Pretreatment liquid and ink set

Abstract

A pretreatment liquid that is used together with an aqueous inkjet ink containing a pigment and water, wherein the pretreatment liquid contains resin microparticles (A), a surfactant (B), a coagulant (C) and water, the surfactant (B) contains a polyoxyalkylene alkyl ether (b-1), and the coagulant (C) contains a polyvalent metal salt and/or a cationic polymer compound and has a water absorptivity at a temperature of 40° C. and a relative humidity of 80% of 75% by mass or less.

Claims

1. An ink set comprising: a pretreatment liquid comprising resin microparticles (A), a surfactant (B), a coagulant (C) and water; and an aqueous inkjet ink comprising a pigment, a water-soluble organic solvent and water, wherein the surfactant (B) comprises a polyoxyalkylene alkyl ether (b-1) represented by a general formula (1) shown below, the coagulant (C) comprises a polyvalent metal salt and/or a cationic polymer compound, and the coagulant (C) has a water absorptivity at a relative humidity of 80% of 75% by mass or less:
R—O-(EO).sub.m-(PO).sub.n—H  General formula (1) wherein R represents an alkyl group of 8 to 22 carbon atoms, an alkenyl group of 8 to 22 carbon atoms, an alkylcarbonyl group of 8 to 22 carbon atoms, or an alkenylcarbonyl group of 8 to 22 carbon atoms, EO represents an ethylene oxide group and PO represents a propylene oxide group, m represents an average number of added moles of EO and is a number from 8 to 100, n represents an average number of added moles of PO, and is a number from 0 to 99, provided that m>n, and when n is not 0, there are no restrictions on an addition sequence of (EO).sub.m and (PO).sub.n, and the addition may be in blocks or may be random.

2. The ink set according to claim 1, wherein a blend amount of the polyoxyalkylene alkyl ether (b-1) is from 5 to 50% by mass relative to a blend amount of the resin microparticles (A).

3. The ink set according to claim 1, wherein the coagulant (C) comprises a divalent metal salt.

4. The ink set according to claim 1, wherein the resin microparticles (A) comprise two or more types of resin microparticles selected from the group consisting of polyurethane resins, polyurethane polyurea resins, (meth)acrylic resins, acrylic-modified polyurethane resins, and polyolefin resins.

5. The ink set according to claim 1, wherein the pretreatment liquid is used on a thermoplastic resin substrate.

Description

EXAMPLES

(1) The pretreatment liquid, and the ink set (recording liquid set) containing the pretreatment liquid and an aqueous inkjet ink, which represent embodiments of the present invention, are described below in further detail using a series of examples and comparative examples. In the following description, unless specifically stated otherwise, “parts” and “%” represent “parts by mass” and “% by mass” respectively.

Examples 1 to 67, Comparative Examples 1 to 14

1. Production of Pretreatment Liquids

(1-1) Titanium Oxide Dispersion Production Example

(2) The materials listed below were placed in a mixing container fitted with a stirrer, and mixing and stirring (premixing) was performed for one hour. Subsequently, a Dyno-Mill with a capacity of 0.6 L filled with 1,800 g of zirconia beads of diameter 1 mm was used to perform the main dispersion, thus obtaining a titanium oxide dispersion (pigment concentration: 50%).

(3) TABLE-US-00001 TIPAQUE CR-50-2 50 parts BYK-190 (solid fraction: 40%) 15 parts 2-propanol 5 parts Ion-exchanged water 30 parts

(4) In the above production example, TIPAQUE CR-50-2 is a titanium oxide manufactured by Ishihara Sangyo Kaisha, Ltd., and BYK-190 is an aqueous solution of a styrene-maleic acid resin manufactured by BYK-Chemie GmbH.

(1-2) PVA103 Varnish Production Example

(5) The materials listed below were placed in a mixing container fitted with a stirrer, and following mixing and stirring for one hour, the mixture was heated to 90° C. and stirring was continued for an additional one hour. The temperature was then cooled to room temperature, and ion-exchanged water was used to adjust the solid fraction concentration to 25%, thus obtaining a PVA103 varnish.

(6) TABLE-US-00002 KURARAY POVAL PVA103 25 parts Ion-exchanged water 75 parts

(7) In the above production example, KURARAY POVAL PVA103 is a polyvinyl alcohol resin (water-soluble resin, melting point: 200° C.) manufactured by KURARAY Co., Ltd.

(1-3) Production Example for Pretreatment Liquid 1

(8) The materials listed below were placed in a mixing container fitted with a stirrer, and following mixing for one hour at room temperature (25° C.), the mixture was heated to 50° C. and stirring was continued for an additional one hour. The mixture was then cooled to room temperature, and filtered through a membrane filter with a pore size of 1 μm, thus obtaining a pretreatment liquid 1.

(9) TABLE-US-00003 Joncryl 7100 (solid fraction: 48%) 10.42 parts EMALEX 715 0.13 parts Aluminum nitrate 5.0 parts Ethanol 5.0 parts Ion-exchanged water 77.1 parts

(10) In the above production example, Joncryl 7100 is styrene-acrylic resin microparticles (melting point: 120° C., solid fraction: 48%) manufactured by BASF Corporation, and EMALEX 715 is a polyoxyalkylene alkyl ether (a compound of general formula (1) in which R represents a lauryl group, m=15 and n=0) manufactured by Nihon Emulsion Co., Ltd.

(1-4) Production Examples for Pretreatment Liquids 2 to 81

(11) With the exception of using the materials shown in Table 1, pretreatment liquids 2 to 81 were produced using the same method as the pretreatment liquid 1.

(12) TABLE-US-00004 TABLE 1 Example Number 1 2 3 4 5 6 7 8 9 10 Pretreatment Liquid Number 1 2 3 4 5 6 7 8 9 10 Binder Resin SUPERCHLON 16.67 resin micro- E-480T particles AUROREN 16.67 (A) AE-301 ARROWBASE 20.00 SB-1230N ARROWBASE 20.00 SB-1200 HITEC S9200 25.00 HITEC E8237 12.50 HITEC E6400 14.29 HITEC E6500 AQUACER 498 Hordamer PE03 Joncryl 7100 10.42 SUPERFLEX 13.16 470 PESRESIN 25.00 A-684G Surfactant Polyoxy- EMALEX 715 0.13 0.13 0.13 0.13 0.13 0.13 0.13 0.13 0.13 0.13 (B) alkylene alkyl ether (b-1) Coagulant Polyvalent Aluminum 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 (C) metal salt nitrate Cationic PAA-HCL-3L polymer PAA-U7030 compound PAS-M-1 PAS-H-1L Catiomaster PE-30 Catiomaster PD-7 Organic solvent EtOH 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Ion-exchanged water 79.45 76.71 64.87 73.20 73.20 69.87 69.87 64.87 77.37 75.58 Blend amount of polyoxyalkylene alkyl 2.6% 2.6% 2.6% 2.6% 2.6% 2.6% 2.6% 2.6% 2.6% 2.6% ether (b-1) relative to blend amount of resin microparticles (A) Example Number 11 12 13 14 15 16 17 18 19 Pretreatment Liquid Number 11 12 13 14 15 16 17 18 19 Binder Resin SUPERCHLON resin micro- E-480T particles AUROREN (A) AE-301 ARROWBASE SB-1230N ARROWBASE SB-1200 HITEC S9200 HITEC E8237 HITEC E6400 14.29 14.29 14.29 14.29 14.29 14.29 HITEC E6500 14.29 AQUACER 498 10.00 Hordamer PE03 12.50 Joncryl 7100 SUPERFLEX 470 PESRESIN A-684G Surfactant Polyoxy- EMALEX 715 0.13 0.13 0.13 0.13 0.13 0.13 0.13 0.13 0.13 (B) alkylene alkyl ether (b-1) Coagulant Polyvalent Aluminum 5.0 5.0 5.0 (C) metal salt nitrate Cationic PAA-HCL-3L 10.0 polymer PAA-U7030 33.3 compound PAS-M-1 10.0 PAS-H-1L 17.9 Catiomaster 10.0 PE-30 Catiomaster 10.0 PD-7 Organic solvent EtOH 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Ion-exchanged water 75.58 79.87 77.37 70.58 47.25 70.58 62.72 70.58 70.58 Blend amount of polyoxyalkylene alkyl 2.6% 2.6% 2.6% 2.6% 2.6% 2.6% 2.6% 2.6% 2.6% ether (b-1) relative to blend amount of resin microparticles (A) Example Number 20 21 22 23 24 25 26 27 28 Pretreatment Liquid Number 20 21 22 23 24 25 26 27 28 Binder Resin AUROREN 16.67 16.67 16.67 16.67 16.67 16.67 16.67 16.67 16.67 resin micro- AE-301 particles (A) Surfactant Polyoxy- Newcol 1008 0.13 (B) alkylene EMULGEN 0.13 alkyl 1108 ether EMULGEN 0.18 (b-1) 1118-70 EMULGEN 0.18 1135-70 EMULGEN 0.21 1150S-60 NONION K-209 0.13 EMALEX 730 0.13 EMALEX 750 0.13 NONION 0.13 K-2100W NONION P-210 NONION P-240 NONION S-215 EMALEX 630 EMALEX 640 EMALEX BHA-20 EMALEX BHA-30 NONION B-250 Coagulant Polyvalent Aluminum 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 (C) metal salt nitrate Organic solvent EtOH 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Ion-exchanged water 73.20 73.20 73.15 73.15 73.12 73.20 73.20 73.20 73.20 Blend amount of polyoxyalkylene alkyl 2.6% 2.6% 2.5% 2.5% 2.5% 2.6% 2.6% 2.6% 2.6% ether (b-1) relative to blend amount of resin microparticles (A) Example Number 29 30 31 32 33 34 35 36 Pretreatment Liquid Number 29 30 31 32 33 34 35 36 Binder Resin AUROREN 16.67 16.67 16.67 16.67 16.67 16.67 16.67 16.67 resin micro- AE-301 particles (A) Surfactant Polyoxy- Newcol 1008 (B) alkylene EMULGEN alkyl 1108 ether EMULGEN (b-1) 1118-70 EMULGEN 1135-70 EMULGEN 1150S-60 NONION K-209 EMALEX 730 EMALEX 750 NONION K-2100W NONION P-210 0.13 NONION P-240 0.13 NONION S-215 0.13 EMALEX 630 0.13 EMALEX 640 0.13 EMALEX 0.13 BHA-20 EMALEX 0.13 BHA-30 NONION B-250 0.13 Coagulant Polyvalent Aluminum 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 (C) metal salt nitrate Organic solvent EtOH 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Ion-exchanged water 73.20 73.20 73.20 73.20 73.20 73.20 73.20 73.20 Blend amount of polyoxyalkylene alkyl 2.6% 2.6% 2.6% 2.6% 2.6% 2.6% 2.6% 2.6% ether (b-1) relative to blend amount of resin microparticles (A) Example Number 37 38 39 40 41 42 43 44 45 46 Pretreatment Liquid Number 37 38 39 40 41 42 43 44 45 46 Binder Resin AUROREN 16.67 16.67 16.67 16.67 16.67 16.67 16.67 16.67 16.67 16.67 resin micro- AE-301 particles (A) Surfactant Polyoxy- EMULGEN (B) alkylene 1118-70 alkyl ether EMULGEN 0.08 0.42 (b-1) 1150S-60 NONION S-215 0.25 1.25 1.75 3.50 NONION E-215 0.13 EMALEX 820 0.13 UNISAFE 0.13 10P-8 UNISAFE 0.13 34S-23 Coagulant Polyvalent Calcium (C) metal lactate salt Calcium ascorbate Calcium acetate Magnesium acetate Aluminum sulfate Aluminum 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 nitrate Organic solvent EtOH 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Ion-exchanged water 73.21 73.21 73.21 73.21 73.08 72.08 71.58 69.83 73.25 72.91 Blend amount of polyoxyalkylene alkyl 2.5% 2.5% 2.5% 2.5% 5.0% 25.0% 35.0% 70.0% 1.0% 5.0% ether (b-1) relative to blend amount of resin microparticles (A) Example Number 47 48 49 50 51 52 53 54 55 Pretreatment Liquid Number 47 48 49 50 51 52 53 54 55 Binder Resin AUROREN 16.67 16.67 16.67 16.67 16.67 16.67 16.67 16.67 16.67 resin micro- AE-301 particles (A) Surfactant Polyoxy- EMULGEN 1.43 1.43 1.43 1.43 1.43 1.43 (B) alkylene 1118-70 alkyl ether EMULGEN 2.92 4.17 7.50 (b-1) 1150S-60 NONION S-215 NONION E-215 EMALEX 820 UNISAFE 10P-8 UNISAFE 34S-23 Coagulant Polyvalent Calcium 5.0 (C) metal lactate salt Calcium 5.0 ascorbate Calcium 5.0 acetate Magnesium 5.0 acetate Aluminum 5.0 sulfate Aluminum 5.0 5.0 5.0 5.0 nitrate Organic solvent EtOH 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Ion-exchanged water 70.41 69.16 65.83 71.90 71.90 71.90 71.90 71.90 71.90 Blend amount of polyoxyalkylene alkyl 35.0% 50.0% 90.0% 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% ether (b-1) relative to blend amount of resin microparticles (A) Example Number 56 57 58 59 60 61 62 Pretreatment Liquid Number 56 57 58 59 60 61 62 Binder Resin AUROREN 16.67 16.67 16.67 16.67 16.67 16.67 16.67 resin micro- AE-301 particles HITEC S9200 (A) HITEC E6500 2.86 SUPERFLEX 470 Surfactant Polyoxy- EMULGEN 1108 (B) alkylene EMULGEN 1.43 1.43 1.43 1.43 1.43 1.43 alkyl ether 1118-70 (b-1) EMULGEN 1.00 1150S-60 Polyoxy- NONION K-204 0.05 alkylene alkyl ether other than (b-1) Other Surfynol 465 1.00 surfactant KF-6015 1.00 Coagulant Polyvalent Calcium acetate 5.0 5.0 5.0 5.0 5.0 5.0 5.0 (C) metal salt Organic solvent 2PrOH 5.0 5.0 5.0 5.0 5.0 1,3-BGmME 5.0 1,2-BD 5.0 Other materials Titanium oxide dispersion Ion-exchanged water 71.90 71.90 71.90 71.85 70.90 70.90 69.47 Blend amount of polyoxyalkylene alkyl 20.0% 20.0% 20.0% 20.0% 20.0% 20.0% 10.0% ether (b-1) relative to blend amount of resin microparticles (A) Example Number 63 64 65 66 67 Pretreatment Liquid Number 63 64 65 66 67 Binder Resin AUROREN 16.67 resin micro- AE-301 particles HITEC S9200 25.00 25.00 25.00 (A) HITEC E6500 2.86 5.71 2.86 5.71 2.86 SUPERFLEX 13.16 470 Surfactant Polyoxy- EMULGEN 1108 0.30 (B) alkylene EMULGEN alkyl ether 1118-70 (b-1) EMULGEN 1.00 1.17 1.00 1.17 1.00 1150S-60 Polyoxy- NONION K-204 alkylene alkyl ether other than (b-1) Other Surfynol 465 surfactant KF-6015 Coagulant Polyvalent Calcium acetate 5.0 5.0 5.0 5.0 5.0 (C) metal salt Organic solvent 2PrOH 5.0 5.0 5.0 5.0 5.0 1,3-BGmME 1,2-BD Other materials Titanium oxide 20.0 20.0 dispersion Ion-exchanged water 69.17 58.12 61.14 49.96 41.14 Blend amount of polyoxyalkylene alkyl 15.0% 10.0% 10.0% 10.0% 10.0% ether (b-1) relative to blend amount of resin microparticles (A) Comparative Example Number 1 2 3 4 5 6 7 8 Pretreatment Liquid Number 68 69 70 71 72 73 74 75 Binder Resin AUROREN resin micro- AE-301 particles HITEC E6400 14.29 14.29 14.29 14.29 14.29 14.29 (A) Water- PVA103 20.00 soluble varnish resin Surfactant Polyoxy- EMULGEN (B) alkylene 1118-70 alkyl EMULGEN 0.21 0.21 ether 1150S-60 (b-1) EMALEX 715 Polyoxy- Butyl 0.13 alkylene triglycol H alkyl NONION K-204 0.13 ether UNILUBE 0.13 other than MS-70K (b-1) NONION A-25B 0.13 Other RHEODOL 0.13 surfactant TW-L120 Surfynol 465 0.13 KF-6015 Coagulant Polyvalent Calcium (C) metal salt chloride Aluminum 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 nitrate Cationic PAS-H-10L polymer compound Other Malonic acid coagulant Organic solvent EtOH 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 Ion-exchanged water 69.79 89.79 75.58 75.58 75.58 75.58 75.58 75.58 Blend amount of polyoxyalkylene alkyl — — 0.0% 0.0% 0.0% 0.0% 0.0% 0.0% ether (b-1) relative to blend amount of resin microparticles (A) Comparative Example Number 9 10 11 12 13 14 Pretreatment Liquid Number 76 77 78 79 80 81 Binder Resin AUROREN 16.67 16.67 16.67 resin micro- AE-301 particles HITEC E6400 14.29 14.29 14.29 (A) Water- PVA103 soluble varnish resin Surfactant Polyoxy- EMULGEN 1.43 1.43 1.43 (B) alkylene 1118-70 alkyl EMULGEN ether 1150S-60 (b-1) EMALEX 715 0.13 Polyoxy- Butyl alkylene triglycol H alkyl NONION K-204 ether UNILUBE other than MS-70K (b-1) NONION A-25B Other RHEODOL surfactant TW-L120 Surfynol 465 KF-6015 0.13 Coagulant Polyvalent Calcium 5.0 (C) metal salt chloride Aluminum 5.0 5.0 nitrate Cationic PAS-H-10L 17.9 polymer compound Other Malonic acid 5.0 coagulant Organic solvent EtOH 5.0 5.0 5.0 5.0 5.0 5.0 Ion-exchanged water 75.58 75.71 71.90 71.90 76.90 62.68 Blend amount of polyoxyalkylene alkyl 0.0% 0.0% 20.0% 20.0% 20.0% 2.6% ether (b-1) relative to blend amount of resin microparticles (A)

(13) Details of the materials shown in Table 1 are as shown below in Table 2 and Table 3. The melting point and glass transition temperature values in Table 2 were measured by differential scanning calorimetry using a DSC-60 Plus manufactured by Shimadzu Corporation. Further, the particle size distribution values represent values measured by the dynamic light scattering method using a Microtrac UPA-EX150 manufactured by MicrotracBEL Corporation.

(14) TABLE-US-00005 TABLE 2 Solid Name fraction Details Binder Resin SUPERCHLON 30% Polyolefin resin microparticles melting D50: 75 nm resin micro- E-480T (chlorinated) manufactured by point: particles Nippon Paper Industries Co., Ltd. 70° C. (A) AUROREN 30% Polyolefin resin microparticles melting D50: 75 nm AE-301 (unchlorinated) manufactured by point: Nippon Paper Industries Co., Ltd. 70° C. ARROWBASE 25% Polyolefin resin microparticles melting D50 85 nm SB-1230N (unchlorinated) manufactured by point Unitika, Ltd. 75° C. ARROWBASE 25% Polyolefin resin microparticles melting D50: 110 nm SB-1200 (unchlorinated) manufactured by point Unitika, Ltd. 80° C. HITEC S9200 20% Polyolefin resin microparticles melting D50: 40 nm (unchlorinated) manufactured by point Toho Chemical Industry Co., Ltd. 90° C. HITEC E8237 40% Polyolefin resin microparticles melting D50: 80 nm (unchlorinated) manufactured by point Toho Chemical Industry Co., Ltd. 106° C. HITEC E6400 35% Polyolefin resin microparticles melting D50: 40 nm (unchlorinated) manufactured by point Toho Chemical Industry Co., Ltd. 120° C. HITEC E6500 35% Polyolefin resin microparticles melting D50: 60 nm (unchlorinated) manufactured by point Toho Chemical Industry Co., Ltd. 140° C. AQUACER 498 50% Paraffin resin microparticles melting D50: 300 nm manufactured by BYK-Chemie point GmbH 60° C. Hordamer PE03 40% Polyethylene resin microparticles melting D50: 170 nm manufactured by BYK-Chemie point GmbH 95° C. Joncryl 7100 48% Styrene-acrylic resin microparticles Glass D50: 100 nm manufactured by BASF Corporation transition temper- ature: −10° C. SUPERFLEX 38% Polyurethane resin microparticles melting D50: 50 nm 470 manufactured by DKS Co., Ltd. point: 95° C. glass transition temper- ature: −30° C. PESRESIN 20% Polyester resin microparticles Glass D50: 60 nm A-684G manufactured by Takamatsu Oil & transition Fat Co., Ltd. temper- ature: 50° C. Coagulant Polyvalent Calcium — — Water absorptivity: A (C) metal salt lactate Calcium — — Water absorptivity: A ascorbate Calcium — — Water absorptivity: A acetate Magnesium — — Water absorptivity: B acetate Calcium — — Water absorptivity: C chloride Aluminum — — Water absorptivity: A sulfate Aluminum — — Water absorptivity: B nitrate Cationic PAA-HCL-3L 50% Polyallylamine hydrochloride Water Mw: 15,000 polymer manufactured by Nittobo absorptivity: B compound Medical Co., Ltd. PAA-U7030 15% Partially methoxycarbonylated Water Mw: 15,000 polyallylamine manufactured absorptivity: A by Nittobo Medical Co., Ltd. PAS-M-1 50% Polymethyldiallylamine Water Mw: 20,000 hydrochloride manufactured absorptivity: B by Nittobo Medical Co., Ltd. PAS-H-1L 28% Polydimethyldiallylammonium Water Mw: 8,500 hydrochloride manufactured by absorptivity: B Nittobo Medical Co., Ltd. PAS-H-10L 28% Polydimethyldiallylammonium Water Mw: hydrochloride manufactured by absorptivity: C 200,000 Nittobo Medical Co., Ltd. Catiomaster 50% Polyepichlorohydrin Water Mw: 9,000 PE-30 manufactured by Yokkaichi absorptivity: B Chemical Co., Ltd. Catiomaster 50% Polyepichlorohydrin Water Mw: 5,000 PD-7 manufactured by Yokkaichi absorptivity: B Chemical Co., Ltd. Other Malonic acid — — Water absorptivity: B surfactant Organic solvent EtOH — Ethanol Boiling point at 1 atmosphere: 78° C. 2PrOH — 2-propanol Boiling point at 1 atmosphere: 83° C. 1,3-BGmME — 1,3-butylene glycol Boiling point at 1 monomethyl ether atmosphere: 158° C. (3-methoxybutanol) 1,2-BD — 1,2-butanediol Boiling point at 1 atmosphere: 192° C.

(15) TABLE-US-00006 TABLE 3 Solid Name fraction Details Surfactant Polyoxy- Newcol 1008 100% Polyoxyalkylene alkyl ether manufactured by Nippon HLB = 14.6 (B) alkylene Nyukazai Co., Ltd., a compound of general formula (1) in alkyl which R = ethylhexyl group, m = 8, n = 0 ether EMULGEN 1108 100% Polyoxyalkylene alkyl ether manufactured by Kao HLB = 13.4 (b-1) Corporation, a compound of general formula (1) in which R = undecanyl group, m = 8, n = 0 EMULGEN  70% Polyoxyalkylene alkyl ether manufactured by Kao HLB = 16.4 1118-70 Corporation, a compound of general formula (1) in which R = undecanyl group, m = 18, n = 0 EMULGEN  70% Polyoxyalkylene alkyl ether manufactured by Kao HLB = 18.0 1135-70 Corporation, a compound of general formula (1) in which R = undecanyl group, m = 35, n = 0 EMULGEN  60% Polyoxyalkylene alkyl ether manufactured by Kao HLB = 18.5 1150S-60 Corporation, a compound of general formula (1) in which R = undecanyl group, m = 50, n = 0 NONION 100% Polyoxyalkylene alkyl ether manufactured by NOF HLB = 13.6 K-209 Corporation, a compound of general formula (1) in which R = lauryl group, m = 9, n = 0 EMALEX 715 100% Polyoxyalkylene alkyl ether manufactured by Nihon HLB = 15.6 Emulsion Co., Ltd., a compound of general formula (1) in which R = lauryl group, m = 15, n = 0 EMALEX 730 100% Polyoxyalkylene alkyl ether manufactured by Nihon HLB = 17.5 Emulsion Co., Ltd., a compound of general formula (1) in which R = lauryl group, m = 30, n = 0 EMALEX 750 100% Polyoxyalkylene alkyl ether manufactured by Nihon HLB = 18.4 Emulsion Co., Ltd., a compound of general formula (1) in which R = lauryl group, m = 50, n = 0 NONION 100% Polyoxyalkylene alkyl ether manufactured by NOF HLB = 19.2 K-2100W Corporation, a compound of general formula (1) in which R = lauryl group, m = 100, n = 0 NONION P-210 100% Polyoxyalkylene alkyl ether manufactured by NOF HLB = 12.9 Corporation, a compound of general formula (1) in which R = octadecyl group, m = 10, n = 0 NONION P-240 100% Polyoxyalkylene alkyl ether manufactured by NOF HLB = 17.6 Corporation, a compound of general formula (1) in which R = octadecyl group, m = 40, n = 0 NONION S-215 100% Polyoxyalkylene alkyl ether manufactured by NOF HLB = 14.2 Corporation, a compound of general formula (1) in which R = stearyl group, m = 15, n = 0 EMALEX 630 100% Polyoxyalkylene alkyl ether manufactured by Nihon HLB = 16.6 Emulsion Co., Ltd., a compound of general formula (1) in which R = stearyl group, m = 30, n = 0 EMALEX 640 100% Polyoxyalkylene alkyl ether manufactured by Nihon HLB = 17.3 Emulsion Co., Ltd., a compound of general formula (1) in which R = stearyl group, m = 40, n = 0 EMALEX 100% Polyoxyalkylene alkyl ether manufactured by Nihon HLB = 14.6 BHA-20 Emulsion Co., Ltd., a compound of general formula (1) in which R = behenyl group, m = 20, n = 0 EMALEX 100% Polyoxyalkylene alkyl ether manufactured by Nihon HLB = 16.0 BHA-30 Emulsion Co., Ltd., a compound of general formula (1) in which R = behenyl group, m = 30, n = 0 NONION B-250 100% Polyoxyalkylene alkyl ether manufactured by NOF HLB = 17.4 Corporation, a compound of general formula (1) in which R = behenyl group, m = 50, n = 0 NONION E-215 100% Polyoxyalkylene alkyl ether manufactured by NOF HLB = 14.2 Corporation, a compound of general formula (1) in which R = oleyl group, m = 15, n = 0 EMALEX 820 100% Polyoxyalkylene alkyl ether manufactured by Nihon HLB = 15.1 Emulsion Co., Ltd., a compound of general formula (1) in which R = heptadecylcarbonyl group, m = 20, n = 0 UNISAFE 10P-8 100% Polyoxyalkylene alkyl ether manufactured by NOF HLB = 7.7 Corporation, a compound of general formula (1) in which R = octadecyl group, m = 10, n = 8 UNISAFE 34S-23 100% Polyoxyalkylene alkyl ether manufactured by NOF HLB = 9.7 Corporation, a compound of general formula (1) in which R = stearyl group, m = 34, n = 23 Polyoxy- Butyl triglycol H 100% Polyoxyalkylene alkyl ether manufactured by Nippon HLB = 14.1 alkylene Nyukazai Co., Ltd., a compound of general formula (1) in alkyl which R = butyl group, m = 4, n = 0 ether NONION K-204 100% Polyoxyalkylene alkyl ether manufactured by NOF HLB = 9.7 other Corporation, a compound of general formula (1) in which than R = lauryl group, m = 4, n = 0 (b-1) UNILUBE 100% Polyoxyalkylene alkyl ether manufactured by NOF HLB = 0.0 MS-70K Corporation, a compound of general formula (1) in which R = stearyl group, m = 0, n = 15 NONION A-25B 100% Polyoxyalkylene alkyl ether manufactured by NOF HLB = 8.0 Corporation, a compound of general formula (1) in which R = lauryl group, m = 25, n = 25 Other RHEODOL 100% Polyoxyethylene sorbitan monolaurate manufactured by Kao HLB = 16.7 surfactant TW-L120 Corporation Surfynol 465 100% Polyethoxylate of 2,4,7,9-tetramethyl-5-decyn-4,7-diol HLB = 13.2 manufactured by Nissin Chemical Industry Co., Ltd. KF-6015 100% A siloxane-based surfactant (polyether-modified) HLB = 4.5 Manufactured by Shin-Etsu Chemical Co., Ltd.
<Measurement of Water Absorption Mass Increase for Coagulant (C)>

(16) In Table 2, the water absorption mass increase (water absorptivity) for each of the materials used as the coagulant (C) was evaluated against the following criteria. Here, the water absorption mass increase means the mass increase in the coagulant (C) upon storage for 24 hours in an environment at 40° C. and 80% RH, and is measured using the method described above.

(17) A: the water absorption mass increase was 40% by mass or less

(18) B: the water absorption mass increase was greater than 40% by mass but not more than 75% by mass

(19) C: the water absorption mass increase was greater than 75% by mass

2. Production of Aqueous Inkjet Inks

(2-1) Production Example for Pigment Dispersing Resin 1

(20) 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 35 parts of styrene, 40 parts of acrylic acid and 25 parts of behenyl 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, 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 by removing the butanol 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. The “aqueous solution” mentioned above describes a solution containing an aqueous medium, and components dispersed and/or dissolved in the aqueous medium. The acid value of the pigment dispersing resin 1, measured using the method described above, was 250 mgKOH/g, and the weight average molecular weight was 13,000.

(2-2) Production Examples for Aqueous Solutions of Pigment Dispersing Resins 2 to 6

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

(2-3) Production Examples for Methyl Ethyl Ketone Solutions of Pigment Dispersing Resins 7 and 8

(22) A reaction container fitted with a gas inlet tube, a thermometer, a condenser and a stirrer was charged with 95 parts of methyl ethyl ketone, and the container was flushed with nitrogen gas. The inside of the container was heated to 80° C., and a mixture containing 70 parts of styrene, 5 parts of acrylic acid, 10 parts of methyl methacrylate and 15 parts of polypropylene glycol methacrylate (BLEMMER PP-500 manufactured by NOF Corporation) as polymerizable monomers and 3.5 parts of a polymerization initiator V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise to the container over a period of three hours to achieve a polymerization reaction. Following completion of the dropwise addition, reaction was continued at 80° C. for a further one hour, an additional 0.7 parts of V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) was then added, and the reaction was continued at 80° C. for a further four hours, thus obtaining a solution of a pigment dispersing resin 7. Subsequently, 25 parts of methyl ethyl ketone was added, and following cooling of the reaction system to normal temperature, the mixed solution was removed from the reaction container, and the solid fraction was adjusted to 30% using methyl ethyl ketone, thus obtaining a methyl ethyl ketone solution (solid fraction: 30%) of the pigment dispersing resin 7. The acid value of the pigment dispersing resin 7, measured using the method described above, was 30 mgKOH/g, and the weight average molecular weight was 25,500.

(23) Further, with the exception of altering the types and amounts of the polymerizable monomers as shown below in Table 4, a methyl ethyl ketone solution (solid fraction: 30%) of a pigment dispersing resin 8 was obtained in the same manner as the pigment dispersing resin 7.

(24) TABLE-US-00007 TABLE 4 Pigment dispersing resin Water-insoluble Water-soluble pigment dispersing resins resins 1 2 3 4 5 6 7 8 Polymerizable Styrene 35 10 20 60 40 20 70 45 monomers Acrylic acid 40 30 30 30 40 80 5 5 Methyl 10 10 20 methacrylate Lauryl 50 50 10 methacrylate Behenyl 25 30 methacrylate PE-350 20 PP-500 15 Acid value 250 180 170 180 230 480 30 30 Weight average molecular 13,000 14,500 15,000 11,500 14,000 7,500 25,500 35,000 weight

(25) In Table 4, “PE-350” represents BLEMMER PE-350 (a polyethylene glycol methacrylate) manufactured by NOF Corporation, and “PP-500” represents BLEMMER PP-500 (a polypropylene glycol methacrylate) manufactured by NOF Corporation.

(2-4) Production Examples for Pigment Dispersions 1C, 1M, 1 Y and 1K

(26) 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 1C. Further, with the exception of replacing the C.I. Pigment Blue 15:3 with each of the pigments shown below, pigment dispersions 1M, 1Y and 1K were obtained in the same manner as the pigment dispersion 1C.

(27) Magenta: FASTOGEN SUPER MAGENTA RG (C.I. Pigment Red 122), manufactured by DIC Corporation

(28) Yellow: LIONOL YELLOW TT-1405G (C.I. Pigment Yellow 14), manufactured by Toyo Color Co., Ltd.

(29) Black: PrinteX 85 (carbon black), manufactured by Orion Engineered Carbons S.A.

(2-5) Production Examples for Pigment Dispersions 2 to 6 (C, M, Y, K)

(30) With the exception of using the aqueous solutions (solid fraction: 30%) of each of the pigment dispersing resins 2 to 6 as the pigment dispersing resin, pigment dispersions 2 to 6 (each including C, M, Y and K) were obtained using the same method as that described for the pigment dispersions 1C, 1M, 1Y and 1K.

(2-6) Production Examples for Pigment Dispersions 7C, 7M, 7Y and 7K)

(31) A mixing container fitted with a stirrer was charged with 33.3 parts of the methyl ethyl ketone solution (solid fraction: 30.3%) of the pigment dispersing resin 7, 50 parts of water and 0.45 parts of dimethylaminoethanol were added under stirring, and the mixture was then stirred for a further 30 minutes. Subsequently, 20 parts of LIONOL BLUE 7358G (C.I. Pigment Blue 15:3) manufactured by Toyo Color Co., Ltd. was added, and following thorough stirring (premixing), a Dyno-Mill with a capacity of 0.6 L filled with 1,800 g of zirconia beads of diameter 1 mm was used to perform the main dispersion. The thus obtained dispersion was then removed from the Dyno-Mill, 15 parts of water was added, and an evaporator was used to remove the methyl ethyl ketone by distillation under reduced pressure. Subsequently, water was used to adjust the pigment concentration to 20%, thus obtaining a pigment dispersion 7C. Further, with the exception of replacing the C.I. Pigment Blue 15:3 with each of the pigments used in the production of the pigment dispersions 1M, 1Y and 1K, pigment dispersions 7M, 7Y and 7K were obtained in the same manner as the pigment dispersion 7C.

(2-7) Production Examples for Pigment Dispersions 8C, 8M, 8Y and 8K)

(32) With the exception of using the methyl ethyl ketone solution (solid fraction: 30%) of the pigment dispersing resin 8 as the pigment dispersing resin, the same method as that described for the pigment dispersions 7C, 7M, 7Y and 7K was used to obtain pigment dispersions 8C, 8M, 8Y and 8K.

(2-8) Production Example for Pigment Dispersion 1W

(33) 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 1 mm was used to perform the main dispersion, thus obtaining a pigment dispersion 1W (pigment concentration: 40%).

(2-9) Production Example for Aqueous Inkjet Ink Set 1 (CMYK)

(34) 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, a 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 dispersions 1M, 1Y and 1K instead of the pigment dispersion 1C, an aqueous inkjet ink set 1 composed of the four colors of cyan (C), magenta (M), yellow (Y) and black (K) was obtained.

(35) TABLE-US-00008 Pigment dispersion 1C 25 parts Joncryl 8211 (solid fraction: 44%) 10 parts 1,2-butanediol 20 parts KF-6015 1 part PROXEL GXL 0.05 parts Ion-exchanged water 43.95 parts

(36) In the above production example, Joncryl 8211 is an acrylic resin emulsion (solid fraction: 44%) manufactured by BASF Corporation.

(2-10) Production Examples for Inkjet Ink Sets 2 to 27 (CMYK)

(37) With the exception of using the materials shown below in Table 5, the same method as that described for the inkjet ink set 1 was used to obtain inkjet ink sets 2 to 27, each composed of the four colors of cyan (C), magenta (M), yellow (Y) and black (K).

(38) TABLE-US-00009 TABLE 5 CMYK Inkjet Ink Set 1 2 3 4 5 6 7 8 Pigment Pigment 25 dispersion dispersion 1 (C, M, Y, K) Pigment 25 dispersion 2 (C, M, Y, K) Pigment 25 dispersion 3 (C, M, Y, K) Pigment 25 dispersion 4 (C, M, Y, K) Pigment 25 dispersion 5 (C, M, Y, K) Pigment 25 dispersion 6 (C, M, Y, K) Pigment 25 dispersion 7 (C, M, Y, K) Pigment 25 dispersion 8 (C, M, Y, K) Pigment Cabojet Self- dispersion Binder Joncryl 8211 10 10 10 10 10 10 10 10 resin Water- 1,2-BD 192 20 20 20 20 20 20 20 20 soluble TEGmEE 256 organic solvent Surfactant KF-6015 1 1 1 1 1 1 1 1 Preservative PROXEL GXL 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Ion-exchanged water 43.95 43.95 43.95 43.95 43.95 43.95 43.95 43.95 Parameters Water-soluble 192.0 192.0 192.0 192.0 192.0 192.0 192.0 192.0 organic solvent weighted boiling point average value at 1 atmosphere Amount of 0 0 0 0 0 0 0 0 solvent having boiling point at 1 atmosphere of 250° C. or higher Amount of 0 0 0 0 0 0 0 0 solvent having boiling point at 1 atmosphere of 220° C. or higher CMYK Inkjet Ink Set 9 10 11 12 13 Pigment Pigment 25 25 25 25 dispersion dispersion 1 (C, M, Y, K) Pigment dispersion 2 (C, M, Y, K) Pigment dispersion 3 (C, M, Y, K) Pigment dispersion 4 (C, M, Y, K) Pigment dispersion 5 (C, M, Y, K) Pigment dispersion 6 (C, M, Y, K) Pigment dispersion 7 (C, M, Y, K) Pigment dispersion 8 (C, M, Y, K) Pigment Cabojet C, M, Y: Self- 50 dispersion K: 25 Binder Joncryl 8211 10 10 10 10 10 resin Water- 1,2-BD 192 20 10 15 18 19 soluble TEGmEE 256 10 5 2 1 organic solvent Surfactant KF-6015 1 1 1 1 1 Preservative PROXEL GXL 0.05 0.05 0.05 0.05 0.05 Ion-exchanged water C, M, Y: 43.95 43.95 43.95 43.95 18.95 K: 43.95 Parameters Water-soluble 192.0 224.0 208.0 198.4 195.2 organic solvent weighted boiling point average value at 1 atmosphere Amount of 0 10 5 2 1 solvent having boiling point at 1 atmosphere of 250° C. or higher Amount of 0 10 5 2 1 solventhaving boiling point at 1 atmosphere of 220° C. or higher CMYK Inkjet Ink Set 14 15 16 17 18 19 20 21 Pigment Pigment 25 25 25 25 25 25 25 25 dispersion dispersion 1 (C, M, Y, K) Binder Joncryl 8211 10 10 10 10 10 10 10 10 resin Water- PGmME 120 soluble 1,3-BGmME 158 organic 1,2-PD 188 solvent 1,2-BD 192 15 18 15 18 3 6 30 40 1,3-PD 214 1,2-HD 224 5 2 3 1 TEGmEE 256 2 1 Surfactant Surfynol 465 KF-6015 1 1 1 1 1 1 1 1 Preservative PROXEL GXL 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Ion-exchanged water 43.95 43.95 43.95 43.95 60.95 57.95 33.95 23.95 Parameters Water-soluble 200.0 195.2 203.2 196.8 192.0 192.0 192.0 192.0 organic solvent weighted boiling point average value at 1 atmosphere Amount of 0 0 2 1 0 0 0 0 solvent having boiling point at 1 atmosphere of 250° C. or higher Amount of 5 2 5 2 0 0 0 0 solvent having boiling point at 1 atmosphere of 220° C. or higher CMYK Inkjet Ink Set 22 23 24 25 26 27 Pigment Pigment 25 25 25 25 25 25 dispersion dispersion 1 (C, M, Y, K) Binder Joncryl 8211 10 10 10 10 10 10 resin Water- PGmME 120 5 soluble 1,3-BGmME 158 15 10 5 organic 1,2-PD 188 20 5 solvent 1,2-BD 192 5 15 20 1,3-PD 214 20 1,2-HD 224 TEGmEE 256 Surfactant Surfynol 465 1.5 KF-6015 1 1 1 1 1 Preservative PROXEL GXL 0.05 0.05 0.05 0.05 0.05 0.05 Ion-exchanged water 43.95 43.95 43.95 43.95 43.95 43.45 Parameters Water-soluble 214.0 188.0 165.5 157.0 183.5 192.0 organic solvent weighted boiling point average value at 1 atmosphere Amount of 0 0 0 0 0 0 solvent having boiling point at 1 atmosphere of 250° C. or higher Amount of 0 0 0 0 0 0 solvent having boiling point at 1 atmosphere of 220° C. or higher

(39) In Table 5, the blend amount of the Cabojet listed below in the inkjet ink set 9 was 50% by mass for C, M and Y, and 25% by mass for K. The blend amount of ion-exchanged water was 18.95% by mass for C, M and Y, and 43.95% by mass for K. Further, of the materials shown in Table 4, abbreviations and details for those materials not included in Tables 1 to 3 are as follows.

(40) Cabojet

(41) Cyan: Cabojet 250C (a self-dispersing cyan pigment aqueous solution, manufactured by Cabot Corporation, pigment concentration: 10%)

(42) Magenta: Cabojet 265M (a self-dispersing magenta pigment aqueous solution, manufactured by Cabot Corporation, pigment concentration: 10%)

(43) Yellow: Cabojet 270 (a self-dispersing yellow pigment aqueous solution, manufactured by Cabot Corporation, pigment concentration: 10%)

(44) Black: Cabojet 200 (a self-dispersing carbon black aqueous solution, manufactured by Cabot Corporation, pigment concentration: 10%)

(45) PGmME: propylene glycol monomethyl ether (boiling point: 120° C.)

(46) 1,2-PD: 1,2-propanediol (boiling point: 188° C.)

(47) 1,3-PD: 1,3-propanediol (boiling point: 214° C.)

(48) 1,2-HD: 1,2-hexanediol (boiling point: 224° C.)

(49) TEGmEE: triethylene glycol monoethyl ether (boiling point: 256° C.)

(50) PROXEL GXL: 1,2-benzoisothiazol-3-one solution (preservative) manufactured by Arch Chemicals, Inc.

(51) In Table 5 and the following Table 6, for the water-soluble organic solvent contained in each ink, the weighted boiling point average at one atmosphere (° C.), and the amount (% by mass) of water-soluble organic solvents having a boiling point at one atmosphere of 250° C. (or 220° C.) and higher are also shown in the table.

(52) <(2-11) Production Examples for Aqueous Inkjet White Inks 1 to 11>

(53) With the exception of using the materials shown below in Table 6, aqueous inkjet white inks 1 to 11 were obtained using the same method as that described for the inkjet cyan ink 1.

(54) TABLE-US-00010 TABLE 6 Aqueous Inkjet White Ink 1 2 3 4 5 6 7 8 9 10 11 Pigment Pigment 25 25 25 25 25 25 25 25 25 25 25 dispersion dispersion 1W Binder Joncryl 8211 10 10 10 10 10 10 10 10 10 10 10 resin Water- PGmME 120 5 soluble 1,3-BGmME 158 15 10 organic 1,2-PD 188 20 5 solvent 1,2-BD 193 20 10 15 18 15 18 5 20 1,3-PD 214 20 1,2-HD 224 5 2 TEGmEE 256 10 5 2 Surfactant Surfynol 465 1 KF-6015 1 1 1 1 1 1 1 1 1 1 Preservative PROXEL GXL 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Ion-exchanged water 43.95 43.95 43.95 43.95 43.95 43.95 43.95 43.95 43.95 43.95 43.95 Parameters Water-soluble organic 193.0 224.5 208.8 199.3 200.8 196.1 214.0 188.0 165.5 157.3 193.0 solvent weighted boiling point average value at 1 atmosphere Amount of solvent 0 10 5 2 0 0 0 0 0 0 0 having boiling point at 1 atmosphere of 250° C. or higher Amount of solvent 0 10 5 2 5 2 0 0 0 0 0 having boiling point at 1 atmosphere of 220° C. or higher

Examples 68 to 160, Comparative Examples 15 to 28

3. Production Examples for Film Substrates Coated with Pretreatment Liquid

(55) Using a K Control Coater K202 manufactured by Matsuo Sangyo Co., Ltd. and a wire bar No. 0, each of the pretreatment liquids prepared above was applied to a film substrate described below with a wet film thickness of 4.0±0.2 μm, and the film substrate with the applied pretreatment liquid was then placed in a 70° C. air oven and dried for 3 minutes, thus producing a film substrate coated with the pretreatment liquid.

(56) <Film Substrates Used for Evaluations>

(57) OPP: a biaxially stretched polypropylene film “OPU-1” manufactured by Mitsui Chemicals Tohcello Inc. (thickness: 20 μm)

(58) PET: a polyethylene terephthalate film “Lumirror T60” manufactured by Toray Industries, Inc. (thickness: 25 μm)

Production Examples for Printed Items

(59) 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, Y from the upstream side. Subsequently, the film 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 10 pL, thereby printing the images described below. Immediately after printing, the printed item was placed in a 70° C. air oven and dried for 5 minutes to complete production of the printed item.

(60) Printing was conducted with the conveyor drive speed set to one of two conditions, namely 30 m/minute or 50 m/minute. Three print images were prepared, an image in which 5 cm×5 cm solid patches are arranged adjacent to one another at a print ratio of 100% in the order CMYK (hereafter called 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) is varied continuously from 40 to 320% (hereafter called the “gradation image”, wherein the print ratio is the same for each color at each total print ratio), and a solid image printed using CMYK at a total print ratio of 320% (hereafter called the “4C solid image”, wherein the print ratio of each color is 80%), and printed items of each image were produced.

(61) Using the combinations of pretreatment liquids and aqueous inkjet ink sets shown below in Table 8, the printed items described above were produced. Using these printed items, or the pretreatment liquid itself, the following evaluations 1 to 5 were performed. The results of the evaluations are as shown in Table 8.

(62) <Evaluation 1: Evaluation of Image Quality>

(63) The gradation image printed item, printed on the OPP film substrate under conveyor drive speed conditions of 30 m/minute or 50 m/minute in accordance with the method described above, was used. Evaluation of the image quality (bleeding, color mixing) was performed by inspecting the dot shape of the image printed item using an optical microscope at a magnification of 200×. The evaluation criteria are as shown below in Table 7, with 2 points or more being deemed a practically applicable level.

(64) TABLE-US-00011 TABLE 7 Evaluation Evaluation criteria points Printed item at 30 m/min Printed item at 50 m/min 6 Dots were independent at all total print ratios, Dots were independent at all total print ratios, and no bleeding or color mixing was observed and no bleeding or color mixing was observed 5 Dots were independent at all total print ratios, Dots were independent in portions having total and no bleeding or color mixing was observed print ratios of 280% or less, and no bleeding or color mixing was observed 4 Dots were independent in portions having total Dots were independent in portions having total print ratios of 280% or less, and no bleeding or print ratios of 240% or less, and no bleeding or color mixing was observed color mixing was observed 3 Dots were independent in portions having total Dots were independent in portions having total print ratios of 240% or less, and no bleeding or print ratios of 200% or less, and no bleeding or color mixing was observed color mixing was observed 2 Dots were independent in portions having total Bleeding or color mixing was observed in print ratios of 200% or less, and no bleeding or portions having total print ratios of 200% or less color mixing was observed 1 Bleeding or color mixing was observed in Bleeding or color mixing was observed in portions having total print ratios of 200% or less portions having total print ratios of 200% or less
<Evaluation 2: Evaluation of Adhesion>

(65) The solid patches image printed item produced under conveyor drive speed conditions of 30 m/minute in accordance with the method described above was used. A cellophane tape manufactured by Nichiban Co., Ltd. (width: 18 mm) was adhered securely to the surface of the image printed item, and the tip of the cellophane tape was then grasped and peeled away from the printed item with the angle maintained at 90°. The adhesion was evaluated by visually inspecting the surface of the printed item and the cellophane tape following the peeling operation.

(66) The evaluation criteria were as follows, with 2 points or more being deemed a practically applicable level. The adhesion was evaluated for both the printed item on the OPP film substrate and the printed item on the PET film substrate. The evaluation for the color that yielded the worst evaluation result among the 4 colors that were evaluated was recorded.

(67) 5: no peeling was observed from the cellophane-adhered surface

(68) 4: the peeled surface area was less than 10% of the cellophane-adhered surface

(69) 3: the peeled surface area was at least 10% but less than 20% of the cellophane-adhered surface

(70) 2: the peeled surface area was at least 20% but less than 30% of the cellophane-adhered surface

(71) 1: the peeled surface area was at least 30% of the cellophane-adhered surface

(72) <Evaluation 3: Evaluation of Drying Properties>

(73) Using the same procedure as that described for the above printed item production examples, a solid patches image was printed onto an OPP film coated with a pretreatment liquid under conveyor drive speed conditions of 30 m/minute. Immediately after printing, the printed item was placed in a 70° C. air oven, and after each one minute, the printed item was removed from the air oven, and the drying properties were evaluated by rubbing the surface with a finger and visually evaluating the state of the printed item.

(74) The evaluation criteria were as follows, with 2 points or more being deemed a practically applicable level.

(75) 4: one minute after placing in the air oven, the printed item had dried, and no ink adhered to the finger upon rubbing

(76) 3: ink adhered to the finger one minute after placing in the air oven, but no ink adhesion occurred after two minutes

(77) 2: ink adhered to the finger two minutes after placing in the air oven, but no ink adhesion occurred after three minutes

(78) 1: ink adhered to the finger from the printed item even after three minutes in the air oven

(79) <Evaluation 4: Evaluation of Blocking Resistance>

(80) The 4C solid image printed item on the OPP film substrate produced under conveyor drive speed conditions of 30 m/minute in accordance with the method described above was used. The image printed item was cut into a 4 cm×4 cm square and overlaid on the rear surface of an OPP film similar to that used in the printed item, and a blocking test was then performed using a permanent strain tester. The environmental conditions during the blocking test included a load of 10 kg/cm.sup.2, a temperature of 40° C., humidity of 80%, and a test period of 24 hours. After 24 hours had passed, the stacked OPP films were pulled apart instantaneously with the angle between the films maintained at 90°, and the blocking resistance was evaluated by visually inspecting the peeled printed surface.

(81) The evaluation criteria were as follows, with 2 points or more being deemed a practically applicable level.

(82) 5: no peeling of the printed surface was observed

(83) 4: the peeled surface area was less than 5% of the printed surface

(84) 3: the peeled surface area was less at least 5% but less than 10% of the printed surface

(85) 2: the peeled surface area was less at least 10% but less than 10% of the printed surface

(86) 1: the peeled surface area was at least 15% of the printed surface

(87) <Evaluation 5: Evaluation of Storage Stability of Pretreatment Liquid>

(88) For each of 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 70° C. After each one week, the sealed container was removed, the viscosity following storage was remeasured in the same manner as above, and the storage stability of the pretreatment liquid was evaluated by calculating the change in viscosity during storage.

(89) The evaluation criteria were as follows, with 2 points or more being deemed a practically applicable level.

(90) 5: the change in viscosity after four weeks storage was less than ±5%

(91) 4: 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%

(92) 3: 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%

(93) 2: 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%

(94) 1: the change in viscosity after one week storage was at least ±5%

(95) TABLE-US-00012 TABLE 8 Evaluation results Pretreat- Inkjet 1 2 3 4 5 ment ink Image Adhesion Drying Blocking Storage liquid set quality OPP film PET film properties resistance stability Example 68 1 1 3 2 2 3 3 2 Example 69 2 1 3 2 2 3 3 2 Example 70 3 1 3 3 3 3 3 3 Example 71 4 1 3 4 3 3 3 2 Example 72 5 1 3 4 3 3 3 3 Example 73 6 1 3 4 3 3 3 3 Example 74 7 1 3 4 3 3 3 3 Example 75 8 1 3 3 3 3 3 3 Example 76 9 1 3 3 2 3 3 3 Example 77 10 1 3 3 2 3 3 3 Example 78 11 1 3 3 2 3 3 3 Example 79 12 1 3 3 2 3 3 3 Example 80 13 1 3 3 2 3 3 3 Example 81 14 1 2 2 2 3 3 3 Example 82 15 1 2 2 2 3 4 3 Example 83 16 1 2 2 2 3 3 3 Example 84 17 1 2 2 2 3 3 3 Example 85 18 1 3 2 2 2 3 3 Example 86 19 1 3 2 2 2 3 3 Example 87 20 1 3 5 4 3 3 2 Example 88 21 1 3 5 4 3 3 2 Example 89 22 1 3 4 4 3 3 3 Example 90 23 1 3 3 3 3 3 4 Example 91 24 1 3 4 3 3 3 4 Example 92 25 1 3 5 5 3 3 2 Example 93 26 1 3 3 3 3 3 4 Example 94 27 1 3 3 2 3 3 4 Example 95 28 1 3 2 2 3 2 3 Example 96 29 1 3 5 4 3 3 2 Example 97 30 1 3 3 3 3 3 2 Example 98 31 1 3 4 3 3 3 3 Example 99 32 1 3 4 3 3 3 4 Example 100 33 1 3 3 3 3 3 4 Example 101 34 1 3 4 3 3 2 3 Example 102 35 1 3 3 3 3 2 3 Example 103 36 1 3 4 3 3 2 3 Example 104 37 1 3 4 3 3 3 3 Example 105 38 1 3 3 3 3 3 2 Example 106 39 1 3 3 3 3 3 2 Example 107 40 1 3 2 2 3 3 2 Example 108 41 1 3 5 4 3 3 4 Example 109 42 1 3 5 4 3 3 4 Example 110 43 1 3 4 4 3 3 4 Example 111 44 1 3 3 2 3 3 4 Example 112 45 1 3 5 4 3 3 2 Example 113 46 1 3 4 4 3 3 5 Example 114 47 1 3 4 3 3 3 5 Example 115 48 1 3 3 3 3 3 5 Example 116 49 1 3 2 2 3 3 3 Example 117 50 1 5 4 3 3 4 4 Example 118 51 1 5 4 3 3 4 4 Example 119 52 1 5 4 3 3 4 4 Example 120 53 1 5 4 3 3 3 4 Example 121 54 1 3 4 3 3 4 4 Example 122 55 1 3 4 3 3 3 4 Example 123 56 1 5 4 3 3 4 4 Example 124 57 1 5 4 3 3 4 4 Example 125 58 1 5 4 3 2 4 4 Example 126 59 1 6 3 3 3 4 3 Example 127 60 1 6 3 3 3 4 3 Example 128 61 1 6 2 2 3 4 3 Example 129 62 1 5 4 3 3 5 5 Example 130 63 1 6 4 3 3 5 5 Example 131 64 1 5 3 3 3 5 5 Example 132 65 1 5 3 3 3 5 5 Example 133 66 1 5 3 3 3 5 4 Example 134 67 1 5 2 2 3 5 4 Example 135 56 2 3 3 2 2 4 omitted Example 136 56 3 5 4 3 2 4 Example 137 56 4 5 4 3 2 3 Example 138 56 5 5 5 3 2 4 Example 139 56 6 5 4 3 2 3 Example 140 56 7 5 5 3 2 4 Example 141 56 8 5 4 3 3 4 Example 142 56 9 2 3 2 2 3 Example 143 56 10 2 4 3 2 4 Example 144 56 11 3 4 3 3 4 Example 145 56 12 4 4 3 3 4 Example 146 56 13 5 4 3 3 4 Example 147 56 14 4 4 3 3 4 Example 148 56 15 5 4 3 3 4 Example 149 56 16 4 4 3 3 4 Example 150 56 17 5 4 3 3 4 Example 151 56 18 3 4 2 4 4 Example 152 56 19 5 4 3 3 4 Example 153 56 20 5 4 3 3 4 Example 154 56 21 3 4 3 2 4 Example 155 56 22 3 4 3 2 4 Example 156 56 23 6 4 3 4 4 Example 157 56 24 6 4 3 4 4 Example 158 56 25 6 4 3 4 4 Example 159 56 26 6 4 3 4 4 Example 160 56 27 6 4 3 3 4 Comparative 68 1 3 1 2 3 1 3 Example 15 Comparative 69 1 4 1 1 2 1 4 Example 16 Comparative 70 1 1 2 1 3 2 1 Example 17 Comparative 71 1 2 2 2 3 3 1 Example 18 Comparative 72 1 2 2 1 3 3 1 Example 19 Comparative 73 1 2 2 2 3 3 1 Example 20 Comparative 74 1 1 2 1 3 2 1 Example 21 Comparative 75 1 2 2 2 3 3 1 Example 22 Comparative 76 1 2 2 2 3 3 1 Example 23 Comparative 77 1 1 2 1 3 2 1 Example 24 Comparative 78 1 4 1 1 1 1 3 Example 25 Comparative 79 1 2 1 1 1 1 3 Example 26 Comparative 80 1 1 5 5 3 5 4 Example 27 Comparative 81 1 2 1 1 1 1 3 Example 28

(96) In Table 8, the results for evaluation 5 (evaluation of the storage stability of the pretreatment liquid) for Examples 135 to 160 are omitted because the storage stability for the pretreatment liquid 56 had already been evaluated in Example 123.

Examples 161 to 174

(97) Combinations of a pretreatment liquid, an aqueous inkjet black ink (the black-colored ink from an aqueous inkjet ink set) and an aqueous inkjet white ink shown below in Table 9 were evaluated for clarity and legibility using a method described below. The evaluation results were as shown in Table 9.

(98) <Evaluation 6: Evaluation of Clarity and Legibility>

(99) An inkjet head KJ4B-QA was installed above a conveyor capable of transporting a substrate, and was filled with the aqueous inkjet black ink (K ink) and the aqueous inkjet white ink (W ink) shown in Table 9, with the color shown in Table 9 installed at the upstream side. In Examples 106 and 107, a W ink was not used, and only a K ink was used. Subsequently, a film substrate coated with the pretreatment liquid shown in Table 9 was secured to the conveyor, the conveyor was driven at a speed of 30 m/minute, and when the substrate passed beneath the installed position of the inkjet head, each of the aqueous inkjet inks was discharged. During printing, the K ink was used to print a text-based image composed of a mixture of hiragana and kanji printed in the MS Mincho font at 4-point and 6-point sizes, whereas the W ink was used to print a white solid image at a print ratio of 100%. Further, the image of the ink provided at the downstream side was printed so as to overlap the image of the ink provided at the upstream side. Immediately after printing, the printed item was placed in a 70° C. air oven and dried for 5 minutes to complete production of the text and white solid printed item.

(100) The thus obtained text and white solid printed item was inspected visually from the inspection surface recorded in Table 9, and the clarity and legibility was evaluated. The evaluation criteria were as follows, with 2 points or more being deemed a practically applicable level.

(101) 4: both the 4-point and 6-point text was clear and easily readable

(102) 3: the 4-point text exhibited slightly inferior clarity but was readable, whereas the 6-point text was clear and easily readable

(103) 2: the 4-point text exhibited poor clarity and was unreadable. The 6-point text exhibited slightly inferior clarity but was readable

(104) 1: both the 4-point and 6-point text exhibited poor clarity and was unreadable

(105) TABLE-US-00013 TABLE 9 Evaluation 6 Inkjet Inkjet Clarity and legibility Pretreatment black white Ink color at Inspection Evaluation liquid ink ink upstream side surface result Example 161 56 1 1 black rear 3 Example 162 56 10 2 black rear 2 Example 163 56 11 3 black rear 2 Example 164 56 12 4 black rear 3 Example 165 56 14 5 black rear 3 Example 166 56 15 6 black rear 3 Example 167 56 22 7 black rear 2 Example 168 56 23 8 black rear 4 Example 169 56 24 9 black rear 4 Example 170 56 25 10 black rear 4 Example 171 56 27 11 black rear 4 Example 172 56 1 1 white front 3 Example 173 66 1 — black front 3 (white ink not used) Example 174 67 1 — black front 3 (white ink not used)

(106) In Table 9, those printed items for which the inspection surface is listed as “rear” describe printed items that were inspected from the film substrate side, whereas those listed as “front” describe printed items that were inspected from the printed layer side.

(107) As shown in Table 8, in Examples 68 to 160, each of which used a pretreatment liquid containing resin microparticles (A), a polyoxyalkylene alkyl ether (b-1) represented by general formula (1), a coagulant (C) having a water absorptivity at a temperature of 40° C. and a relative humidity of 80% of 75% by mass or less, and water, the image quality, adhesion, drying properties and blocking resistance of the printed items, and the storage stability of the pretreatment liquid were all of practically applicable levels. Further, printed items produced using the pretreatment liquids of the compositions described above, an aqueous inkjet black ink and an aqueous inkjet white ink exhibited good clarity and legibility.

(108) Among Examples 68 to 134, which used the inkjet ink set 1, the pretreatment liquids 50 to 52, 56 and 57, and 62 to 66, which were used in Examples 117 to 119, 123 and 124, and 129 to 133 respectively, exhibited image quality of 5 points or higher, and had scores of 3 points or higher for all of the other evaluations, confirming extremely favorable quality levels.

(109) All of the above pretreatment liquids contained a polyolefin resin as the resin microparticles (A), contained a polyoxyalkylene alkyl ether (b-1) represented by general formula (1) in which R is an alkyl group of 10 to 18 carbon atoms, m is from 15 to 50, and m+n is from 15 to 55 as the surfactant (B), contained a calcium salt as the coagulant (C), and also contained a water-soluble organic solvent having at least one hydroxyl group with a boiling point at one atmosphere of 75 to 180° C. As a result, it can be stated that a pretreatment liquid of this this type of composition is extremely useful in achieving the objects of the present invention.

(110) On the other hand, Comparative Examples 15 and 16 were systems that did not contain the resin microparticles (A), and the results for the adhesion and blocking resistance of the printed items were poor. Further, Comparative Examples 17 to 24 were systems that did not contain the polyoxyalkylene alkyl ether (b-1) represented by general formula (1), and each of these pretreatment liquids exhibited poor storage stability. Comparative Examples 17, 21 and 24 also suffered from poor image quality and adhesion for the printed items, and these results suggest that the polyoxyalkylene alkyl ether (b-1) represented by general formula (1) not only improves the storage stability, but also contributes to preventing any deterioration in the image quality and adhesion of the printed items.

(111) Furthermore, Comparative Examples 25 and 28 were systems that contained a polyvalent metal salt or a cationic polymer compound having a water absorptivity greater than 75% by mass as a coagulant. Comparative Example 26 was a system that contained an organic acid as a coagulant. In each of these comparative examples, the results for the adhesion, drying properties and blocking resistance of the printed items were inferior. Moreover, the pretreatment liquid 80 used in Comparative Example 27 was a system that did not contain a coagulant, and the image quality was markedly inferior.

(112) The results described above indicate that a pretreatment liquid having the composition described in the present invention is able to provide a combination of favorable image quality, adhesion, drying properties and blocking resistance for printed items formed on impermeable substrates such as film substrates, as well as favorable storage stability for the pretreatment liquid.