PRETREATMENT LIQUID, INK SET AND PRINTED MATTER

Abstract

A pretreatment liquid that can be used together with an aqueous inkjet ink comprising a pigment and water, wherein the pretreatment liquid comprises a coagulant (A), a surfactant (B), a resin (C) and water, the coagulant (A) comprises a metal salt that includes at least a polyvalent metal salt, the surfactant (B) comprises a polyoxyalkylene alkylamine represented by the following general formula (1).

##STR00001##

Claims

1. A pretreatment liquid that can be used together with an aqueous inkjet ink comprising a pigment and water, wherein the pretreatment liquid comprises a coagulant (A), a surfactant (B), a resin (C) and water, the coagulant (A) comprises a metal salt that includes at least a polyvalent metal salt, and the surfactant (B) comprises a polyoxyalkylene alkylamine represented by the following general formula (1). ##STR00004## [In general formula (1), R represents a linear or branched alkyl group having 6 to 22 carbon atoms, a linear or branched alkenyl group having 6 to 22 carbon atoms, a linear or branched alkylcarbonyl group having 6 to 22 carbon atoms, or, a linear or branched alkenylcarbonyl group having 6 to 22 carbon atoms. EO represents an ethylene oxide group, and PO represents a propylene oxide group. m represents the average addition mole number of EO and is 1 to 100, n represents the average addition mole number of PO and is 0 to 99, and m>n. When n is not 0, there are no restrictions on the addition sequence of the (EO)m and (PO)n, and the addition may be in blocks or may be random. Further, o represents the average addition mole number of EO and is 1 to 100, p represents the average addition mole number of PO and is 0 to 99, and o>p. When p is not 0, there are no restrictions on the addition sequence of the (EO)o and (PO)p, and the addition may be in blocks or may be random.]

2. The pretreatment liquid according to claim 1, wherein the polyvalent metal salt in the coagulant (A) comprises a calcium salt.

3. The pretreatment liquid according to claim 1, wherein the surfactant (B) comprises a polyoxyalkylene alkylamine wherein R in the general formula (1) is a linear or branched alkyl group having 8 to 20 carbon atoms, or a linear or branched alkenyl group having 8 to 20 carbon atoms.

4. The pretreatment liquid according to claim 1, further comprising an acetylene diol-based surfactant.

5. The pretreatment liquid according to claim 1, wherein the resin (C) comprises one or more types of resin particles selected from the group consisting of polyurethane resin particles, polyurethane polyurea resin particles, poly(meth)acrylic resin particles, acrylic-modified polyurethane resin particles, and, polyolefin resin particles.

6. An ink set comprising: the pretreatment liquid according to claim 1, and an aqueous inkjet ink comprising a pigment and water.

7. A substrate to which a pretreatment liquid has been applied, having a layer formed from the pretreatment liquid according to claim 1 on the substrate.

8. A printed matter obtained by printing an aqueous inkjet ink comprising a pigment and water on the substrate to which a pretreatment liquid has been applied according to claim 7.

Description

EXAMPLES

[0226] The pretreatment liquid, and a recording liquid set containing the pretreatment liquid and the aqueous inkjet ink of the embodiments which represent embodiments of the present invention are described below in further detail using examples and comparative examples. Note that, in the following description, unless specifically stated otherwise, “parts” and “%” represent “parts by mass” and “% by mass” respectively.

[0227] After the materials listed below mixed for one hour at room temperature while stirring, the mixture was heated to 90° C. and mixed for an one hour. Subsequently, the mixture was then cooled to room temperature to obtain a PVA103 varnish.

TABLE-US-00001 PVA103 (polyvinyl alcohol manufactured by KURARAY 25 parts Co., Ltd (degree of saponification: 98 to 99% (fully saponified), degree of polymerization: 300)) Ion-exchanged water 75 parts

[0228] A mixing container fitted with a stirrer was prepared and the materials described below were added sequentially. After mixing for one hour at room temperature while gently stirring, the mixture was heated to 60° C. and mixed for a further one hour. Subsequently, the mixture was cooled to room temperature and filtered through a membrane filter having a pore size of 1 μm to obtain a pretreatment solution 1.

TABLE-US-00002 Calcium acetate 10 parts Surfactant 1 1 part PVA103 varnish 20 parts 2-propanol (iPrOH) 4 parts PROXEL GXL (preservative, 1,2-benzisothiazol-3-one 0.1 part solution, manufactured by Arch Chemicals, Inc.) Ion-exchanged water 64.9 parts

[0229] With the exception of using the materials illustrated in Table 1, the same methods as that described for the pretreatment liquid 1 was used to produce the pretreatment liquids 2 to 106. Note that, the details of the materials used are described in the following Tables 2 to 4.

TABLE-US-00003 TABLE 1-1 Example number 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 Pretreatment liquid number 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 Coagulant Metal salt Calcium acetate 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 (A) Surfactant General Surfactant 1 1 1 1 (B) formula (1) Surfactant 2 1 Surfactant 3 1 Surfactant 4 1 Surfactant 5 1 Surfactant 6 1 Surfactant 7 1 Surfactant 8 1 Surfactant 9 1 Surfactant 10 1 Surfactant 11 1 Surfactant 12 1 Surfactant 13 1 Surfactant 14 1 Surfactant 15 1 Surfactant 16 1 Resin (C) Water-soluble PVA103 varnish 20 resin DISPER BYK-190 20 Resin particle Neo Cryl XK-188 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 Organic solvent 2PrOH 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 Preservative PROXEL GXL 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Ion exchange water 64.9 64.9 64.9 64.9 64.9 64.9 64.9 64.9 64.9 64.9 64.9 64.9 64.9 64.9 64.9 64.9 64.9 64.9 Blending amount of surfactant of general 20.0% 12.5% 11.2% 11.2% 11.2% 11.2% 11.2% 11.2% 11.2% 11.2% 11.2% 11.2% 11.2% 11.2% 11.2% 11.2% 11.2% 11.2% formula (1) relative to resin (c) Example number 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 Pretreatment liquid number 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 Coagulant Metal salt Calcium acetate 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 (A) Surfactant General Surfactant 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 formula (1) (B) Other Surfynol 440 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Resin (C) Water-soluble PVA103 varnish 20 resin DISPER BYK-190 20 10 Resin particle Superchlon E-480T 20 Auroren AE-301 20 10 10 10 10 ARROWBASE 20 SB-1230N ARROWBASE 20 SB-1200 Neo Cryl XK-190 20 10 Neo Cryl XK-188 20 10 10 10 Neo RezR-600 20 10 10 Neo RezR-9621 20 10 SUPERFLEX 620 20 SUPERFLEX 650 20 Organic solvent 2PrOH 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 Preservative PROXELGXL 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Ion exchange water 63.9 63.9 63.9 63.9 63.9 63.9 63.9 63.9 63.9 63.9 63.9 63.9 63.9 63.9 63.9 63.9 63.9 63.9 Blending amount of surfactant of general 20.0% 12.5% 16.7% 16.7% 20.0% 20.0% 11.1% 11.2% 15.2% 13.2% 16.7% 19.2% 13.3% 13.4% 15.9% 14.7% 11.8% 12.9% formula (1) relative to resin (c) Example number 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 Pretreatment liquid number 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 Coagulant Metal salt Calcium acetate 10 10 10 10 10 10 10 10 (A) Calcium nitrate 10 Calcium lactate 8 8 8 Calcium forate 10 Magnesium acetate 10 Aluminum nitrate 10 Sodium nitrate 10 Cationic polymer PAA-HCL-3L 10 compound PAS-M-1 10 Surfactant General Surfactant 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 0.05 1 formula (1) (B) Other Surfynol440 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Resin (C) Water-soluble PVA103 varnish 5 20 resin DISPER BYK-190 5 5 Resin particle ARROWBASE 20 20 20 20 20 20 20 20 20 20 20 SB-123ON Neo Cryl XK-190 10 10 10 Neo Cryl XK-188 10 10 10 Neo RezR-600 10 10 10 Neo RezR-9621 10 10 10 HITECE-5403P 5 Chemipearl W950 5 Organic solvent 2PrOH 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 Preservative PROXELGXL 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Anti-foaming agent TEGO ® 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Foamex845 pH adjusting agent TEA 1 1 Ion exchange water 63.9 58.9 58.9 58.9 58.9 57.8 62.8 63.8 63.8 65.8 63.8 63.8 63.8 63.8 63.8 63.8 66.8 66.7 Blending amount of surfactant of general 12.1% 10.3% 9.8% 11.0% 10.2% 10.2% 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% 1.0% 2.0% formula (1) relative to resin (c) Example number 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 Pretreatment liquid number 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 Coagulant Metalsalt Calcium lactate 8 8 8 8 8 8 8 8 5 (A) Calcium acetate 0.5 1.3 3.0 4.5 20 15 5 Calcium nitrate 30 34 20 Surfactant General Surfactant 1 0.3 5.5 4.25 4.95 4 0.55 2 3 1 1 1 1 1 1 1 1 1 1 formula (1) (B) Other Surfynol 440 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Resin (C) Resin particle ARROWBASE 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 SB-1230N Organic solvent 2PrOH 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 Preservative PROXEL GXL 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Anti-foaming agent TEGO ® 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Foamex845 Ion exchange water 66.5 61.3 62.6 61.9 62.8 66.3 64.8 63.8 73.3 72.5 70.8 69.3 53.8 58.8 43.8 39.8 53.8 63.8 Blending amount of surfactant of general 6.0% 110.0% 85.0% 99.0% 80.0% 11.0% 40.0% 60.0% 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% formula (1) relative to resin (c) Example number 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 Pretreatment liquid number 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 Coagulant Metal salt Calcium lactate 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 8 (A) Calcium acetate Calcium nitrate Surfactant General Surfactant 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 (B) formula (1) Other Surfynol 104 1 Surfynol 465 1 1 1 1 1 1 1 1 1 1 1 1 1 Surfynol 485 1 Surfynol SE 1 BYK-349 1 EMULGEN 1 1150S-60 Resin (C) Resin particle ARROWBASE 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 SB-1230N Organic solvent 2PrOH 4 4 4 4 4 4 1 2 30 40 5 MB 4 1,2-PD 4 BOH 4 1,3-PD 4 1,5-PD 4 Gly 4 Preservative PROXELGXL 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Anti-foaming agent TEGO ® 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Foamex845 Ion exchange water 65.8 65.8 65.8 65.8 65.8 65.8 65.8 65.8 65.8 65.8 65.8 65.8 68.8 67.8 39.8 29.8 54.8 54.8 Blending amount of surfactant of general 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% formula (1) relative to resin (c) Example number 91 92 93 94 95 96 97 98 99 100 Pretreatment liquid number 91 92 93 94 95 96 97 98 99 100 Coagulant Metal salt Calcium lactate 5 5 5 5 5 5 5 5 5 5 (A) Calcium acetate Calcium nitrate Surfactant General Surfactant 1 0.5 0.5 (B) formula (1) Surfactant 2 1 1 1 1 0.5 Surfactant 3 0.5 Surfactant 4 1 1 1 1 Other Surfynol465 1 1 1 1 1 1 1 1 1 1 Resin (C) Resin particle Neo Cryl XK-188 2 60 45 20 10 10 10 10 10 10 ARROWBASE 10 10 10 10 10 SB-1230N Neo RezR-9621 10 Organic solvent 2PrOH 5 5 5 5 MB 1,2-PD 5 5 5 5 5 5 1 1 EtOH 1,3-PD 1,5-PD 1 Gly 1 Preservative PROXEL GXL 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Anti-foaming agent TEGO ® 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Foamex845 Ion exchange water 85.8 27.8 42.8 67.8 67.8 67.8 66.8 66.8 66.8 66.8 Blending amount of surfactant of general 112.4% 3.7% 5.0% 11.2% 14.4% 14.4% 14.4% 12.1% 14.4% 14.4% formula (1) relative to resin (c) Comparative example number 1 2 3 4 5 6 Pretreatment liquid number 101 102 103 104 105 106 Coagulant Metal salt Calcium lactate 5 5 5 5 (A) Other coagulants Malonic acid 5 Surfactant General Surfactant 1 1 (B) formula (1) Surfactant 2 1 1 Surfynol 465 1 1 1 1 Other BYK-349 1 EMULGEN 1 1150S-60 Resin (C) Resin particle Neo Cryl XK-188 10 10 10 10 10 ARROWBASE 10 10 10 10 10 SB-1230N Organic solvent 2PrOH 1,2-PD 5 5 5 5 5 5 Preservative PROXEL GXL 0.1 0.1 0.1 0.1 0.1 0.1 Anti-foaming agent TEGO ® 0.1 0.1 0.1 0.1 0.1 0.1 Foamex845 Ion exchange water 67.8 72.8 68.8 68.8 68.8 87.8 Blending amount of surfactant of general 14.4% 14.4% 0.0% 0.0% 0.0% — formula (1) relative to resin (c)

TABLE-US-00004 TABLE 2 Name Solid fraction Details Coagulant Metal salt Calcium nitrate 100% (A) Calcium lactate 100% Calcium formate 100% Calcium acetate 100% Magnesium acetate 100% Aluminum nitrate 100% Sodium nitrate 100% Cationic PAA-HCL-3L 50% Polyallylamine hydrochloride manufactured polymer by Nittobo Medical Co., Ltd. compound PAS-M-1 50% Polymethyldiallylamine hydrochloride manufactured by Nittobo Medical Co., Ltd. Other coagulants Organic acid Malonic acid 100% Organic solvent 2PrOH — 2-propanol Boiling point at one atmosphere: 83° C. MB — 3-methoxybutanol Boiling point at one atmosphere: 150° C. 1,2-PD — 1,2-propanediol Boiling point at one atmosphere: 188° C. EtOH — Ethanol Boiling point at one atmosphere: 78° C. 1,3-PD — 1,3-propanediol Boiling point at one atmosphere: 214° C. 1,5-PD — 1,5-pentanediol Boiling point at one atmosphere: 242° C. Gly — Glycerin Boiling point at one atmosphere: 290° C.

TABLE-US-00005 TABLE 3 Name Solid fraction Details Surfactant Surfactant Surfactant 1 100% R in general formula (1) = lauryl group, m = 2, o = 2, n = 0, p = 0 (B) in general Surfactant 2 100% R in general formula (1) = stearyl group, m = 2, o = 2, n = 0, p = 0 formula (1) Surfactant 3 100% R in general formula (1) = oleyl group, m = 2, o = 2, n = 0, p = 0 Surfactant 4 100% R in general formula (1) = beef tallow alkyl group, m = 2, o = 2, n = 0, p = 0 Surfactant 5 100% R in general formula (1) = palm alkyl group, m = 2, o = 2, n = 0, p = 0 Surfactant 6 100% R in general formula (1) = hexyl group, m = 2, o = 2, n = 0, p = 0 Surfactant 7 100% R in general formula (1) = ethylhexyl group, m = 2, o = 2, n = 0, p = 0 Surfactant 8 100% R in general formula (1) = behenyl group, m = 2, o = 2, n = 0, p = 0 Surfactant 9 100% R in general formula (1) = lauryl group, m = 100, o = 100, n = 0, p = 0 Surfactant 10 100% R in general formula (1) = lauryl group, m = 20, o = 30, n = 0, p = 0 Surfactant 11 100% R in general formula (1) = lauryl group, m = 1, o = 1, n = 0, p = 0 Surfactant 12 100% R in general formula (1) = lauryl group, m = 5, o = 5, n = 0, p = 0 Surfactant 13 100% R in general formula (1) = lauryl group, m = 50, o = 60, n = 0, p = 0 Surfactant 14 100% R in general formula (1) = lauryl group, m = 80, o = 75, n = 0, p = 0 Surfactant 15 100% R in general formula (1) = lauryl group, m = 2, o = 2, n = 1, p = 1 Surfactant 16 100% R in general formula (1) = lauryl group, m = 100, o = 90, n = 80, p = 85 Other Acetylene Surfynol 104 100% Acetylenediol-based surfactant manufactured by Air Sur- diol-based Products and Chemicals, Inc. (HLB = 4.0) factants Surfynol 440 100% Acetylenediol-based surfactant manufactured by Air Products and Chemicals, Inc. (HLB = 8) Surfynol 465 100% Acetylenediol-based surfactant manufactured by Air Products and Chemicals, Inc. (HLB = 13) Surfynol 485 100% Acetylenediol-based surfactant manufactured by Air Products and Chemicals, Inc. (HLB = 17) Surfynol SE 81% Acetylenediol-based surfactant manufactured by Air Products and Chemicals, Inc. (HLB = 6) Silicone-based BYK-349 100% Silicone-based surfoctant manufactured by BYK Chemie Japan Polyoxyethylene EMULGEN 60% Polyoxyethylene alkyl ether-based surfactant alkyl 1150S-60 manufactured by Kao Corporation ether-based Anti-foaming agent TEGO ® Foamex 845 20% Organic modified siloxane copolymer/silica manufactured by Evonik Japan pH adjusting agent TEA — Triethanolamine Preservative PROXEL 20% 1,2-benzisothiazol-3-one (dipropylene glycol solution) GXL manufactured by Arch Chemicals Inc.

TABLE-US-00006 TABLE 4 Solid Details Name fraction Resin Water- PVA103 100% Polyvinyl alcohol (nonionic) manufactured by KURARAY Co., Ltd. (C) soluble resin DISPER BYK-190 40% Styrene-maleic acid-based resin (anionic) manufactured by BYK Chemie Japan Resin par- Superchlon E-480T 30% Chlorinated polyolefin resin microparticle (anionic) manufactured by Nippon Paper Chemicals Co., Ltd D50: 75 nm ticle Auroren AE-301 30% Non-chlorinated polyolefin resin microparticle (anionic) manufactured by Nippon Paper Chemicals Co., Ltd D50: 75 nm ARROWBASE SB-1230N 25% Non-chlorinated polyolefin resin microparticle (anionic) manufactured by Unitika Ltd. D50: 85 nm ARROWBASE SB-1200 25% Non-chlorinated polyolefin resin microparticle (anionic) manufactured by Unitika Ltd. D50: 110 nm Neo Cryl XK-190 45% Acrylic resin particle (anionic) manufactured by DSM Coating Resins D50: 100 nm Neo Cryl XK-188 44.5% Acrylic resin particle (anionic) manufactured by DSM Coating Resins D50: 120 nm Neo Rez R-600 33% Polyurethane resin particle (anionic) manufactured by DSM Coating Resins D50: 70 nm Neo Rez R-9621 38% Polyurethane resin particle (anionic) manufactured by DSM Coating Resins D50: 40 nm HITEC E-5403P 30% Polyethylene resin particle (nonionic) manufactured by Toho Chemical Industry Co., Ltd. D50: 50 nm Chemipearl W950 40% Polyethylene resin particle (anionic) manufactured by Mitsui Chemical Inc. D50: 500 nm SUPERFLEX 620 30% Polyurethane resin microparticle (cationic) manufactured by DKS Co., Ltd. D50: 20 nm SUPERFLEX 650 26% Polyurethane resin microparticle (cationic) manufactured by DKS Co., Ltd. D50: 10 nm

[0230] For the pretreatment liquids produced above, the viscosity at 25° C. was measured using an E-type viscometer (TVE-20L manufactured by Toki Sangyo Co., Ltd.), and the pretreatment liquid was then placed in a sealed container and stored in a still state in a thermostatic chamber set to 50° C. The sealed container took out from the thermostatic chamber weekly, the viscosity and the storage stability of the pretreatment liquid was evaluated by calculating the change in viscosity during storage. The evaluation criteria are as follows, and an AA, A, or B evaluation is deemed to be a practically applicable level.

(Evaluation Criteria)

[0231] AA: the change in viscosity after four weeks storage was less than ±5%

[0232] A: the change in viscosity after three weeks storage was less than ±5, but the change in viscosity after four weeks storage was at least ±5%

[0233] B: the change in viscosity after two weeks storage was less than ±5%, but the change in viscosity after three weeks storage was at least ±5%

[0234] C: the change in viscosity after one week storage was less than ±5%, but the change in viscosity after two weeks storage was at least ±5%

[0235] D: the change in viscosity after one week storage was at least ±5%

[0236] A K Control Coater K202 manufactured by Matsuo Sangyo Co., Ltd. and a wire bar No. 0 were used to apply the pretreatment liquids prepared as described above to a wet film thickness of 4.0±0.2 μm on the substrate. Subsequently, the substrate to which the pretreatment liquid had been applied was dried in a 70° C. air oven for 1 minute to produce a substrate having the pretreatment liquid applied thereon.

[0237] OK topcoat+coated paper made by Oji Paper Co., Ltd. 104.7 g/m.sup.2
PET: polyethylene terephthalate film “FE2001” (thickness of 12 μm) manufactured by Futamura Chemical Co. Ltd.

[0238] The exterior of a substrate coated with a pretreatment liquid based on the method described was observed visually, and with a magnifying glass. The evaluation criteria are as follows, and an AA, A, or B evaluation is deemed to be a practically applicable level.

(Evaluation Criteria)

[0239] AA: no cissing or coating unevenness was observed visually or with a magnifying glass

[0240] A: very little coating unevenness when observed with a magnifying glass, but no cissing or coating unevenness was observed visually

[0241] B: some coating unevenness when observed with a magnifying glass, but no cissing or coating unevenness was observed visually

[0242] C: cissing or coating unevenness was observed visually

TABLE-US-00007 TABLE 5 Evaluation result Pre- Coating unevenness treatment Storage OK PET liquid stability topcoat film Example 1 1 AA A A Example 2 2 AA A A Example 3 3 AA A A Example 4 4 AA A A Example 5 5 AA A A Example 6 6 AA A A Example 7 7 AA A A Example 8 8 A A B Example 9 9 A A B Example 10 10 AA A A Example 11 11 AA A A Example 12 12 AA A A Example 13 13 AA A A Example 14 14 AA A A Example 15 15 AA A A Example 16 16 AA A A Example 17 17 AA A A Example 18 18 AA A A Example 19 19 AA AA AA Example 20 20 AA AA AA Example 21 21 AA AA AA Example 22 22 AA AA AA Example 23 23 AA AA AA Example 24 24 AA AA AA Example 25 25 AA AA AA Example 26 26 AA AA AA Example 27 27 AA AA AA Example 28 28 AA AA AA Example 29 29 AA AA AA Example 30 30 AA AA AA Example 31 31 AA AA AA Example 32 32 AA AA AA Example 33 33 AA AA AA Example 34 34 AA AA AA Example 35 35 AA AA AA Example 36 36 AA AA AA Example 37 37 AA AA AA Example 38 38 AA AA AA Example 39 39 AA AA AA Example 40 40 AA AA AA Example 41 41 AA AA AA Example 42 42 AA AA AA Example 43 43 AA AA AA Example 44 44 AA AA AA Example 45 45 AA AA AA Example 46 46 AA AA AA Example 47 47 AA AA AA Example 48 48 AA AA AA Example 49 49 AA AA AA Example 50 50 AA AA AA Example 51 51 AA AA AA Example 52 52 AA AA AA Example 53 53 B AA A Example 54 54 A AA AA Example 55 55 AA AA AA Example 56 56 A AA AA Example 57 57 AA AA AA Example 58 58 AA AA AA Example 59 59 AA AA AA Example 60 60 AA AA AA Example 61 61 AA AA AA Example 62 62 AA AA AA Example 63 63 AA AA AA Example 64 64 AA AA AA Example 65 65 AA AA AA Example 66 66 AA AA AA Example 67 67 AA AA AA Example 68 68 AA AA AA Example 69 69 A AA AA Example 70 70 B AA AA Example 71 71 AA AA AA Example 72 72 AA AA AA Example 73 73 AA AA A Example 74 74 AA AA AA Example 75 75 AA AA A Example 76 76 AA AA AA Example 77 77 AA A A Example 78 78 AA A A Example 79 79 AA AA AA Example 80 80 AA AA AA Example 81 81 AA AA AA Example 82 82 AA AA AA Example 83 83 AA AA AA Example 84 84 AA AA AA Example 85 85 AA AA A Example 86 86 AA AA AA Example 87 87 AA AA AA Example 88 88 A AA AA Example 89 89 AA AA AA Example 90 90 AA AA AA Example 91 91 AA AA AA Example 92 92 A AA A Example 93 93 AA AA AA Example 94 94 AA AA AA Example 95 95 AA AA AA Example 96 96 AA AA AA Example 97 97 AA AA AA Example 98 98 AA AA AA Example 99 99 AA AA AA Example 100 100 AA AA AA Comparative 101 C A A Example 1 Comparative 102 AA B C Example 2 Comparative 103 D B C Example 3 Comparative 104 D B C Example 4 Comparative 105 C B C Example 5 Comparative 106 AA C C Example 6

[0243] A reaction container fitted with a gas inlet tube, a thermometer, a condenser and a stirrer was charged with 95 parts of butanol, and the container was flushed with nitrogen gas. The inside of the container was heated to 110° C., and a mixture containing 45 parts of styrene, 30 parts of acrylic acid and 25 parts of lauryl methacrylate as polymerizable monomers and 6 parts of a polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise to the container over a period of two hours to achieve a polymerization reaction. Following completion of the dropwise addition, the reaction was continued at 110° C. for a further three hours, an additional 0.6 parts of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was then added, and the reaction was continued at 110° C. for a further one hour, thus obtaining a solution of a pigment dispersing resin 1. Following cooling of the solution to room temperature, dimethylaminoethanol was added to completely neutralize the solution, and 100 parts of water was then added to generate an aqueous solution. Subsequently, the aqueous solution was heated to at least 100° C., and the butanol was removed by azeotropic distillation with water so as to adjust the solid fraction to 30%, an aqueous solution (solid fraction: 30%) of the pigment dispersing resin 1 was obtained. Note that, the acid value of the pigment dispersing resin 1, measured using the method described above, was 230 mgKOH/g, and the weight average molecular weight was 25,000.

[0244] With the exception of altering the types and amounts of the polymerizable monomers as shown below in Table 6, aqueous solutions (solid fraction: 30%) of pigment dispersing resins 2 to 4 were obtained in the same manner as the above pigment dispersing resin 1.

TABLE-US-00008 TABLE 6 Pigment dispersing resin 1 2 3 4 Polymerizable Styrene 45 45 45 45 monomer Acrylic acid 30 30 30 30 2-ethylhexyl acrylate 25 Behenyl acrylate 25 Butyl acrylate 25 Lauryl methacrylate 25 Acid value 230 225 232 230 Weight average molecular weight 25,000 15,000 20,000 13,000

[0245] Twenty parts of LIONOL BLUE 7358G (C.I. Pigment Blue 15:3) manufactured by Toyo Color Co., Ltd., 20 parts of the aqueous solution (solid fraction: 30%) of the pigment dispersing resin 1 and 60 parts of water were mixed together and premixed using a stirrer, and the mixture was then subjected to a main dispersion using a Dyno-Mill with a capacity of 0.6 L filled with 1,800 g of zirconia beads of diameter 0.5 mm, thus obtaining a pigment dispersion liquid 1C. Further, with the exception of replacing the C.I. Pigment Blue 15:3 with each of the pigments shown below, pigment dispersion liquids 1M (Magenta), 1Y (Yellow), and 1K (Black) were obtained in the same manner as the pigment dispersion liquid 1C.

Magenta: FASTOGEN SUPER MAGENTA RG (C.I. Pigment Red 122), manufactured by DIC Corporation
Yellow: LIONOL YELLOW TT-1405G (C.I. Pigment Yellow 14), manufactured by Toyo Color Co., Ltd
Black: PrinteX 85 manufactured by Orion Engineered Carbons S.A

(Carbon Black)

[0246] With the exception of using the aqueous solutions (solid fraction: 30%) of each of the pigment dispersing resins 2 to 4 as the pigment dispersing resin, pigment dispersion liquids 2 to 4 (each including C, M, Y and K) were obtained using the same methods as that described for the pigment dispersion liquids 1C, 1M, 1Y and 1K.

[0247] Forty parts of TIPAQUE CR-90-2 (titanium oxide) manufactured by Ishihara Sangyo Kaisha, Ltd., 20 parts of the aqueous solution (solid fraction: 30%) of the pigment dispersing resin 1, and 40 parts of water were mixed, and following premixing using a stirrer, a Dyno-Mill with a capacity of 0.6 L filled with 1,800 g of zirconia beads of diameter 0.5 mm was used to perform the main dispersion, thus obtaining a pigment dispersion liquid 1W (pigment concentration: 40%).

[0248] With the exception of using the aqueous solution (solid fraction: 30%) of the pigment dispersing resins 2 to 4 as the pigment dispersing resin, pigment dispersion liquids 2W to 4W were obtained using the same methods as that described for the pigment dispersion liquid 1W.

[0249] The materials listed below were added sequentially to a mixing container fitted with a stirrer, and thorough stirring was performed until a uniform mixture was obtained. Subsequently, filtration was performed using a membrane filter having a pore size of 1 μm to remove coarse particles that can cause inkjet head blockages, thus obtaining an aqueous inkjet cyan ink 1. Further, with the exception of using each of the pigment dispersion liquids 1M, 1Y and 1K instead of the pigment dispersion liquid 1C, an aqueous inkjet ink set 1 composed of the four colors of cyan (C), magenta (M), yellow (Y) and black (K) was obtained.

TABLE-US-00009 Pigment dispersion liquid 1C 25 parts NeoCrylXK-190 (solid fraction 45%) 15 parts 1,2-propanediol 20 parts KF-6015 1 part PROXEL GXL 0.1 part Ion-exchanged water 38.9 parts

[0250] In the above production example, NeoCryl XK-190 is an acrylic resin emulsion (solid fraction: 45%) manufactured by DSM Coating Resins.

[0251] With the exception of using the materials described in Table 7, Inkjet color ink sets 2 to 21 each composed of the four colors; cyan (C), magenta (M), yellow (Y), and black (K) were obtained using the same methods as that described for the Inkjet ink set 1.

[0252] Note that, abbreviations and details for those materials included in Table 7 are as follows:

[0253] PGmME: propylene glycol monomethyl ether (boiling point at one atmosphere at 120° C.)

[0254] MB: 3-methoxybutanol (boiling point at one atmosphere at 150° C.)

[0255] 1,2-PD: 1,2-propanediol (boiling point at one atmosphere at 188° C.)

[0256] 1,2-BD: 1,2-butanediol (boiling point at one atmosphere at 192° C.)

[0257] 1,3-PD: 1,3-propanediol (boiling point at one atmosphere at 214° C.)

[0258] 1,2-HD: 1,2-hexanediol (boiling point at one atmosphere at 224° C.)

[0259] TEGmEE: triethylene glycol monoethyl ether (boiling point at one atmosphere at 256° C.)

[0260] KF-6015: siloxane-based surfactant manufactured by Nissin Chemical Industry Co., Ltd.

TABLE-US-00010 TABLE 7 Inkjet color ink set (CMYK) 1 2 3 4 5 6 7 8 9 10 11 Pigment Pigment dispersion 25 25 25 25 25 25 25 25 liquid 1 (C, M, Y, K) disper- Pigment dispersion 25 sion liquid 2 (C, M, Y, K) Pigment dispersion 25 liquid 3 (C, M, Y, K) Pigment dispersion 25 liquid 4 (C, M, Y, K) Binder Neo Cryl XK-190 15 15 15 15 15 15 15 15 15 15 15 Resin Water- PGmME Boiling Point: soluble 120° C. organic MB Boiling Point: solvent 150° C. 1,2-PD Boiling Point: 20 20 20 20 188° C. 1,2-BD Boiling Point: 10 15 18 19 15 18 15 192° C. 1,3-PD Boiling Point: 214° C. 1,2-HD Boiling Point: 5 2 3 224° C. TEGmEE Boiling Point: 10 5 2 1 2 256° C. Surfac- Surfynol 465 tant KF-6015 1 1 1 1 1 1 1 1 1 1 1 Preser- PROXEL GXL 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 vative Ion exchange water 38.9 38.9 38.9 38.9 38.9 38.9 38.9 38.9 38.9 38.9 38.9 Weighted boiling point average 188.0 188.0 188.0 188.0 224.0 208.0 198.4 195.2 200.0 195.2 203.2 at one atmosphere of water- soluble organic solvent Amount of solvent in which 0 0 0 0 10 5 2 1 0 0 2 boiling point at one atm is 250° C. or higher Amount of solvent in which 0 0 0 0 10 5 2 1 5 2 5 boiling point at one atm is 220° C. or higher Inkjet color ink set (CMYK) 12 13 14 15 16 17 18 19 20 21 Pigment Pigment dispersion 25 25 25 25 25 25 25 25 25 25 dispersion liquid 1 (C, M, Y, K) Pigment dispersion liquid 2 (C, M, Y, K) Pigment dispersion liquid 3 (C, M, Y, K) Pigment dispersion liquid 4 (C, M, Y, K) Binder Resin Neo Cryl XK-190 15 15 15 15 15 15 15 15 15 15 PGmME Boiling Point: 5 120° C. MB Boiling Point: 10 5 150° C. 1,2-PD Boiling Point: 15 15 188° C. 1,2-BD Boiling Point: 18 8 30 10 20 5 15 5 192° C. 1,3-PD Boiling Point: 20 214° C. 1,2-HD Boiling Point: 1 224° C. TEGmEE Boiling Point: 256° C. 1 Surfactant Surfynol 465 1 KF-6015 1 1 1 1 1 1 1 1 1 1 Preservative PROXEL GXL 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Ion exchange water 38.9 50.9 28.9 18.9 38.9 38.9 43.9 38.9 38.9 37.9 Weighted boiling point average at one 196.8 192.0 192.0 192.0 214.0 192.0 188.0 153.0 181.5 189.0 atmosphere of water-soluble organic solvent Amount of solvent in which boiling point 1 0 0 0 0 0 0 0 0 0 at one atm is 250° C. or higher Amount of solvent in which boiling point 2 0 0 0 0 0 0 0 0 0 at one atm is 220° C. or higher

[0261] With the exception of using the materials described in Table 8, the aqueous inkjet white inks 1 to 21 were obtained by the same methods as the inkjet cyan ink 1.

TABLE-US-00011 TABLE 8 Aqueous inkjet white ink 1 2 3 4 5 6 7 8 9 10 11 Pigment Pigment dispersion 30 30 30 30 30 30 30 30 dispersion liquid 1W Pigment dispersion 30 liquid 2W Pigment dispersion 30 liquid 3W Pigment dispersion 30 liquid 4W Binder Resin Neo Cryl XK-190 15 15 15 15 15 15 15 15 15 15 15 Water- PGmME Boiling Point: soluble 120° C. organic MB Boiling Point: solvent 150° C. 1,2-PD Boiling Point: 20 20 20 20 188° C. 1,2-BD Boiling Point: 10 15 18 19 15 18 15 192° C. 1,3-PD Boiling Point: 214° C. 1,2-HD Boiling Point: 224° C. TEGmEE Boiling Point: 256° C. Surfactant Surfynol 465 KF-6015 1 1 1 1 1 1 1 1 1 1 1 Preservative PROXEL GXL 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Ion exchange water 33.9 33.9 33.9 33.9 33.9 33.9 33.9 33.9 33.9 33.9 33.9 Weighted boiling point average at one 188.0 188.0 188.0 188.0 224.0 208.0 198.4 195.2 200.0 195.2 203.2 atmosphere of water-soluble organic solvent Amount of solvent in which boiling 0 0 0 0 10 5 2 1 0 0 2 point at one atm is 250° C. or higher Amount of solvent in which boiling 0 0 0 0 10 5 2 1 5 2 5 point at one atm is 220° C. or higher Aqueous inkjet white ink 12 13 14 15 16 17 18 19 20 21 Pigment Pigment dispersion 30 30 30 30 30 30 30 30 30 30 dispersion liquid 1W Pigment dispersion liquid 2W Pigment dispersion liquid 3W Pigment dispersion liquid 4W Binder Resin Neo Cryl XK-190 15 15 15 15 15 15 15 15 15 15 PGmME Boiling Point: 5 120° C. MB Boiling Point: 10 5 150° C. 1,2-PD Boiling Point: 15 15 188° C. 1,2-BD Boiling Point: 18 8 30 40 20 5 15 5 192° C. 1,3-PD Boiling Point: 20 214° C. 1,2-HD Boiling Point: 224° C. TEGmEE Boiling Point: 256° C. Surfactant Surfynol 465 1 KF-6015 1 1 1 1 1 1 1 1 1 1 Preservative PROXEL GXL 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Ion exchange water 33.9 45.9 23.9 13.9 33.9 33.9 38.9 33.9 33.9 32.9 Weighted boiling point average at one 196.8 192.0 192.0 192.0 214.0 192.0 188.0 153.0 181.5 189.0 atmosphere of water-soluble organic solvent Amount of solvent in which boiling 1 0 0 0 0 0 0 0 0 0 point at one atm is 250° C. or higher Amount of solvent in which boiling 2 0 0 0 0 0 0 0 0 0 point at one atm is 220° C. or higher

[0262] Tables 7 and 8 collectively show the weighted boiling point average at one atmosphere (° C.), and the amount (% by mass) of water-soluble organic solvent having a boiling point at one atmosphere of 250° C. (or 220° C.) or higher of the water-soluble organic solvent contained in each ink.

[0263] The following evaluations were performed using the combinations of the color inks and the white ink illustrated in Table 9 as an inkjet ink set. The results are illustrated in Table 10.

TABLE-US-00012 TABLE 9 Aqueous inkjet ink set 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 Inkjet color ink set 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 (CMYK) Inkjet white ink 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21

TABLE-US-00013 TABLE 10-1 Pretreat- Evaluation result ment Inkjet Mixed color bleeding Solid filling Drying Coating film liquid ink set OK topcoat PET film OK topcoat PET film property Adhesion durability Example 101 1 1 A A A A AA B B Example 102 2 1 A A A A AA B B Example 103 3 1 A A A A AA A A Example 104 4 1 A A A A AA A A Example 105 5 1 A A A A AA A A Example 106 6 1 A A A A AA A A Example 107 7 1 A A A A AA A A Example 108 8 1 B B B B AA A A Example 109 9 1 A B A B AA A A Example 110 10 1 B B B B AA A A Example 111 11 1 A A A A AA A A Example 112 12 1 A A A A AA A A Example 113 13 1 A A A A AA A A Example 114 14 1 A A A A AA A A Example 115 15 1 A A A A AA A A Example 116 16 1 A A A A AA A A Example 117 17 1 A A A A AA A A Example 118 18 1 A A A A AA A A Example 119 19 1 AA AA AA AA AA B B Example 120 20 1 AA AA AA AA AA B B Example 121 21 1 AA AA AA AA AA A A Example 122 22 1 AA AA AA AA AA A A Example 123 23 1 AA AA AA AA AA A A Example 124 24 1 AA AA AA AA AA A A Example 125 25 1 AA AA AA AA AA A A Example 126 26 1 AA AA AA AA AA A A Example 127 27 1 AA AA AA AA AA A A Example 128 28 1 AA AA AA AA AA A A Example 129 29 1 AA AA AA AA AA B A Example 130 30 1 AA AA AA AA AA B A Example 131 31 1 AA AA AA AA AA AA AA Example 132 32 1 AA AA AA AA AA AA AA Example 133 33 1 AA AA AA AA AA AA AA Example 134 34 1 AA AA AA AA AA AA AA Example 135 35 1 AA AA AA AA AA A A Example 136 36 1 AA AA AA AA AA AA AA Example 137 37 1 AA AA AA AA AA AA AA Example 138 38 1 AA AA AA AA AA AA AA Example 139 39 1 AA AA AA AA AA AA AA Example 140 40 1 AA AA AA AA AA AA AA Example 141 41 1 AA AA AA AA AA AA AA Example 142 42 1 AA AA AA AA A AA AA Example 143 43 1 AA AA AA AA A B B Example 144 44 1 AA AA AA AA AA A A Example 145 45 1 AA AA AA AA AA A A Example 146 46 1 AA AA AA AA AA A A Example 147 47 1 AA AA AA AA AA A A Example 148 48 1 A A A A AA A A Example 149 49 1 A A A A AA A A Example 150 50 1 B B B B AA A A

TABLE-US-00014 TABLE 10-2 Pretreat- Evaluation result ment Inkjet Mixed color bleeding Solid filling Drying Coating film liquid ink set OK topcoat PET film OK topcoat PET film property Adhesion durability Example 151 51 1 B B B B AA A A Example 152 52 1 B B B B AA A A Example 153 53 1 A B A B AA A A Example 154 54 1 A A A A AA A A Example 155 55 1 AA AA AA AA AA A A Example 156 56 1 A B AA AA A A A Example 157 57 1 AA A AA AA AA A A Example 158 58 1 A A AA AA A A A Example 159 59 1 AA AA AA AA AA A A Example 160 60 1 AA AA AA AA AA A A Example 161 61 1 AA AA AA AA AA A A Example 162 62 1 AA AA AA AA AA A A Example 163 63 1 B B B B AA A A Example 164 64 1 B B A A AA A A Example 165 65 1 A A AA AA AA A A Example 166 66 1 AA AA AA AA AA A A Example 167 67 1 AA AA A AA AA A A Example 168 68 1 AA AA AA AA AA A A Example 169 69 1 AA AA A A A A A Example 170 70 1 AA AA A A B B B Example 171 71 1 AA AA AA AA AA A A Example 172 72 1 AA AA AA AA AA A A Example 173 73 1 AA A AA A AA A A Example 174 74 1 AA AA AA AA AA A A Example 175 75 1 AA A AA A AA A A Example 176 76 1 AA AA AA AA AA A A Example 177 77 1 A A A A AA A A Example 178 78 1 A A A A AA A A Example 179 79 1 AA AA AA AA AA A A Example 180 80 1 AA AA AA AA AA A A Example 181 81 1 AA AA AA AA AA A A Example 182 82 1 AA A AA A A A A Example 183 83 1 A B A B B B B Example 184 84 1 B B B B B B B Example 185 85 1 AA A AA A AA A A Example 186 86 1 AA AA AA AA AA A A Example 187 87 1 AA AA AA AA AA A A Example 188 88 1 AA A AA A A A A Example 189 89 1 AA AA AA AA AA A A Example 190 90 1 AA AA AA AA AA A A Example 191 91 1 A A A A A A A Example 192 92 1 A A A A B B B Example 193 93 1 AA AA AA AA AA A A Example 194 94 1 AA AA AA AA AA A A Example 195 95 1 AA AA AA AA AA AA AA Example 196 96 1 AA AA AA AA AA AA AA Example 197 97 1 AA AA AA AA AA AA AA Example 198 98 1 AA AA AA AA AA AA AA Example 199 99 1 AA A AA A A AA AA Example 200 100 1 A A A A B A A

TABLE-US-00015 TABLE 10-3 Pretreat- Evaluation result ment Inkjet Mixed color bleeding Solid filling Drying Coating film liquid ink set OK topcoat PET film OK topcoat PET film property Adhesion durability Example 201 95 2 AA AA AA AA A A AA Example 202 95 3 AA AA AA AA AA AA AA Example 203 95 4 AA AA AA AA A AA AA Example 204 95 5 B B B B B B B Example 205 95 6 A B A B B B B Example 206 95 7 A B A B A A B Example 207 95 8 A A A A A A A Example 208 95 9 A B A B A A A Example 209 95 10 A A A A A A A Example 210 95 11 A B A B A B B Example 211 95 12 A A A A A B A Example 212 95 13 AA A AA AA AA AA AA Example 213 95 14 AA A AA AA AA AA AA Example 214 95 15 AA A AA AA A AA A Example 215 95 16 A A AA AA A A A Example 216 95 17 AA A AA AA AA AA AA Example 217 95 18 AA AA AA AA AA AA AA Example 218 95 19 AA AA AA A AA AA AA Example 219 95 20 AA AA AA AA AA AA AA Example 220 95 21 AA AA AA AA AA AA AA Comparative 101 1 B C B C C C C Example 7 Comparative 102 1 C C C C C B B Example 8 Comparative 103 1 C C C C C B B Example 9 Comparative 104 1 C C C c C B B Example 10 Comparative 105 1 C C C c c B B Example 11 Comparative 106 1 B C B C c D C Example 12

[0264] An inkjet head KJ4B-QA (manufactured by Kyocera Corporation, design resolution: 600 dpi) was installed above a conveyor capable of transporting a substrate, and was filled with one of the aqueous inkjet ink sets produced above in the order K, C, M, and Y from the upstream side. Subsequently, the substrate coated with the pretreatment liquid that had been prepared in the manner described above was secured to the conveyor, the conveyor was driven at a constant speed, and when the substrate passed beneath the installed position of the inkjet head, each of the inkjet inks was discharged using a drop volume of 3 pL, thereby printing the images described below Immediately after printing, the printed matter was placed in a 70° C. air oven and dried for 3 minutes to complete production of the printed matter.

[0265] Printing was conducted with the conveyor drive speed set to one of three conditions, namely 25 m/minute, 50 m/minute, and 75 m/minute. Further, an image in which 5 cm×5 cm solid patches were arranged adjacent to one another at a print ratio of 100% in the order CMYK (hereinafter, referred to as the “solid patches image”), a 4-color (CMYK) image in which the total print ratio (the total of the print ratios for each of the colors) was varied continuously from 40 to 320% (hereafter called the “gradation image”. wherein the print ratio was the same for each color at each total print ratio), and a solid image printed using CMYK at a total print ratio of 320% (hereinafter, referred to as the “4C solid image”, wherein the print ratio of each color was 80%), and printed items of each image were produced. Further, when using a PET film as the substrate, a W was solid printed on the image prepared by printing with the CMYK ink at a print ratio of 100% to create a printed matter.

Examples 101 to 220 and Comparative Examples 7 to 12

[0266] Using the combinations of pretreatment liquids and aqueous inkjet ink sets shown below in Table 10, the printed matters were produced. Using these printed matters, or, the pretreatment liquid itself, the following evaluations were performed. Further, the evaluation results are as illustrated in Table 10.

[0267] A gradation image printed matter prepared on a substrate coated with a pretreatment liquid under conveyor drive speed conditions of 25 m/minute, 50 m/minute, and 75 m/minute based on the methods described above was used. The mixed color bleeding and the color unevenness were evaluated by observing the dot shape of the image printed matter using an optical microscope at a magnification of 200×. The evaluation criteria are as follows, and an AA, A, or B evaluation is deemed to be a practically applicable level.

(Evaluation Criteria)

[0268] AA: mixed color bleeding and color unevenness was not observed at 75 m/minute

[0269] A: mixed color bleeding and color unevenness was observed at 75 m/minute, but mixed color bleeding and color unevenness was not observed at 50 m/minute

[0270] B: mixed color bleeding and color unevenness was observed at 50 m/minute, but mixed color bleeding and color unevenness was not observed at 25 m/minute

[0271] C: mixed color bleeding and color unevenness was observed at 25 m/minute

[0272] Solid patches images at a print ratio of 100% were printed on a substrate coated with a pretreatment liquid under conveyor drive speed conditions of 25 m/minute, 50 m/minute, and 75 m/minute based on the methods described above. The filling was evaluated by observation using an optical microscope at a magnification of 200×, and verifying the presence of voids and streaks. The evaluation criteria are as follows, and an AA, A, or B evaluation is deemed to be a practically applicable level. Note that, the filling was evaluated for each solid printed matter prepared at the different conveyor speeds.

(Evaluation Criteria)

[0273] AA: voids and streaks were not observed at all three printing speeds.

[0274] A: voids and streaks were not observed at 50 m/min and 75 m/min, but voids and streaks were observed at 100 m/min.

[0275] B: voids and streaks were not observed at 50 m/min, but voids and streaks were observed at 75 m/min and 100 m/min.

[0276] C: but voids and streaks were observed at all three printing speeds.

[0277] 4C solid patches image printed matter prepared on a substrate coated with a pretreatment liquid under conveyor drive speed conditions of 50 m/minute based on the methods described above were used. A cellophane tape manufactured by Nichiban Co., Ltd. (width: 18 mm) was adhered securely to the surface of the image printed matter, and the tip of the cellophane tape peeled away with the angle maintained at 90°. Moreover, the adhesion was evaluated by visually inspecting the surface of the printed matter and the cellophane tape following the peeling operation. The evaluation criteria are as follows, and an AA, A, or B evaluation is deemed to be a practically applicable level. Further, Table 10 shows the evaluation for the color that yielded the worst evaluation result among the 5 colors that were evaluated.

(Evaluation Criteria)

[0278] AA: the peeled surface area was less than 5% of the cellophane-adhered surface

[0279] A: the peeled surface area was at least 5% but less than 10% of the cellophane-adhered surface

[0280] B: the peeled surface area was at least 10% but less than 20% of the cellophane-adhered surface

[0281] C: the peeled surface area was at least 20% but less than 30% of the cellophane-adhered surface

[0282] D: the peeled surface area was no less than 30% of the cellophane-adhered surface

[0283] 4C solid patches image printed matter prepared on a substrate coated with a pretreatment liquid under conveyor drive speed conditions of 50 m/minute based on the methods described above were used Immediately after printing, the printed matter was placed in a 70° C. air oven, and after each minute, the printed matter was removed from the air oven, and the drying property was evaluated by rubbing the surface with a finger and visually examining the state of the printed matter. The evaluation criteria are as follows, and an AA, A, or B evaluation is deemed to be a practically applicable level.

(Evaluation Criteria)

[0284] AA: one minute after placing in the air oven, the printed matter had dried, and no ink adhered to the finger upon rubbing

[0285] A: ink adhered to the finger one minute after placing in the air oven, but no ink adhesion occurred after two minutes

[0286] B: ink adhered to the finger two minutes after placing in the air oven, but no ink adhesion occurred after three minutes

[0287] C: ink adhered to the finger from the printed matter even after three minutes in the air oven

[0288] 4C solid patches image printed matter prepared on a PET film substrate coated with a pretreatment liquid under conveyor drive speed conditions of 50 m/minute based on the methods described above were used Immediately after printing, the printed matter was placed in a 70° C. air oven, and after drying for three minutes, the printed matter was removed from the air oven. The removed printed matter was rubbed with a cotton swab soaked in water. The coating film durability was evaluated by verifying the number of rubs until the ink peeled and the undercoat became visible. The evaluation criteria are as follows, and an AA, A, or B evaluation is a practically applicable level.

(Evaluation Criteria)

[0289] AA: the number of rubs until the undercoat became visible was no less than 20 times

[0290] A: the number of rubs until the undercoat became visible was 15 to 19 times

[0291] B: the number of rubs until the undercoat became visible was 11 to 14 times

[0292] C: the number of rubs until the undercoat became visible was no more than 10 times

[0293] The pretreatment liquid 101 described in Table 1 is a system which used a coagulant and not a metal salt or a cationic polymer compound, the pretreatment liquid 102 is a system free of the coagulant (A), the pretreatment liquids 103 to 105 are systems free of the surfactant (B) in general formula (1), and the pretreatment liquid 106 is a system free of the resin (C). None of these pretreatment liquids reached a practical level in the plurality of items evaluated for the ink set.

[0294] On the other hand, it was verified that all of the pretreatment liquids 1 to 100 which simultaneously comprise the coagulant (A), the surfactant (B), and the resin (C) have a quality that is at least a practically applicable level for all of the items evaluated for the ink set. These results indicate that, if any one of the structural components is not present, the effect of the present invention cannot be exhibited, and as a result, the deterioration of the storage stability, the image quality, the adhesion, the drying property, and the coating film durability occurs.

PRETREATMENT LIQUID, INK SET AND PRINTED MATTER

Assignee

Inventors

Cpc classification

Classification Explorer

C09D11/10

CHEMISTRY; METALLURGY

Classification Explorer

C09D11/38

CHEMISTRY; METALLURGY

Classification Explorer

B41M5/502

PERFORMING OPERATIONS; TRANSPORTING

Classification Explorer

C09D11/322

CHEMISTRY; METALLURGY

Classification Explorer

C09D11/40

CHEMISTRY; METALLURGY

Classification Explorer

C09D11/54

CHEMISTRY; METALLURGY

International classification

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C09D11/54

CHEMISTRY; METALLURGY

Classification Explorer

B41M5/50

PERFORMING OPERATIONS; TRANSPORTING

Abstract

Claims

Description