JP2000178487A - Ink for ink-jet printer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ink for ink-jet printer capable of providing a printed film having excellent adhesion to various kinds of wrapping film, and durability by using a polyamide resin in combination with a terpene-phenol resin as a film-formable resin, and further using a specific compound as a cross-linking agent of the latter resin. SOLUTION: This ink for ink-jet printer comprises (A) a coloring matter, (B) a polyamide resin, (C) a terpene-phenol resin (preferably the one having hydroxy group), (D) a titanium chelate compound (preferably β-diketone chelate compound), and (E) an organic solvent consisting essentially of ethanol. The component B is preferably the one obtained by subjecting a dimer acid with diamines to a condensation reaction. Further, the resin having 50-150 acid value in combination with the resin having <=20 acid value is preferably used as the component B. When the polyamide resin having <=20 acid value is used in combination, the component E is preferably a solvent obtained by adding n-propyl alcohol and/or iso-propyl alcohol to ethanol.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polypropylene film, a nylon film, a cellophane film, a PE film,
The present invention relates to an ethanol-based ink for a jet printer, which has excellent adhesion to various packaging films such as T-films, excellent abrasion resistance, resistance to oils such as animal oils and vegetable oils, and excellent jetting stability.

[0002]

2. Description of the Related Art Printing by a jet printer is a method in which ink is ejected from a nozzle and adheres to a recording material. Since the nozzle and the recording material are not in contact with each other, a curved or irregular irregular shape is formed. Good printing can be performed on the surface having the surface. Jet printers are widely used for various purposes such as printing of serial numbers on various food containers such as beverage cans and PET bottles. Jet inks with excellent adhesion and durability to metals, glass and various plastics are used. Many have been proposed.

On the other hand, at present, conventional jet inks have not been obtained which have sufficient adhesion and durability to packaging films such as polypropylene films, nylon films, cellophane films, and PET films. Since the main component of the organic solvent used in the conventional ink is highly toxic methyl ethyl ketone, there is a strong demand for an ethanol-based ink having excellent adhesion and durability to various packaging films.

[0004]

SUMMARY OF THE INVENTION The problem to be solved by the present invention is adhesion to various packaging films,
An object of the present invention is to provide an ethanol-based ink for a jet printer which has excellent durability and good jetting 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, by using a polyamide resin, a terpene phenol resin, and a titanium chelate compound together, various packaging films have been obtained. The present inventors have found that a printed film having excellent adhesion and durability can be obtained, and have reached the present invention.

That is, the present invention relates to a jet printer ink containing a colorant, a film-forming resin, and an organic solvent containing ethanol as a main component, comprising a polyamide resin, a terpene phenol resin, and a titanium chelate compound. An ink for a jet printer is provided.

Next, the present invention will be described in detail. The film-forming resin used in the present invention essentially comprises a polyamide resin and a terpene phenol resin, which are thermoplastic resins.

The polyamide resin used in the present invention is a chain polymer having an amide group (—CO—NH—) in the molecule.
Is a resin having, for example, condensation of aminocarboxylic acid,
And the condensation of a dibasic acid with an amine. As the polyamide resin used in the present invention, those obtained by a condensation reaction of dimer acid and diamines are particularly preferable, and those having a molecular weight of 1,000 to 8,000 are particularly preferable.

In order to obtain a printed film having excellent durability by crosslinking described later, it is preferable to include the polyamide resin having an acid value of 50 or more among the above-mentioned polyamide resins having a carboxyl group, particularly, an acid value of 50 to 150. Most preferably, the above-mentioned polyamide resin is contained. Acid value 5
The polyamide resin having 0 or more is not particularly limited, and specifically, GAX-11 manufactured by Henkel
-966, GAX-12-250 and the like.

The polyamide resin having an acid value of 50 or more may be used alone, but the polyamide resin having an acid value of 50 or more and the polyamide resin having no carboxyl group have an acid value of 20 or less. When used in combination with a polyamide resin, compared to the case where the former is used alone, the flexibility of the printed film is superior due to cross-linking, the printed material is folded onto sheets, films, etc., and the adhesion by hand rubbing is also excellent. Is preferred.

The polyamide resin having an acid value of 20 or less is not particularly limited, but is preferably a resin obtained by a condensation reaction between dimer acid and a diamine. Specifically, Henskel versamide 725, 74
Sunmide 615A, 6 manufactured by Sanwa Chemical Industry Co., Ltd.
40 and the like. These may be used as a mixture of two or more.

The content of these polyamide resins in the ink composition is 5 to 1 from the viewpoint of obtaining sufficient durability of the print film.
A range of 5% by weight is preferred.

The terpene phenol resin used in the present invention is a copolymer of terpene, a purified polymer of α-pinene and β-pinene obtained from pine essential oil, and a phenol such as bisphenol A. The molar ratio of the terpene to the phenol can be any as long as it is soluble in the alcoholic solvent used in the present invention. Among them, terpene phenol resins containing a (phenolic) hydroxyl group are preferred. Such a material is not particularly limited, but specifically, YP made by Yashara Chemical
-902, YS Polystar S-145, Mighty Ace G-125, 150 and the like.

The ratio of the polyamide resin to the terpene phenol resin used in the present invention is not particularly limited, but is preferably in the range of 10 to 100 parts by weight of the terpene phenol resin per 100 parts by weight of the polyamide resin.
Within this range, the effect of imparting adhesion by the addition of the terpene phenolic resin and the effect of imparting durability by crosslinking are fully exhibited, the flexibility of the printed film is good, and the printed matter can be folded into sheets, films, etc. Excellent adhesion due to hand fir.

The titanium chelate compound used in the present invention acts as an effective cross-linking agent for terpene phenol resins which are a part of the film-forming resin, especially terpene phenol resins containing hydroxyl groups. In the presence of a large excess of the organic solvent containing ethanol as a main component in the present invention, the titanium chelate compound does not substantially exhibit cross-linking with the film-forming resin. Upon release, a crosslinking reaction occurs.

The titanium chelate compound is not particularly limited, and examples thereof include a glycol chelate compound, a β-diketone chelate compound, a hydroxycarboxylic acid chelate compound and a ketoester chelate compound. Use is preferred. Specific examples of such a product include Organix TC-100 and TC-401 manufactured by Matsumoto Pharmaceutical Co., Ltd.
Is mentioned.

The content of the titanium chelate compound in the ink composition is preferably in the range of 1 to 8% by weight based on the total amount of the polyamide resin and the terpene phenol resin.

As the coloring agent which can be used in the present invention, those which have been conventionally used in various coloring fields can be used without particular limitation. Examples thereof include monoazo, disazo, metal complex salt, anthraquinone, and the like. Examples include oil-soluble dyes such as phthalocyanine and triallylmethane, inorganic pigments such as carbon black, titanium oxide, zinc white and zinc sulfide, and organic pigments such as monoazo, disazo, phthalocyanine, and quinacudrine.

The organic solvent used in the present invention contains ethanol as a main component. As an organic solvent used in combination with ethanol, lower alcohols having relatively low toxicity, such as methyl ethyl ketone, are not relatively high in toxicity, such as normal propyl alcohol and isopropyl alcohol.
Methanol and the like can be mentioned. One of these may be used in combination with ethanol, or two or more may be used in combination.

In particular, when the above-mentioned polyamide resin having an acid value of 20 or less is used in combination, not only ethanol alone but also normal propyl alcohol as an organic solvent is used in order to enhance the dissolution stability of the resin. as well as/
Alternatively, it is preferable to contain isopropyl alcohol.

In order to improve the print film performance such as abrasion resistance, transfer resistance, and scratch resistance of the ink film printed with the ink for a jet printer of the present invention, the ink is provided with:
If necessary, silicone compounds, fluorine compounds,
Alternatively, a compound soluble in the solvent system used in the present invention, such as a fatty acid amide wax, may be added.

The silicone compound is not particularly restricted but includes silicone oil, modified silicone oil,
Silicone resin, etc., specifically, KF-56 (silicone oil) manufactured by Shin-Etsu Chemical Co., Ltd., TSF-410 (higher fatty acid modified silicone oil) manufactured by Toshiba Silicone, TSF-4446,4460 (polyether modified silicone oil) ), TSF-4710 (amino-modified silicone oil), KP-316,3 manufactured by Shin-Etsu Chemical Co., Ltd.
60A (silicone resin) and the like.
You may mix and use more than one kind.

The fluorine compound is not particularly restricted but includes fluorine surfactants and the like.
Megafac F-470, F manufactured by Dainippon Ink and Chemicals, Inc.
-173, F-177 and the like. These may be used as a mixture of two or more kinds, or may be used as a mixture with the above-mentioned silicone compound.

Examples of the fatty acid amide wax include, but are not particularly limited to, saturated fatty acid amide, unsaturated fatty acid amide, modified fatty acid amide, and the like, which provide excellent scratch resistance, abrasion resistance, and transfer resistance to a print film. From the viewpoint of providing, it is preferable to use a modified fatty acid amide. Specifically, Tenka Polymer's amide polymer Ex-1, E
x-2 and the like, and may be used as a mixture with the above-mentioned silicone compound and fluorine compound.

The ink jet printers include, for example, a continuous type (charge control type) and an on-demand type (piezo type, thermal type, etc.). In the present invention, both types of ink for a jet printer can be prepared.

On-demand jet printer inks include, for example, colorants, polyamide resins, terpene phenol resins, titanium chelate compounds,
Ethanol is adjusted to the above weight ratio, and if necessary, a lower alcohol other than ethanol, a silicone-based compound, a fluorine-based compound, or a fatty acid amide-based wax or the like that is soluble in a solvent system is combined. , Can be prepared by mixing.

The continuous-type jet printer ink needs to provide the ink with an appropriate electric conductivity, which is not required for the on-demand type jet printer ink. In this case, a conductivity-imparting agent is further added.

In order to adjust the electric conductivity, various conductivity-imparting agents such as inorganic salts such as lithium nitrate and sodium thiocyanate, quaternary ammonium salts and metal complex salts can be used. In order not to lower the film performance such as water resistance, it is preferable to use a water-insoluble organic conductivity imparting agent. Such examples include, but are not particularly limited to, quaternary ammonium salts of naphtholsulfonic acid and alkali metal salts of boron complexes of benzylic acid.

In preparing a continuous jet ink for a jet printer, a minimum necessary amount of purified water may be added only when necessary to make the specific resistance appropriate. It is preferred to use a small amount.

[0030]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention includes the following embodiments. 1. An ink for a jet printer containing a colorant, a film-forming resin, and an organic solvent containing ethanol as a main component, comprising a polyamide resin, a terpene phenol resin, and a titanium chelate compound.

2. 2. The ink according to the above 1, wherein the polyamide resin is a resin obtained by a condensation reaction between dimer acid and diamines.

3. 2. The ink according to the above 1 or 2, wherein normal propyl alcohol and / or isopropyl alcohol is used in combination as an organic solvent.

4. The ink according to any one of the above 1, 2 and 3 for a continuous recording method, comprising a water-insoluble organic conductive agent as a conductivity imparting agent.

The preferred embodiment of the present invention will be described as follows. The weight ratio of the polyamide resin obtained by the condensation reaction between dimer acids having an acid value of 50 to 150 and diamines and the polyamide resin obtained by the condensation reaction between dimer acids having an acid value of 0 to 20 and diamines (the former / (The latter) = 50 / 50-85 / 15, and the weight ratio of the entire polyamide resin to the terpene phenol resin (the former / the latter) = 75 / 25-90 / 10.

The titanium chelate compound is added in an amount of 0.5 to 10 parts by weight and the colorant is added in an amount of 3 to 10 parts by weight based on 100 parts by weight of the total of the polyamide resin and the terpene phenol resin.
8 parts by weight and the remainder of ethanol are added to make up to 100% by weight.

The mixture is filtered using a filter of 0.5 to 0.1 μ to obtain an ink for a jet printer.

[0037]

The present invention will be described below in detail with reference to examples. In the following description, "parts" indicates parts by weight.

Example 1 C.I. I. Solvent Black 43 6.0 parts GAX-12-250 6.5 parts (chain polyamide resin obtained by condensing dimer acid and diamines manufactured by Henkel Acid value: 53) YP-902 3.5 parts (hydroxy group containing by Yasuhara Chemical) Terpene phenolic resin) Quaternary ammonium salt of naphtholsulfonic acid 4.0 parts Megafac F-177 0.4 parts (Dainippon Ink and Chemicals, fluorinated surfactant) KF-56 0.1 parts (Shin-Etsu Chemical Co., Ltd.) 0.2 parts of Amide Polymer Ex-1 (modified fatty acid amide manufactured by Tenka Polymer) 0.2 parts of Organix TC-401 (titanium chelate compound Ti (C5H7O2) 4 manufactured by Matsumoto Pharmaceutical Co., Ltd.) 80.0 parts of ethanol

After sufficiently stirring and dissolving the above composition,
This solution was filtered using a 0.5 μm membrane filter to obtain an ink for a jet printer.

Example 2 C. I. Solvent Black 43 6.0 parts GAX-11-966 7.5 parts (chain polyamide resin obtained by condensing dimer acid and diamines manufactured by Henkel Acid value: 98) YP-902 3.5 parts No. of naphthol sulfonic acid Quaternary ammonium salt 3.0 parts Megafax F-177 0.4 parts KF-56 0.1 parts Amide polymer Ex-1 0.2 parts Organix TC-401 0.4 parts Ethanol 80.0 parts

After thoroughly stirring and dissolving the above composition,
This solution was filtered using a 0.5 μm membrane filter to obtain an ink for a jet printer.

Example 3 C.I. I. Solvent Black 43 6.0 parts GAX-11-966 4.5 parts Versamide 744 3.5 parts (Higher molecular weight chain polyamide resin obtained by condensing dimer acid and diamines manufactured by Henkel Acid value: 3 ) YP-902 2.0 parts Quaternary ammonium salt of naphtholsulfonic acid 4.0 parts Megafac F-177 0.4 parts KF-56 0.1 parts Amide polymer Ex-1 0.2 parts ORGATICS TC- 100 0.2 (Titanium chelate compound (C3H7O) 2Ti (C5H7O2) 2, manufactured by Matsumoto Pharmaceutical Co., Ltd.) 80.0 parts of Solmix A-7 Is further contained.)

After sufficiently stirring and dissolving the above formulation,
This solution was filtered using a 0.5 μm membrane filter to obtain an ink for a jet printer.

Example 4 C.I. I. Solvent Blue 136 4.0 parts GAX-11-966 6.5 parts Versamide 744 2.0 parts Mighty Ace G-125 3.5 parts (terpene phenolic resin manufactured by Yashara Chemical) Quaternary ammonium salt of naphtholsulfonic acid 4.0 Part TSF-4460 0.2 part (Toshiba Silicone polyether-modified silicone oil) KF-56 0.1 part Amide polymer Ex-1 0.2 part Organix TC-401 0.3 part Solmix A-750 3.0 parts Methanol 30.0 parts

After thoroughly stirring and dissolving the above composition,
This solution was filtered using a 0.5 μm membrane filter to obtain an ink for a jet printer. As a result, ink for a jet printer was obtained.

Example 5 C.I. I. Solvent Black 3 4.0 parts GAX-11-966 4.0 parts Versamide 744 1.5 parts YP-902 2.0 parts Megafax F-177 0.3 parts KF-56 0.05 parts Amide polymer Ex-1 0.15 parts ORGATICS TC-401 0.2 parts Solmix AP-7 89.0 parts

After sufficiently stirring and dissolving the above formulation,
This solution was filtered using a 0.5 μm membrane filter to obtain an ink for a jet printer.

COMPARATIVE EXAMPLE 1 The above-mentioned composition, except that ORGATICS TC-401 was removed from the composition of Example 1, was sufficiently stirred and dissolved, and the solution was filtered using a 0.5 μm membrane filter. An ink for a jet printer was obtained.

COMPARATIVE EXAMPLE 2 The above-mentioned composition, except that ORGATICS TC-401 was removed from the composition of Example 5, was sufficiently stirred and dissolved, and the solution was filtered using a 0.5 μm membrane filter. An ink for a jet printer was obtained.

Using the inks of Examples 1 to 4 and Comparative Example 1,
Using a commercially available continuous printer, a polypropylene film (OPP film) manufactured by Nimura Chemical
Printing was performed on the corona discharge treated surface of “FOR-30”.
As a result, a clear printed image was obtained, and the ejection stability was good.

Further, a commercially available on-demand type (piezo type) printer using the inks of Example 5 and Comparative Example 2 was used.
Using a polypropylene film made by Nimura Chemical (OP
P film) Printing was performed on the corona-treated surface of “FOR-30”. As a result, a clear printed image was obtained, and the ejection stability was good.

Next, the adhesion, rubbing resistance, abrasion resistance, and oil resistance of each printed image printed on the printing material were evaluated by the following methods. Table shows the results. It is shown in FIG.

Adhesion: "Cellotape" (Nichiban Co., Ltd.)
Of peeling of the printed image in the peeling test using a cellophane adhesive tape (made of cellophane). ○: No peeling △: Partial peeling but legible × Peeled and legible

Fir resistance: Presence or absence of peeling of the printed image after fifty hand fir times. ○: No peeling △: Partial peeling but legible × Peeled and legible

Abrasion resistance: A rubbing tester was used to apply a felt to a printed portion at a load of 0.5 kg / cm 2 using felt.
The presence or absence of peeling of the printed image rubbed 0 times is evaluated. ○: No peeling △: Partial peeling but legible × Peeled and legible

Abrasion resistance: The printed portion was rubbed 100 times with the pad of a finger, and the presence or absence of peeling of the printed image was evaluated. ○: No peeling △: Partial peeling but legible × Peeled and legible

Oil resistance: Apply rapeseed oil to the printed image,
After leaving for 4 hours, the presence or absence of peeling of the printed image by scraping the oil with Bencott (made by Asahi Kasei Kogyo). ○: No peeling △: Partial peeling but legible × Peeled and legible

[0058]

[Table 1]

Table. As shown in FIG. 1, the ink compositions of the present invention in Examples 1 to 5 had good adhesion, corrosive resistance, oil resistance, and abrasion resistance to the corona discharge treated OPP film. On the other hand, Comparative Examples 1 and 2 in which the titanium chelate compound was not added exhibited better adhesiveness and ink compared to the inks of Examples.
Oil resistance and abrasion resistance were inferior, although the oil resistance was the same.

[0060]

According to the present invention, a polyamide resin and a terpene phenol resin are used as a film-forming resin in a jet printer ink containing a colorant, a film-forming resin, and an organic solvent containing ethanol as a main component. By using a titanium chelate compound as a resin crosslinking agent, an ink with excellent adhesion, abrasion resistance, oil resistance, and other durability to various packaging films, and good jetting stability can be obtained. Can do things.

Claims (4)

[Claims] 1. An ink for a jet printer containing a colorant, a film-forming resin, and an organic solvent containing ethanol as a main component, comprising a polyamide resin, a terpene phenol resin, and a titanium chelate compound. Printer ink. 2. The polyamide resin as claimed in claim 1, wherein the polyamide resin is obtained by a condensation reaction between dimer acid and diamines.
The ink described. 3. The ink according to claim 1, wherein normal propyl alcohol and / or isopropyl alcohol are used in combination as the organic solvent. 4. The ink according to claim 1, which is for a continuous recording system and contains a water-insoluble organic conductive agent as a conductivity-imparting agent.