NONAQUEOUS INK COMPOSITION

Abstract

An object of the present invention is to provide a nonaqueous ink composition offering excellent adhesion to printing media, rub resistance, and solvent resistance, even when printed on roll materials (acrylic, PET, etc.), board materials (glass, plastics, etc.), and other nonabsorbent media, even in a high-speed printing mode, while also exhibiting excellent discharge stability. As a solution, a nonaqueous ink composition containing a chlorinated polyolefin resin and a ketone resin is provided, wherein the chlorinated polyolefin resin and ketone resin together account for at least 10 percent by mass in the ink composition, the chlorine content in the chlorinated polyolefin resin is 30 to 50 percent by mass, and the chlorinated polyolefin resin and ketone resin are contained at a ratio by mass, calculated by “Chlorinated polyolefin resin/Ketone resin,” of 3/7 to 7/3.

Claims

1. A nonaqueous ink composition containing a chlorinated polyolefin resin and a ketone resin, wherein the chlorinated polyolefin resin and the ketone resin together account for at least 10 percent by mass in the ink composition, a chlorine content in the chlorinated polyolefin resin is 30 to 50 percent by mass; and the chlorinated polyolefin resin and the ketone resin are contained at a ratio by mass, calculated by “Chlorinated polyolefin resin/Ketone resin,” of 3/7 to 7/3.

2. The nonaqueous ink composition according to according to claim 1, wherein a mass-averaged molecular weight of the chlorinated polyolefin resin is 20,000 to 100,000.

3. The nonaqueous ink composition according to claim 1, used for inkjet printing.

4. The nonaqueous ink composition according to claim 2, used for inkjet printing.

Description

EXAMPLES

[0054] The present invention is explained in greater detail by citing examples below;

[0055] however, it should be noted that the present invention is not limited to these examples. It should also be noted that, unless otherwise specified, “%” indicates “percent by mass,” while “part” indicates “part by mass.”

[0056] The following materials were used in the Examples and Comparative Examples described below.

<Dispersants>

[0057] SOLSPERSE 39000 (manufactured by Lubrizol) [0058] SOLSPERSE 56000 (manufactured by Lubrizol) [0059] PB822: AJISPER PB822 (manufactured by Ajinomoto Fine-Techno)

<Pigments>

[0060] MA7: Carbon Black MA7 (manufactured by Mitsubishi Chemical) [0061] D7110F: Heliogen Blue D7110F (manufactured by BASF) [0062] G01: Levascreen Yellow GO1 (manufactured by LANXESS) [0063] RGT: FASTOGEN Super Magenta RGT (manufactured by DIC)

<Chlorinated Polyolefin Resins>

[0064] 390S: SUPERCHLON 390S (manufactured by Nippon Paper Industries, chlorinated polypropylene, chlorine content 36%, mass-averaged molecular weight 80,000) [0065] 814HS: SUPERCHLON 814HS (manufactured by Nippon Paper Industries, chlorinated polypropylene, chlorine content 41%, mass-averaged molecular weight 20,000) [0066] 803M: SUPERCHLON 803M (manufactured by Nippon Paper Industries, chlorinated polypropylene, chlorine content 30%, mass-averaged molecular weight 160,000) [0067] L206: SUPERCHLON L-206 (manufactured by Nippon Paper Industries, chlorinated polypropylene, chlorine content 32%, mass-averaged molecular weight 9,000)

<Ketone Resins>

[0068] SK: VariPlus SK (manufactured by Evonik, aromatic ketone-formaldehyde condensed hydrogenated ketone resin) [0069] AP: VariPlus AP (manufactured by Evonik, aromatic ketone-formaldehyde condensed ketone resin)

<Acrylic Resin>

[0070] BR-87: Dianal BR-87 (manufactured by Mitsubishi Rayon, glass transition temperature 105° C., mass-averaged molecular weight 25,000)

<Vinyl Chloride-Vinyl Acetate Resin>

[0071] SOLBIN C: SOLBIN C (manufactured by Nissin Chemical Industry, vinyl chloride/vinyl acetate =87/13)

<Polyester Resin>

[0072] FC1565: Diacron FC1565 (manufactured by Mitsubishi Rayon, polyester resin)

<Solvents>

[0073] DEDG: Diethylene glycol diethyl ether [0074] EDM: Diethylene glycol ethyl methyl ether [0075] PC: Propylene carbonate [0076] DPMA: Dipropylene glycol methyl ether acetate

Examples 1 to 11 and Comparative Examples 1 to 10

(Manufacturing of Colored Base Inks>

<Manufacturing of Nonaqueous Black Base Inkjet Ink>

[0077] Ten parts of pigment dispersant (SOLSPERSE 39000) were dissolved in 65 parts of diethylene glycol diethyl ether, into which 25 parts of pigment (MA7) were mixed under agitation, after which the mixture was kneaded using a bead mill, to obtain a nonaqueous black base inkjet ink.

<Manufacturing of Nonaqueous Cyan Base Inkjet Ink>

[0078] Ten parts of pigment dispersant (SOLSPERSE 56000) were dissolved in 65 parts of diethylene glycol diethyl ether, into which 25 parts of pigment (D7110F) were mixed under agitation, after which the mixture was kneaded using a bead mill, to obtain a nonaqueous cyan base inkjet ink.

<Manufacturing of Nonaqueous Yellow Base Inkjet Ink>

[0079] Ten parts of pigment dispersant (PB822) were dissolved in 65 parts of diethylene glycol diethyl ether, into which 25 parts of pigment (G01) were mixed under agitation, after which the mixture was kneaded using a bead mill, to obtain a nonaqueous yellow base inkjet ink.

<Manufacturing of Nonaqueous Magenta Base Inkjet Ink>

[0080] Ten parts of pigment dispersant (SOLSPERSE 56000) were dissolved in 65 parts of diethylene glycol diethyl ether, into which 25 parts of pigment (RGT) were mixed under agitation, after which the mixture was kneaded using a bead mill, to obtain a nonaqueous magenta base inkjet ink.

<Manufacturing of Nonaqueous Inkjet Ink Compositions>

[0081] The respective materials were mixed under agitation according to the recipes in Table 1 (the blending ratio of each material is indicated by percent by mass), to obtain the nonaqueous inkjet ink compositions in Examples 1 to 11 and Comparative Examples 1 to 10.

(Printing Method and Printed Matters)

[0082] Each of the nonaqueous inkjet ink compositions in Examples 1 to 11 and Comparative Examples 1 to 10 was charged to a commercial inkjet printer, which was then used to perform solid printing on each printing medium in a high-speed printing mode, to obtain the printed matters in Examples 1 to 11 and Comparative Examples 1 to 10.

<Evaluation>

[0083] The following properties were evaluated on the printed matters obtained using the nonaqueous inkjet ink compositions in Examples 1 to 11 and Comparative Examples 1 to 10. In the following evaluations, A and B represent levels acceptable for practical use, while C and D represent levels not acceptable for use as a product.

(Viscosity)

[0084] The nonaqueous inkjet ink compositions in Examples 1 to 11 and Comparative Examples 1 to 10 were measured for viscosity at 25° C. using a viscometer (RE100L manufactured by Toki Sangyo).

(Adhesion)

[0085] The nonaqueous inkjet ink compositions in Examples 1 to 11 and Comparative Examples 1 to 10 were printed on each of the printing media indicated under Adhesion in Table 1, after which a piece of clear adhesive tape (product name: CELLOTAPE (registered trademark), manufactured by Nichiban) was pressed onto the printed surface and then peeled, and the results were evaluated based on the degree of separation of the printed coating film.

Evaluation Criteria

[0086] A: There was no peeling. [0087] B: There was some peeling. [0088] C: The coating film peeled by at least a half. [0089] D: The coating film peeled completely.

(Discharge Stability)

[0090] The nonaqueous inkjet ink compositions in Examples 1 to 11 and Comparative Examples 1 to 10 were printed on polyvinyl chloride sheets (product name: Kapjet Gloss Banner, manufactured by Filmolux), and the results were evaluated based on the number of sheets on which unprinted areas appeared.

Evaluation Criteria

[0091] A: Unprinted areas appeared on the 71st or subsequent sheet, or no unprinted areas appeared until the 100th sheet. [0092] B: Unprinted areas appeared on any of the 51st through 70th sheets. [0093] C: Unprinted areas appeared on any of the 31st through 50th sheets. [0094] D: Unprinted areas appeared on the 30th or earlier sheet.

(Rub Resistance)

[0095] The nonaqueous inkjet ink compositions in Examples 1 to 11 and Comparative Examples 1 to 10 were transferred onto a polyvinyl chloride sheet (product name: Kapjet Gloss Banner, manufactured by Filmolux) using a Mayer bar (0.15 mm), after which the coating film was rubbed 100 times with a bleached cloth using a Gakushin color fastness tester (manufactured by Daiei Kagaku Seiki MFG) under a force of 500 g, and the degree of removal of the coating film was visually observed and the result was evaluated according to the criteria below: [0096] A: The coating film was not removed. [0097] B: The coating film had surface abrasions. [0098] C: The coating film was somewhat removed. [0099] D: The coating film was visibly removed.

(Solvent Resistance)

[0100] The nonaqueous inkjet ink compositions in Examples 1 to 11 and Comparative Examples 1 to 10 were transferred onto a polyvinyl chloride sheet (product name: Kapjet Gloss Banner, manufactured by Filmolux) using a Mayer bar (0.15 mm), after which the coating film was rubbed five times with an ethanol-moistened bleached cloth using a Gakushin color fastness tester (manufactured by Daiei Kagaku Seiki MFG) under a force of 200 g, and the degree of removal of the coating film was visually observed and the result was evaluated according to the criteria below: [0101] A: The coating film was not removed. [0102] B: The coating film had surface abrasions. [0103] C: The coating film was somewhat removed. [0104] D: The coating film was visibly removed.

TABLE-US-00001 TABLE 1 Example 1 2 3 4 5 6 7 8 9 10 11 Black Black Black Black Black Black Black Black Yellow Magenta Cyan Pigments MA7 4 4 4 4 4 4 4 4 G01 3 RGT 3 D7110F 3 Dispersants PB822 1 1 SOLSPERSE 56000 1 SOLSPERSE 39000 1 1 1 1 1 1 1 1 Resin Chlorinated 390S 8 8 6 10 5 11 12 8 8 8 polyolefin 814HS 8 resin 802M L206 Ketone resin SK 8 8 10 6 11 5 12 8 8 8 AP 8 Acrylic resin BR-87 Vinyl chloride- SOLBIN C vinyl acetate resin Solvent DEDG 39 39 39 39 39 39 39 31 40 40 40 EDM 20 20 20 20 20 20 20 20 20 20 20 PC 10 10 10 10 10 10 10 10 10 10 10 DPMA 10 10 10 10 10 10 10 10 10 10 10 Total 100 100 100 100 100 100 100 100 100 100 100 Viscosity (mPa .Math. s) 6.0 8.0 6.0 5.8 6.2 5.6 8.2 10.5 6.0 6.0 8.0 Adhesion Glass A A A A A A A A A A A Acrylic A A A A A A A A A A A Aluminum sheet A A A A A A A A A A A PE A A A A A A A A A A A PP A A A A A A A A A A A PET A A A A A A A A A A A ABS A A A A A A A A A A A PVC A A A A A A A A A A A Discharge stability A A A A A A A C A A A Rub resistance A A A A A A A A A A A Solvent resistance A A A A A A A A A A A Comparative Example 1 2 3 4 5 6 7 8 9 10 Black Black Black Black Black Black Black Black Black Black Pigments MA7 4 4 4 4 4 4 4 4 4 4 G01 RGT D7110F Dispersants PB822 SOLSPERSE 56000 SOLSPERSE 39000 1 1 1 1 1 1 1 1 1 1 Resin Chlorinated 390S 16 13 3 4 polyolefin 814HS resin 802M 16 L206 16 Ketone resin SK 3 13 16 4 AP Acrylic resin BR-87 16 Vinyl chloride- SOLBIN C 16 vinyl acetate resin Polyester resin FC1985 16 Solvent DEDG 39 39 39 39 39 39 47 39 39 39 EDM 20 20 20 20 20 20 20 20 20 20 PC 10 10 10 10 10 10 10 10 10 10 DPMA 10 10 10 10 10 10 10 10 10 10 Total 100 100 100 100 100 100 100 100 100 100 Viscosity (mPa .Math. s) 6.3 6.3 5.6 5.2 11.0 5.9 3.0 6.0 16.0 7.0 Adhesion Glass A A A B A A A A C A Acrylic A A A A A A A B B A Aluminum sheet A A A A A A A A A B PE D C C A D D C D D D PP A B C C A A C D D D PET A A A B A A B A D A ABS A A A B A A B B B A PVC A A A A A A A A A A Discharge stability A A B B C B A A C C Rub resistance A A B C A C C A A B Solvent resistance A A B C A A B A A B [0105] Glass: Alkali-free glass (product name: EAGLE XG, manufactured by Hiraoka Special Glass Mfg.) [0106] Acrylic: Methacrylic resin sheet (product name: SUMIPEX AS, manufactured by Sumika Acryl) [0107] Aluminum sheet: Aluminum composite sheet (product name: DIBOND, manufactured JetGraph) [0108] PE: Polyethylene sheet (product name: 07-127-01, manufactured by Hagitec) [0109] PP: Polypropylene sheet (product name: POLYSAME PW-C6, manufactured by Sekisui Seikei) [0110] PET: PET resin sheet (product name: E-5100 (100 μm), manufactured by Toyobo) [0111] ABS: ABS resin sheet (product name: ABS-1100-N1-G, manufactured by Sekisui Seikei) [0112] PVC: Vinyl chloride sheet (product name: HP-319, manufactured by Sekisui Seikei)

[0113] According to the results of Examples 1 to 11 shown in Table 1, these nonaqueous ink compositions conforming to the compositional makeup proposed by the present invention had viscosities appropriate for inkjet printing, and the obtained inks also demonstrated balanced properties such as excellent adhesion, discharge stability, rub resistance, and solvent resistance. On the other hand, Comparative Examples 1 to 10 failed to provide inks that excelled in all of these properties.

[0114] In addition, both Comparative Examples 2 and 3 failed to achieve sufficient adhesion to the polyethylene sheet and polypropylene sheet; whereas Example 1, which falls in the middle of these Comparative Examples in terms of the ratio of chlorinated polyolefin resin and ketone resin, demonstrated excellent adhesion to all sheets including polyethylene sheets and polypropylene sheets, thereby confirming the excellent effects of the present invention.