet printing comprises at least one binder selected from a polyamide resin, a toluenesulfonic acid formaldehyde resin and an amine-modified silicone acrylic resin, at least one dye selected from dyes having imino group and, as desired, further at least one colorant selected from colorants other than the dyes having the imino group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to metal, glass,
Adhesion, heat resistance,
Forming a printed film that can form a printed film having excellent wear resistance and water resistance and that 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 jet printing, which is excellent in bleeding prevention property and bleeding prevention property.

[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 base material such as paper by an inkjet printing method. As a method of testing the adhesion of the film formed by the ink jet printing method, a method of performing dot printing or pattern printing using a jet printer and testing the film formed by this printing by a grid tape method. However, a coating that is considered to have sufficient adhesion in the evaluation by this test method has not been obtained so far.

In addition, when the above-mentioned substrate is subjected to ink-jet printing and dried, and then the substrate is superimposed on the printed film and a load is applied, the printed film is transferred to the surface of the superposed substrate. There was a disadvantage that it would. Furthermore, in order to improve the durability of a product having a pattern film formed by inkjet printing, it is required to further improve the heat resistance, abrasion resistance and water resistance of the print film,
Further, in order to improve the quality of printing, it is required to further improve the bleeding preventing property and the bleeding preventing property of the ink composition for jet printing.

[0004]

However, at present, a print film that sufficiently satisfies all of the above conditions has not been obtained with the conventional ink composition for jet printing. The object of the present invention is to solve the above problems of the conventional ink composition for jet printing, namely, adhesion, heat resistance, abrasion resistance, it is possible to form a print film excellent in water resistance, In addition, even when a base material is superimposed on the printed film, a printed film which is not transferred to the surface of the superposed substrate can be formed, and the ink for jet printing has excellent anti-smearing and anti-slipping properties. It is to provide a composition.

[0005]

Means for Solving the Problems The inventors of the present invention have made 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, By using a dye having an imino group as, it is possible to form a printed film having excellent adhesion, heat resistance, abrasion resistance, water resistance and the like. It has been found that a printed film that is not transferred to the substrate surface can be formed, and that an ink composition for jet printing having excellent bleeding prevention and bleeding prevention properties can be obtained.

That is, the ink composition for jet printing of the present invention is selected from at least one binder selected from a polyamide resin, a toluenesulfonic acid formaldehyde resin, and an amine-modified silicone acrylic resin, and a dye having an imino group. It is characterized by containing at least one dye.

Further, the ink composition for jet printing of the present invention comprises at least one kind of binder selected from polyamide resin, toluenesulfonic acid formaldehyde resin and modified silicone acrylic resin, and at least one selected from dyes having imino groups. It is characterized by containing at least one colorant selected from one type of dye and a colorant other than a dye having an imino group.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the ink composition for jet printing of the present invention will be described in detail. The polyamide resin used in the present invention is a polyamide containing amino acids, lactams, or diamines and dicarboxylic acids as main components. Specific examples of such components include ε-caprolactam, enantholactam, lactams such as ω-laurolactam, amino acids such as 12-aminododecanoic acid,
Tetramethylenediamine, hexamethylenediamine, undecamethyleneamine, dodecamethylenediamine, 2,
2,4-trimethylhexamethylenediamine, 2,4
4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, m-xylylenediamine, p-xylylenediamine, 1,3-bisaminomethylcyclohexane, bis-p-aminocyclohexylmethane, bis-p-aminocyclohexylpropane , Diamines such as isophoronediamine, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecandioic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, dimer There are dicarboxylic acids such as acids.

These components 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. In particular, polyamides useful in the present invention include nylon 6, nylon 66 and nylon 6.
10, nylon 11, nylon 12, and copolymers and mixtures of these polyamides. There is no particular limitation on the degree of polymerization of the polyamide used here.

The toluenesulfonic acid formaldehyde resin used in the present invention has a structure represented by the following general formula, and may be either an ortho type or a para type.

Embedded image (Where n is a number of 2-3)

The amine-modified silicone acrylic resin used in the present invention is obtained by reacting an acrylic acid or an acrylate ester polymer with an organopolysiloxane, and usually has a molecular weight of 10,000 to 150,000, preferably It is obtained by preparing a silicone acrylic resin comprising 10,000 to 50,000 block polymer or graft polymer, and then substituting a part or all of the functional groups of the silicone acrylic resin with a secondary amine.

The above-mentioned acrylic acid or acrylic ester polymer is obtained by polymerizing a monomer such as an α, β-unsaturated acid or an ester thereof, and usually has a molecular weight of 500 to 80,000, preferably 1 to 1,000. 000-15,
000 polymers or copolymers. As the α, β-unsaturated acid or its ester, acrylic acid, methacrylic acid, and their methyl ester, ethyl ester, butyl ester, stearyl ester, 2-ethylhexyl ester, 2-hydroxyethyl ester, 3-hydroxypropyl ester And the like. Examples of the comonomer that can be copolymerized with the α, β-unsaturated acid or its ester include maleic acid, itaconic acid, fumaric acid, styrene, α-methylstyrene, vinyl acetate, vinyl propionate, and the like. it can.
When the acrylic acid or acrylate ester-based polymer is a copolymer, the proportion of acrylic acid, methacrylic acid, or their esters in the total copolymer is usually 10 to 75 mol. %, Preferably 25-60
Mol%.

It is preferable to use a linear polymer having a hydroxyl group as the above-mentioned organopolysiloxane, and examples thereof include compounds represented by the following formula. HO-Si (CH ₃ ) ₂ -O- (Si (CH ₃ ) ₂ -O) _n -Si (CH ₃ ) ₂ -OH (where n is a number from 10 to 5000) May be substituted with an ethyl group, a vinyl group or a phenyl group.
However, an organopolysiloxane having a methyl group of 50 mol% or more, preferably 60 mol% or more is preferable.

Examples of the secondary amine include aliphatic secondary amines having an NH group such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine and diamylamine. In the present invention, the above-mentioned polyamide resin, toluenesulfonic acid formaldehyde resin and silicone acrylic resin amine-modified product may be used alone, or may be used in the form of a mixture of two or three types. It is also possible.

In the present invention, as the dye having an imino group, 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 used without any particular limitation. For example, CI Solvent Black 2
8, CI Solvent Blue 70, CI Basic Blue 5, CI
Basic Blue 7, CI Basic Violet 1, CI BasicVi
olet 3, CI Basic Red 1, CI Basic Red 8, CI
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 25 parts by weight, per 100 parts by weight of the binder.
Suitably, it is 0 parts by weight.

The ink composition for jet printing of the present invention contains a solvent and, if necessary, a coloring agent other than a dye having an imino group, a conductivity adjusting agent, a surfactant, an ultraviolet absorber, a quencher, Additives such as dispersants and preservatives can be blended. In the present invention, the solvent is used for appropriately adjusting the viscosity of the ink composition. Accordingly, various solvents can be used without particular limitation as long as they are compatible with the other components of the ink composition. Representative examples of the solvent used in the present invention include acetone,
Ketones such as methyl ethyl ketone and cyclohexanone,
Examples thereof include alcohols such as methanol, ethanol and isopropanol, and ethers such as cellosolve and butyl cellosolve. The amount of the solvent in the ink composition is determined in consideration of the viscosity, surface tension and the like of the ink composition, but is usually 60 to 95% by weight, preferably 70 to 90% by weight of the ink composition. Is appropriate.

The above-mentioned coloring agent which can be used in the present invention is preferably a coloring agent which is compatible with other ink components and is soluble in a solvent. Typical examples are CI Solvent Black 22 and CI Solvent Black 27
, CI Solvent Black 29, CI Solvent Red 83 1
, CI Solvent Red 125, CI Solvent Red 132,
CI Solvent Blue 47, CI Solvent Blue 48, C.
I. Solvent Yellow 88, CI Solvent Yellow 89,
Dyes such as basic dyes and acid dyes, and inorganic or organic pigments such as titanium oxide, carbon black, zinc sulfide, oil smoke, graphite, red iron oxide, phthalocyanine blue, phthalocyanine green, brilliant carmine 6B, and lake red C are exemplified. However, when an insoluble dye or pigment is used, the particle size is usually preferably 3 μm or less, particularly preferably 0.5 μm or less in order to prevent nozzle clogging. The amount of the coloring agent is usually 50 to 400 parts by weight, preferably 8 to 100 parts by weight of the binder.
A suitable amount is from 0 to 250 parts by weight.

Examples of the above-mentioned conductivity adjusting agent which can be used in the present invention include lithium nitrate, lithium nitrite, ammonium sulfite, ammonium formate, ammonium acetate, lithium halide, sodium thiocyanate and the like. Further, the above-mentioned surfactants, ultraviolet absorbers, quenchers, dispersants, preservatives and the like which can be used in the present invention are those usually used in ink compositions for jet printing. The jet printing ink composition of the present invention may contain these additives in an amount of 0.1 to 5% by weight of the ink composition.

The ink composition for jet printing of the present invention comprises:
It is necessary that the composition has properties adapted to the ink jet printing method, so that the composition has a viscosity of usually 1 to 1.
10 centipoise (20 ° C), surface tension is usually 20
~ 60 dynes / cm, specific resistance is usually 200 ~ 3,0
It is preferable that the specific gravity is usually within the range of 0.8 to 1.2. When preparing the ink composition of the present invention, after mixing and stirring each component, the mixture is filtered and purified using a filter having a pore size of about 1/10 or less of the nozzle diameter of the jet printer to be used, for example. I do.

The ink composition for jet printing of the present invention comprises:
A conventionally known jet printer can be used. As such a jet printer, for example,
There are 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 the 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. Water can be suppressed. The object to be printed using the ink composition 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, the surface of a base material such as metal, glass, and plastic, paper coated with a resin on the surface, a transparent sheet for an overhead project, and the like.

The ink composition for jet printing of the present invention comprises:
Compared with the conventional ink composition for jet printing, adhesion, heat resistance, abrasion resistance, it is possible to form a print film excellent in water resistance, and even when a substrate is overlaid on the print film In addition, it is possible to form a printed film that is not transferred to the surface of the substrate that has been superimposed, and it is excellent in bleeding prevention and bleeding prevention during printing.

[0023]

The present invention will be described below in more detail with reference to Examples and Comparative Examples. Examples 1 to 5 and Comparative Examples 1 to 4 GAX11-966 (trade name, manufactured by Henkel Hakusui Co .; molecular weight: about 9000) was used as a polyamide resin, and SAN-TOP was used as a toluenesulfonic acid formaldehyde resin.
(Trade name, manufactured by Sun-May Chemical Co., Ltd .; molecular weight: about 500), an amine-modified methyl methacrylate / dimethylpolysiloxane copolymer (molecular weight: about 20,000) as an amine-modified silicone acrylic resin, and methyl methacrylate as a silicone acrylic resin. -Using a dimethylpolysiloxane copolymer (molecular weight: about 2,000), Neo Cryl B-817 (trade name, manufactured by Kaneka Corporation; molecular weight: about 20,000, acid value: 599) as an acrylic resin, an imino group-containing dye, a colorant, and a solvent Each of the substances described in Table 1 was used as a conductivity adjuster, and the substances were mixed in the amounts (parts by weight) described in Table 1 and uniformly mixed, and then filtered through a membrane filter having a pore size of 1.0 μm. Ink for jet printing corresponding to each example and each comparative example A composition was prepared.

Each of the obtained ink compositions is jetted in a predetermined image by a jet printer to form a print film on a stainless steel plate, a glass plate, or a polyethylene terephthalate film (PET), respectively. , Transfer resistance, heat resistance, dot bleeding / repelling, abrasion resistance,
Each test of water resistance was performed as follows, and the test of storage stability of each ink was performed as follows.

<Adhesion> A 100 mm square test was conducted according to JIS K5401 to check the peeling state with a cellophane tape, and the number of bonded pieces in 100 pieces (the squares remaining without being peeled) Number). <Transfer resistance>: The same substrate plate is superimposed on the printed film and pressed with a force of 10 kgf / cm ² ,
After standing at 24 ° C. for 24 hours, the presence or absence of transfer to the superposed substrates was examined, and evaluated according to the following criteria. ：: no transfer at all, ×: transfer was partially observed.

<Heat resistance>: After leaving in a constant temperature bath 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, ×: Bleed or bleed.

<Abrasion resistance>: The printed film portion is weighted 75
The printed film was rubbed 100 times with a rubbing tester of 0 kg / cm ² to check whether or not the printed film portion was peeled off, and evaluated according to the following criteria. ：: No abnormality, ×: Print film peeling was partially observed. <Water resistance>: After immersion in water at room temperature for 24 hours, the above-mentioned abrasion resistance test was performed and evaluated according to the following criteria. ：: No abnormality, ×: Print film peeling was partially observed.

<Storage stability>: 60 ° C., 20 ° C., or −
Each was left at 5 ° C. for one month, and the viscosity was measured with an Ostwald viscometer and evaluated according to the following criteria. ：: Difference from initial viscosity is within 0.5 centipoise, ×: Difference from initial viscosity is 0.6 centipoise or more. The results were as shown in Tables 2 and 3.

[0029]

[Table 1]

[0030]

[Table 2]

[0031]

[Table 3]

[0032]

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. It is excellent in heat resistance, heat resistance, abrasion resistance, and water resistance, and is not transferred to the surface of the superposed substrate even when the substrate is overlaid on the printed film.

Claims (2)

[Claims] (1) a binder containing at least one binder selected from a polyamide resin, a toluenesulfonic acid formaldehyde resin, and an amine-modified silicone acrylic resin; and at least one dye selected from dyes having imino groups. Jet printing ink composition. 2. At least one kind of binder selected from polyamide resin, toluenesulfonic acid formaldehyde resin and modified silicone acryl resin amine, at least one kind of dye selected from dyes having imino group, and dye having imino group An ink composition for jet printing comprising at least one colorant selected from colorants other than the above.