Inkjet pigment ink

Abstract

Provided is an inkjet pigment ink which contains a pigment that is selected from the group consisting of C.L. Pigment Yellow 74 having a transmittance of 70% or more, C.I. Pigment Red 269 having a transmittance of 70% or more, C.I. Pigment Red 122 having a transmittance of less than 70% and C.I. Pigment Yellow 150; a water-soluble solvent that is selected from the group consisting of glycol ethers and diols; water; and a pigment dispersing resin that is a copolymer which contains a monomer A, a monomer B and a monomer C as unit components. The monomer A is an alkyl (meth)acrylate ester; the monomer B is styrene, α-methyl styrene or benzyl (meth)acrylate; and the monomer C is (meth)acrylic acid.

Claims

1. An inkjet pigment ink, comprising: C.I. Pigment Red 122; a water-soluble solvent selected from the group consisting of a glycol ether and a diol; water; and a pigment dispersing resin which is copolymer consisting essentially of a monomer A, a monomer B, and a monomer C as unit components, wherein the C.I. Pigment Red 122 is a pigment subject to a hydrophilic treatment and has a transmittance of less than 70%, and wherein: the transmittance is a transmittance of an aqueous layer measured by a turbidimeter when a 1.00% by weight pigment is added to water, is shaken, and is left for an hour, and then the aqueous layer is collected, and is measured in a 50 mm angular cell; the monomer A is an alkyl (meth)acrylate ester having a C18-C24 alkyl group; the monomer B is styrene, α-methyl styrene, or benzyl (meth)acrylate; and the monomer C is (meth)acrylic acid.

2. The inkjet pigment ink according to claim 1, wherein an acid value of the pigment dispersing resin is 50 mgKOH/g or more and 400 mgKOH/g or less.

3. The inkjet pigment ink according to claim 1, wherein the monomer A is selected from the group consisting of stearyl (meth)acrylate and behenyl (meth)acrylate.

4. The inkjet pigment ink according to claim 1, wherein the monomer B is styrene.

5. The inkjet pigment ink according to claim 1, wherein an adsorption rate of a dispersant with respect to the pigment is 10% or more when a dispersing element comprising the pigment, the dispersant and the solvent has a pigment/dispersed resin (non-volatile matter) ratio of 4/1.

6. The inkjet pigment ink according to claim 1, wherein the glycol ether is selected from the group consisting of a (poly)alkylene glycol monoalkyl ether and a (poly)alkylene glycol dialkyl ether.

7. The inkjet pigment ink according to claim 1, wherein the diol is selected from a C3-C6 alkanediol.

8. The inkjet pigment ink according to claim 1, which comprises an aqueous emulsion.

9. An ink set of yellow, magenta, cyan, and black inks, which comprises the inkjet pigment ink according to claim 1.

10. A printed material, which is printed with the inkjet pigment ink according to claim 1.

11. An inkjet pigment ink, which comprises: C.I. Pigment Red 269; a water-soluble solvent selected from the group consisting of a glycol ether and a diol; water; and a pigment dispersing resin being a copolymer consisting essentially of a monomer A, a monomer B, and a monomer C as unit components; wherein the C.I. Pigment Red 269 has a transmittance of less than 70%, and wherein the transmittance is a transmittance of an aqueous layer measured by a turbidimeter when a 1.00% by weight pigment is added to water, is shaken, and is left for an hour, and then the aqueous layer is collected, and is measured in a 50 mm angular cell, and the monomer A is an alkyl (meth)acrylate ester having a C18-C24 alkyl group, the monomer B is styrene, α-methyl styrene, or benzyl (meth)acrylate, and the monomer C is (meth)acrylic acid.

12. The inkjet pigment ink according to claim 11, wherein an acid value of the pigment dispersing resin is 50 mgKOH/g or more and 400 mgKOH/g or less.

13. The inkjet pigment ink according to claim 11, wherein the monomer A is selected from the group consisting of stearyl (meth)acrylate, and behenyl (meth)acrylate.

14. The inkjet pigment ink according to claim 11, wherein the monomer B is styrene.

15. The inkjet pigment ink according to claim 11, wherein an adsorption rate of a dispersant with respect to the pigment is 10% or more when a dispersing element comprising the pigment, the dispersant, and the solvent has a pigment/dispersed resin (non-volatile matter) ratio of 7/3.

16. The inkjet pigment ink according to claim 11, wherein the glycol ethers is selected from the group consisting of a (poly)alkylene glycol monoalkyl ether and a (poly)alkylene glycol dialkyl ether.

17. The inkjet pigment ink according to claim 11, wherein the diols is selected from a C3-C6 alkanediol.

18. The inkjet pigment ink according to claim 11, which comprises an aqueous emulsion.

19. An ink set of yellow, magenta, cyan, and black inks, which comprises the inkjet pigment ink according to claim 11.

20. A printed material, which is printed with the inkjet pigment ink according to claim 11.

Description

EXAMPLES

(1) Hereinafter, the invention is further specifically described by giving Examples and Comparative Examples for each embodiment. In description below, “part” and “%” are based on a weight unless otherwise mentioned.

Embodiment I

(Manufacturing Example 1) Synthesis of Dispersing Resin 1

(2) 93.4 parts of triethylene glycol monomethyl ether was put in a reaction container including a gas introduction pipe, a thermometer, a condenser, and a stirrer, and replacement by nitrogen gas was performed. An inside of the reaction container was heated to 110° C., a mixture of 35.0 parts of lauryl methacrylate, 35.0 parts of styrene, 30.0 parts of acrylic acid, and 6.0 parts of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was dripped for 2 hours, and a polymerization reaction was conducted. After the dripping was completed, the reaction was further conducted at 110° C. for 3 hours, and then 0.6 parts of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the reaction was further continued at 110° C. for an hour to obtain a solution of dispersing resin 1. A weight-average molecular weight of dispersing resin 1 was about 16,000.

(3) Further, cooling was performed up to room temperature, and then 37.1 parts of dimethylaminoethanol was added, and neutralization was conducted. The amount corresponds to an amount at which acrylic acid is 100% neutralized. Further, 200 parts of water was added to form an aqueous solution. 1 g of sample was taken, the sample was heated and dried at 180° C. for 20 minutes to measure a non-volatile matter, and water was added so that a non-volatile matter of the aqueous resin solution corresponds to 20%. In this way, an aqueous solution in which a non-volatile matter corresponds to 20% of dispersing resin 1 was obtained.

(Manufacturing Example 2) Synthesis of Dispersing Resin 2

(4) 93.4 parts of butanol was put in a reaction container including a gas introduction pipe, a thermometer, a condenser, and a stirrer, and replacement by nitrogen gas was performed. An inside of the reaction container was heated to 110° C., a mixture of 35.0 parts of lauryl methacrylate, 35.0 parts of styrene, 30.0 parts of acrylic acid, and 6.0 parts of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was dripped for 2 hours, and a polymerization reaction was conducted. After the dripping was completed, the reaction was further conducted at 110° C. for 3 hours, and then 0.6 parts of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the reaction was further continued at 110° C. for an hour to obtain a solution of dispersing resin 2. A weight-average molecular weight of dispersing resin 2 was about 16,000.

(5) Further, cooling was performed up to room temperature, and then 37.1 parts of dimethylaminoethanol was added, and neutralization was conducted. The amount corresponds to an amount at which acrylic acid is 100% neutralized. Further, 200 parts of water was added to form an aqueous solution, and then the aqueous solution was heated to 90° C. or more, and azeotropic removal of butanol was conducted from the mixture of butanol and water. In response to an internal temperature reaching 100° C., a 1 g sample was taken, the sample was heated and dried at 180° C. for 20 minutes to measure a non-volatile matter, and water was added so that a non-volatile matter of the aqueous resin solution corresponds to 20%. In this way, an aqueous solution excluding an organic solvent in which a non-volatile matter corresponds to 20% of dispersing resin 2 was obtained.

Manufacturing Examples 3 to 15

(6) Synthesis was performed similarly to Manufacturing Example 1 except that a material, an input amount, and a reaction temperature described in Table 1 were used, and solutions of dispersing resin 3 to 15 were obtained. Further, dimethylaminoethanol was added to achieve 100% neutralization, an aqueous solution was formed similarly to Manufacturing Example 1, and aqueous solutions of dispersing resin 3 to 15 were obtained.

Comparative Manufacturing Examples 1 and 2

(7) Synthesis was performed similarly to Manufacturing Example 1 except that a material, an input amount, and a reaction temperature described in Table 1 were used, and solutions of comparative dispersing resin 1 and 2 were obtained. Further, dimethylaminoethanol was added to achieve 100% neutralization, an aqueous solution was formed similarly to Manufacturing Example 1, and aqueous solutions of comparative dispersing resin 1 and 2 were obtained.

(8) (Manufacturing Example of Resin Fine Particle)

(9) 40 parts of ion-exchanged water and 0.2 parts of AKUARON KH-10 (manufactured by DAI-ICHI KOGYO SEIYAKU CO., LTD.) as a surfactant were put in a reaction container including an agitator, a thermometer, a dropping funnel, and a reflux apparatus, and 1% of a pre-emulsion in which 40 parts of 2-ethyl hexyl acrylate, 50 parts of methyl methacrylate, 7 parts of styrene, 2 parts of dimethylacrylamide, 1 part of methacrylic acid, 53 parts of ion-exchanged water, and 1.8 parts of AKUARON KH-10 (manufactured by DAI-ICHI KOGYO SEIYAKU CO., LTD.) as a surfactant were mixed in advance was further separately added. An internal temperature was increased to 60° C., replacement by nitrogen gas was sufficiently performed, and then 10% of 10 parts of 5% aqueous solution of potassium persulfate and 20 parts of 1% aqueous solution of anhydrous sodium bisulfite were added, and polymerization was started. An inside of a reaction system was maintained at 60° C. for 5 minutes, and then a remainder of a pre-emulsion, and a remainder of a 5% aqueous solution of potassium persulfate and a 1% aqueous solution of anhydrous sodium bisulfite were dripped for 1.5 hours while an internal temperature was maintained at 60° C., and agitation was further continued for 2 hours. After verifying that an inversion rate exceeds 98% through a measurement of solid content, a temperature was cooled down up to 30° C. Diethylaminoethanol was added to set a pH value to 8.5, and solid content was adjusted to 40% using ion-exchanged water to obtain a resin fine particle water dispersion. The solid content was searched for using a baking residue at 150° C. for 20 minutes. The obtained resin fine particle water dispersion was set to resin fine particle 1.

(Example 1) Manufacture of Dispersing Element and Manufacture of Ink

(10) 20 parts of FAST Yellow 7416 (manufactured by Sanyo Color Works, LTD.), which is Pigment Yellow 74 as a pigment, 42.9 parts of dispersing resin 1, and 37.1 parts of water were preliminarily dispersed by Dispar, and then a main dispersion was performed for 2 hours using DYNO-MILL having a volume of 0.6 L and filled with zirconia beads 1,800 g having a diameter of 0.5 mm, and a pigment dispersing element was obtained. In this instance, a ratio of a pigment to a non-volatile matter of a dispersing resin is pigment/dispersing resin (non-volatile matter)=7/3.

(11) (Affinity Test of Pigment with Respect to Water)

(12) 1.00% by weight of a pigment is added to water, is shaken 50 times, and is left for an hour. Thereafter, an aqueous layer is collected, and is put in a 50 mm angular cell of a turbidimeter (NDH2000, manufactured by NIPPON DENSHOKU INDUSTRIES CO., LTD). A transmittance of an aqueous layer was measured in a result of a measurement using a turbidimeter (NDH2000, manufactured by NIPPON DENSHOKU INDUSTRIES CO., LTD).

(13) (Measurement of Viscosity of Dispersing Element)

(14) A viscosity of a pigment dispersing element was measured using an E-type viscometer (“ELD-type viscometer” manufactured by TOKI SANGYO CO., LTD) at 25° C. on condition of an engine speed 20 rpm.

(15) (Temporal Preservation Stability of Dispersing Element)

(16) A pigment dispersing element was preserved for a week in a constant-temperature oven at 70° C., stimulated over time, and then a viscosity change of the pigment dispersing element was measured before and after the passage of time. A case in which a rate of change of a viscosity before and after the preservation for a week at 70° C. is less than ±10% was indicated by a symbol ∘, a case in which the rate of change is ±10% or more and less than ±20% was indicated by a symbol Δ, and a case in which the rate of change is ±20% or more was indicated by a symbol x.

(17) (Adsorption Rate of Resin (%))

(18) 15 parts of water was added to 5 parts of a prepared pigment dispersing element, and was sufficiently shaken, and then was turned at 30,000 rpm for 4 hours using an ultracentrifuge. Thereafter, a supernatant was collected, and solid content was measured to calculate a concentration of a resin in the supernatant. An adsorption rate was calculated based on the following equation.
Adsorption rate (%)=(Initial amount of input dispersant−Amount of dispersant of supernatant)×100/Initial amount of input dispersant

(19) When an adsorption rate of a resin (%) falls below 10%, affinity between a pigment and an adsorption site of a dispersant is insufficient, and temporal stability deteriorates.

(20) A case in which an absorbed amount of a resin of a pigment dispersing element is 10% or more was indicated by a symbol ∘, and a case in which the absorbed amount is less than 10% was indicated by a symbol x.

(21) (Manufacture of Ink)

(22) Further, 20 parts of a pigment dispersing element, 40 parts of triethylene glycol monomethyl ether, 27.5 parts of water, and 12.5 parts of resin fine particle 1 were mixed to manufacture an ink. In this instance, 100 parts of an ink contains 4 parts of a pigment, 1.7 parts of a dispersing resin, and 5 parts of a resin fine particle.

(23) (Measurement of Viscosity of Ink)

(24) A viscosity of an ink was measured using an E-type viscometer (“ELD-type viscometer” manufactured by TOKI SANGYO CO., LTD) at 25° C. on condition of an engine speed 20 rpm.

(25) (Temporal Preservation Stability of Ink)

(26) An ink was preserved for a week in a constant-temperature oven at 70° C., stimulated over time, and then a viscosity change of the ink was measured before and after the passage of time. A case in which a rate of change of a viscosity before and after the preservation for a week at 70° C. is less than ±10% was indicated by a symbol ∘, a case in which the rate of change is ±10% or more and less than ±20% was indicated by a symbol Δ, and a case in which the rate of change is ±20% or more was indicated by a symbol x.

(27) (Print Evaluation of Ink)

(28) A cartridge of an inkjet printer (“PM-750C” manufactured by Epson Corp.) was filled with an ink, and printing was performed on coated paper (OK topcoat+manufactured by Oji Paper Co., Ltd., paper weight in gsm 104.7 g/m.sup.2). A printed sample was observed through a magnifying glass, and connection between dots, color unevenness, and the like were evaluated. A significantly excellent printing quality was indicated by a symbol ⊚, an excellent printing quality was indicated by a symbol ∘, a generally satisfactory printing quality was indicated by a symbol Δ, and a poor printing quality was indicated by a symbol x.

(29) (Tolerance Test of Printed Material)

(30) The printed material was rubbed with a cotton swab to which ethanol was transfused, and a tolerance test was conducted. A case in which rubbing was performed 50 times or more until an ink peels off, and a ground is exposed was indicated by ∘, and a case in which the rubbing was performed less than 50 times was indicated by x.

Examples 2 to 16

(31) A dispersing element was manufactured similarly to Example 1 except that a dispersing resin and a solvent described in Table 2 were used, and an ink was manufactured and evaluated.

Comparative Examples 1 to 6

(32) A dispersing and a manufacture and evaluation of an ink were performed similarly to Example 1 except that a dispersing resin and a solvent described in Table 2 were used.

(Example 17) Manufacture of Dispersing Element and Manufacture of Ink

(33) 20 parts of Permanent Carmine 3810 (manufactured by Sanyo Color Works, LTD.), which is C.I. Pigment Red 269 as a pigment, 42.9 parts of dispersing resin 1, 37.1 parts of water were preliminarily dispersed by Dispar, and then a main dispersion was performed for 2 hours using DYNO-MILL having a volume of 0.6 L and filled with zirconia beads 1,800 g having a diameter of 0.5 mm, and a pigment dispersing element was obtained. In this instance, a ratio of a pigment to a non-volatile matter of a dispersing resin is pigment/dispersing resin (non-volatile matter)=7/3 (Affinity test of pigment with respect to water). 1.00% by weight of a pigment is added to water, is shaken 50 times, and is left for an hour. Thereafter, an aqueous layer is collected, and is put in a 50 mm angular cell of a turbidimeter (NDH2000, manufactured by NIPPON DENSHOKU INDUSTRIES CO., LTD). A transmittance of an aqueous layer was measured in a result of a measurement using a turbidimeter (NDH2000, manufactured by NIPPON DENSHOKU INDUSTRIES CO., LTD).

(34) (Measurement of Viscosity of Dispersing Element)

(35) A viscosity of a pigment dispersing element was measured using an E-type viscometer (“ELD-type viscometer” manufactured by TOKI SANGYO CO., LTD) at 25° C. on condition of an engine speed 20 rpm.

(36) (Temporal Preservation Stability of Dispersing Element)

(37) A pigment dispersing element was preserved for a week in a constant-temperature oven at 70° C., stimulated over time, and then a viscosity change of the pigment dispersing element was measured before and after the passage of time. A case in which a rate of change of a viscosity before and after the preservation for a week at 70° C. is less than ±10% was indicated by a symbol ∘, a case in which the rate of change is ±10% or more and less than ±20% was indicated by a symbol Δ, and a case in which the rate of change is ±20% or more was indicated by a symbol x.

(38) (Adsorption Rate of Resin (%))

(39) 15 parts of water was added to 5 parts of a prepared pigment dispersing element, and was sufficiently shaken, and then was turned at 30,000 rpm for 4 hours using an ultracentrifuge. Thereafter, a supernatant was collected, and solid content was measured to calculate a concentration of a resin in the supernatant.

(40) An adsorption rate was calculated based on the following equation.
Adsorption rate (%)=(Initial amount of input dispersant−Amount of dispersant of supernatant)×100/Initial amount of input dispersant

(41) When an adsorption rate of a resin (%) falls below 10%, affinity between a pigment and an adsorption site of a dispersant is insufficient, and temporal stability deteriorates.

(42) A case in which an absorbed amount of a resin of a pigment dispersing element is 10% or more was indicated by a symbol ∘, and a case in which the absorbed amount is less than 10% was indicated by a symbol x.

(43) (Manufacture of Ink)

(44) Further, 20 parts of a pigment dispersing element, 40 parts of triethylene glycol monomethyl ether, 27.5 parts of water, and 12.5 parts of resin fine particle 1 were mixed to manufacture an ink. In this instance, 100 parts of an ink contains 4 parts of a pigment, 1.7 parts of a dispersing resin, and 5 parts of a resin fine particle.

(45) (Measurement of Viscosity of Ink)

(46) A viscosity of an ink was measured using an E-type viscometer (“ELD-type viscometer” manufactured by TOKI SANGYO CO., LTD) at 25° C. on condition of an engine speed 20 rpm.

(47) (Temporal Preservation Stability of Ink)

(48) An ink was preserved for a week in a constant-temperature oven at 70° C., stimulated over time, and then a viscosity change of the ink was measured before and after the passage of time. A case in which a rate of change of a viscosity before and after the preservation for a week at 70° C. is less than ±10% was indicated by a symbol ∘, a case in which the rate of change is ±10% or more and less than ±20% was indicated by a symbol Δ, and a case in which the rate of change is ±20% or more was indicated by a symbol x.

(49) (Print Evaluation of Ink)

(50) A cartridge of an inkjet printer (“PM-750C” manufactured by Epson Corp.) was filled with an ink, and printing was performed on coated paper (OK topcoat+manufactured by Oji Paper Co., Ltd., paper weight in gsm 104.7 g/m.sup.2). A printed sample was observed through a magnifying glass, and connection between dots, color unevenness, and the like were evaluated. A significantly excellent printing quality was indicated by a symbol ⊚, an excellent printing quality was indicated by a symbol ∘, a generally satisfactory printing quality was indicated by a symbol Δ, and a poor printing quality was indicated by a symbol x.

(51) (Tolerance Test of Printed Material)

(52) The printed material was rubbed with a cotton swab to which ethanol was transfused, and a tolerance test was conducted. A case in which rubbing was performed 50 times or more until an ink peels off, and a ground is exposed was indicated by ∘, and a case in which the rubbing was performed less than 50 times was indicated by x.

Examples 17 to 20

(53) A dispersing element was manufactured similarly to Example 17 except that a dispersing resin and a solvent described in Table 3 were used, and an ink was manufactured and evaluated.

Comparative Examples 7 to 10

(54) A dispersing and a manufacture and evaluation of an ink were performed similarly to Example 17 except that a dispersing resin and a solvent described in Table 3 were used.

(55) TABLE-US-00001 TABLE 1 Reaction solvent Triethylene glycol Diethylene glycol Dripping mixture Manufacturing Dispersed monomethyl monohexyl 1,2- Behenyl Stearyl Stearyl Lauryl Pentadecyl Example resin ether ether butanediol Butanol acrylate methacrylate acrylate methacrylate methacrylate 1 1 93.4 35 2 2 93.4 35 3 3 93.4 35 4 4 93.4 35 5 5 93.4 35 6 6 93.4 35 7 7 93.4 47 8 8 93.4 23 9 9 89 35 10  10  98.35 35 11  11  93.4 35 12  12  93.4 50 13  13  93.4 50 14  14  93.4 35 15  15  93.4 40 Ref. 1 Ref. 1 93.4 70 Ref. 2 Ref. 2 93.4 3 hours from Dripping mixture completion Reaction Manufacturing α-methyl Benzyl Benzyl Methacrylic Acrylic of dripping temperature Example Styrene styrene methacrylate acrylate acid acid V-601 V-65 V-601 V-65 ° C. 1 35 30 6 0.6 110° 2 35 30 6 0.6 110 3 35 30 6 0.6 110 4 35 30 6 0.6 110 5 35 30 6 0.6 110 6 35 30 6 0.6 110 7 47 6 6 0.6 110 8 23 54 6 0.6 110 9 35 30 10 1 130 10  35 30 1.5 0.15 110 11  35 30 6 0.6 110 12  20 30 6 0.6 110 13  20 30 6 0.6 110 14  35 30 6 0.6 110 15  20 40 6 0.6 110 Ref. 1 30 6 0.6 110 Ref. 2 70 30 6 0.6 110 Neutralization Final material Manufacturing Neutralization Non-volatile Theoretical Example percentage % Dimethylaminoethanol matter % Acid value Mw 1 100 37.1 20 234 16000 2 100 37.1 20 234 16000 3 100 37.1 20 234 16000 4 100 37.1 20 234 16000 5 100 37.1 20 234 16000 6 100 37.1 20 196 16000 7 100 7.4 20 47 16000 8 100 66.8 20 421 16000 9 100 37.1 20 234 1500 10  100 37.1 20 234 35000 11  100 37.1 20 234 16000 12  100 37.1 20 234 16000 13  100 37.1 20 234 16000 14  100 37.1 20 234 16000 15  100 49.5 20 312 16000 Ref. 1 100 37.1 20 234 16000 Ref. 2 100 37.1 20 234 16000 V-601: Radical polymerization initiator (manufactured by WAKO PURE CHEMICAL INDUSTRIES, LTD.) V-65: Radical polymerization initiator (manufactured by WAKO PURE CHEMICAL INDUSTRIES, LTD.) MTG: Triethylene glycol monomethyl ether

(56) TABLE-US-00002 TABLE 2 Pigment: Pigment Yellow 74 Dispersed resin Pigment Manufacture of ink (part) Dispersed Transmittance Dispersing Example. resin Composition Mw Types (%) element Water MTG BDG HDG PDO BDO 1 1 LMA/St/AA = 35/35/30 16000 FAST 93.95 20 27.5 40 Yellow 7416 2 1 ↑ 16000 FAST 93.95 20 35.5 2 30 Yellow 7416 3 2 ↑ 16000 FAST 93.95 20 33.5 30 Yellow 7416 4 3 LMA/α- 16000 FAST 93.95 20 32.5 5 30 MeSt/AA = 35/35/30 Yellow 7416 5 4 LMA/BzMA/AA = 16000 FAST 93.95 20 27.5 30 35/35/30 Yellow 7416 6 5 LMA/BzA/AA = 16000 FAST 93.95 20 27.5 40 35/35/30 Yellow 7416 7 6 LMA/St/MAA = 16000 FAST 93.95 20 27.5 40 35/35/30 Yellow 7416 8 7 LMA/St/AA = 47/47/6 16000 FAST 93.95 20 27.5 40 Yellow 7416 9 8 LMA/St/AA = 30/30/50 16000 FAST 93.95 20 27.5 40 Yellow 7416 10 9 LMA/St/AA = 35/35/30 1500 FAST 93.95 20 27.5 40 Yellow 7416 11 10 ↑ 35000 FAST 93.95 20 27.5 40 Yellow 7416 12 11 PDMA/St/AA = 16000 FAST 93.95 20 27.5 40 35/35/30 Yellow 7416 13 1 LMA/St/AA = 35/35/30 16000 FAST 93.95 20 30 5 45 Yellow 7416 14 12 STMA/St/AA = 16000 FAST 93.95 20 33.5 30 50/20/30 Yellow 7416 15 13 SA/St/AA = 50/20/30 16000 FAST 93.95 20 32.5 5 30 Yellow 7416 16 14 VA/St/AA = 35/35/30 16000 FAST 93.95 20 27.5 30 Yellow 7416 Ref. 1 1 LMA/St/AA = 35/35/30 16000 FAST 93.95 20 27.5 Yellow 7416 Ref. 2 Ref. 1 LMA/AA = 70/30 16000 FAST 93.95 20 27.5 40 Yellow 7416 Ref. 3 Ref. 2 St/AA = 70/30 16000 FAST 93.95 20 27.5 40 Yellow 7416 Ref. 4 1 LMA/St/AA = 35/35/30 16000 HANSA 47.51 20 27.5 40 Brilliant Yellow 5GX01 Ref. 5 1 ↑ 16000 HANSA 47.51 20 35.5 2 30 Brilliant Yellow 5GX01 Ref. 6 1 ↑ 16000 Paliotol 44.63 20 35.5 2 30 Gelb Dispersing element Ink Manufacture of ink (part) Temporal Temporal Fixing preservation Adsorption preservation Printing Tolerance Example. HDO 2PY Gly resin 1 Viscosity stability rate (%) Viscosity stability quality test 1 12.5 16 ◯ ◯ 17 7.3 ◯ ◯ ◯ 2 12.5 ↑ ↑ ◯ 16 7.1 ◯ ⊙ ◯ 3 4 12.5 24.7 ◯ ◯ 17 7.1 ◯ ◯ ◯ 4 12.5 22.1 ◯ ◯ 16 7.2 ◯ ◯ ◯ 5 10 12.5 31.2 ◯ ◯ 15 7.4 ◯ ◯ ◯ 6 12.5 28.9 ◯ ◯ 15 7 ◯ ◯ ◯ 7 12.5 29.1 ◯ ◯ 19 7.5 ◯ ◯ ◯ 8 12.5 80.9 Δ ◯ 65 6.8 Δ ◯ ◯ 9 12.5 18.1 ◯ ◯ 13 7.1 Δ ◯ ◯ 10 12.5 12.1 Δ ◯ 17 6.5 Δ Δ ◯ 11 12.5 56.6 Δ ◯ 23 8.4 Δ ◯ ◯ 12 12.5 26 ◯ ◯ 20 7.1 ◯ ◯ ◯ 13 26 ◯ ◯ 19 7.1 ◯ ◯ Δ 14 4 12.5 ↑ ↑ ◯ 24 7.6 ◯ ◯ ◯ 15 12.5 ↑ ↑ ◯ 23 7.6 ◯ ◯ ◯ 16 10 12.5 ↑ ↑ ◯ 33 7.9 ◯ ◯ ◯ Ref. 1 40 12.5 ↑ ↑ ◯ 20 7.9 ◯ X ◯ Ref. 2 12.5 31.8 X ◯ 16 9.2 X ◯ ◯ Ref. 3 12.5 15.4 ◯ ◯ 22 7 X ◯ ◯ Ref. 4 12.5 18.3 X X  7 7.2 X ◯ ◯ Ref. 5 12.5 18.4 X X  6 7.1 X ◯ ◯ Ref. 6 12.5 23.8 X X  6 8.3 X X ◯ MTG: Triethylene glycol monomethyl ether BDG: Diethylene glycol monobutyl ether HDG: Diethylene glycol monohexyl ether PDO: 1,2-propanediol BDO: 1,2-butanediol HDO: 2-methyl-2,4-pentanediol 2PY: 2-pyrrolidone Gly: Glycerin ↑: Same as above Need to measure: Adsorption rate increases as hydrophobicity in adsorption portion of pigment and dispersant increases. When surface coverage decreased to less than 10%, temporal stability deteriorates.

(57) TABLE-US-00003 TABLE 3 Pigment: Pigment Red 269 Dispersed resin Manufacture of ink Dispersed Pigment Dispersing Example resin Mw Types Transmittance element Water MTG BDG HDG PDO BDO Ex. 17 1 LMA/St/AA = 16000 Permanent 81.63 20 27.5 40 35/35/30 Carmine 3810 Part Part Part Ex. 18 12 STMA/St/AA = 16000 Permanent 81.63 20 35.5 2 Part 30 50/20/30 Carmine 3810 Part Part Part Ex. 19 ↑ ↑ 16000 Permanent 81.63 20 33.5 30 Carmine 3810 Part Part Part Ex. 20 15 VA/St/AA = 40/20/40 16000 Permanent 81.63 20 32.5 5 Part 30 Carmine 3810 Part Part Part Ref. Ex. 7 1 LMA/St/AA = 16000 Permanent 81.63 20 27.5 35/35/30 Carmine 3810 Part Part Ref. Ex. 8 Ref. 1 LMA/AA = 70/30 16000 Permanent 81.63 20 27.5 40 Carmine 3810 Part Part Part Ref. Ex. 9 Ref. 2 St/AA = 70/30 16000 Permanent 81.63 20 27.5 40 Carmine 3810 Part Part Part Ref. 1 LMA/St/AA = 16000 Fastogen Super 42.56 20 27.5 40 Ex. 10 35/35/30 Red Part Part Part 7066B(PV19) Dispersing element Ink Manufacture of ink Temporal Temporal Fising preservation Adsorption preservation Printing Tolerance Example HDO 2PY Gly resin 1 Viscosity stability rate (%) Viscosity stability quality test Ex. 17 12.5 17 ◯ ◯ 22 7.2 ◯ ◯ ◯ Part Ex. 18 12.5 16 ⊙ ◯ 20 7.3 ⊙ ◯ ◯ Part Ex. 19 4 Part 12.5 ↑ ↑ ◯ 23 7.8 ◯ ⊙ ◯ Part Ex. 20 12.5 15.8 ↑ ◯ 26 7 ⊙ ◯ ◯ Part Ref. Ex. 7 40 12.5 17 ↑ ◯ 20 7.8 ◯ X ◯ Part Part Ref. Ex. 8 12.5 25.1 X ◯ 16 9.4 X ◯ ◯ Part Ref. Ex. 9 12.5 24.5 ◯ ◯ 32 7.2 X ◯ ◯ Part Ref. 12.5 18.3 X X 6 7.2 X ◯ ◯ Ex. 10 Part MTG: Triethylene glycol monomethyl ether BDG: Diethylene glycol monobutyl ether HDG: Diethylene glycol monohexyl ether PDO: 1,2-propanediol BDO: 1,2-butanediol HDO: 2-methyl-2,4-pentanediol 2PY: 2-pyrrolidone Gly: Glycerin ↑: Same as above PK Water/1.3-PD/MTG/BDG = 55/3/37/5 TKT Water/1.3-PD/MTG/BDG = 46/49/2/2 BDG Water/1.3-PD/MTG/BDG = 55/3/21/21

Embodiment II

(Manufacturing Example 1) Synthesis of Dispersing Resin 1

(58) 93.4 parts of triethylene glycol monomethyl ether was put in a reaction container including a gas introduction pipe, a thermometer, a condenser, and a stirrer, and replacement by nitrogen gas was performed. An inside of the reaction container was heated to 110° C., a mixture of 35.0 parts of behenyl methacrylate, 35.0 parts of styrene, 30.0 parts of acrylic acid, and 6.0 parts of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was dripped for 2 hours, and a polymerization reaction was conducted. After the dripping was completed, the reaction was further conducted at 110° C. for 3 hours, and then 0.6 parts of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the reaction was further continued at 110° C. for an hour to obtain a solution of dispersing resin 1. A weight-average molecular weight of dispersing resin 1 was about 16,000. Further, cooling was performed up to room temperature, and then 37.1 parts of dimethylaminoethanol was added, and neutralization was conducted. The amount corresponds to an amount at which acrylic acid is 100% neutralized. Further, 200 parts of water was added to form an aqueous solution. 1 g of sample was taken, the sample was heated and dried at 180° C. for 20 minutes to measure a non-volatile matter, and water was added so that a non-volatile matter of the aqueous resin solution corresponds to 20%. In this way, an aqueous solution in which a non-volatile matter corresponds to 20% of dispersing resin 1 was obtained.

(Manufacturing Example 2) Synthesis of Dispersing Resin 2

(59) 93.4 parts of butanol was put in a reaction container including a gas introduction pipe, a thermometer, a condenser, and a stirrer, and replacement by nitrogen gas was performed. An inside of the reaction container was heated to 110° C., a mixture of 35.0 parts of behenyl methacrylate, 35.0 parts of styrene, 30.0 parts of acrylic acid, and 6.0 parts of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was dripped for 2 hours, and a polymerization reaction was conducted. After the dripping was completed, the reaction was further conducted at 110° C. for 3 hours, and then 0.6 parts of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the reaction was further continued at 110° C. for an hour to obtain a solution of dispersing resin 2. A weight-average molecular weight of dispersing resin 2 was about 16,000.

(60) Further, cooling was performed up to room temperature, and then 37.1 parts of dimethylaminoethanol was added, and neutralization was conducted. The amount corresponds to an amount at which acrylic acid is 100% neutralized. Further, 200 parts of water was added to form an aqueous solution, and then the aqueous solution was heated to 90° C. or more, and azeotropic removal of butanol was conducted from the mixture of butanol and water. In response to an internal temperature reaching 100° C., 1 g of sample was taken, the sample was heated and dried at 180° C. for 20 minutes to measure a non-volatile matter, and water was added so that a non-volatile matter of the aqueous resin solution corresponds to 20%. In this way, an aqueous solution excluding an organic solvent in which a non-volatile matter corresponds to 20% of dispersing resin 2 was obtained.

Manufacturing Examples 3 to 15

(61) Synthesis was performed similarly to Manufacturing Example 1 except that a material, an input amount, and a reaction temperature described in Table 1 were used, and solutions of dispersing resin 3 to 15 were obtained. Further, dimethylaminoethanol was added to achieve 100% neutralization, an aqueous solution was formed similarly to Manufacturing Example 1, and aqueous solutions of dispersing resin 3 to 15 were obtained.

Comparative Manufacturing Examples 1 and 2

(62) Synthesis was performed similarly to Manufacturing Example 1 except that a material, an input amount, and a reaction temperature described in Table 1 were used, and solutions of comparative dispersing resin 1 and 2 were obtained. Further, dimethylaminoethanol was added to achieve 100% neutralization, an aqueous solution was formed similarly to Manufacturing Example 1, and aqueous solutions of comparative dispersing resin 1 and 2 were obtained.

(63) (Manufacturing Example of Resin Fine Particle)

(64) 40 parts of ion-exchanged water and 0.2 parts of AKUARON KH-10 (manufactured by DAI-ICHI KOGYO SEIYAKU CO., LTD.) as a surfactant were put in a reaction container including an agitator, a thermometer, a dropping funnel, and a reflux apparatus, and 1% of a pre-emulsion in which 40 parts of 2-ethyl hexyl acrylate, 50 parts of methyl methacrylate, 7 parts of styrene, 2 parts of dimethylacrylamide, 1 part of methacrylic acid, 53 parts of ion-exchanged water, and 1.8 parts of AKUARON KH-10 (manufactured by DAI-ICHI KOGYO SEIYAKU CO., LTD.) as a surfactant were mixed in advance was further separately added. An internal temperature was increased to 60° C., replacement by nitrogen gas was sufficiently performed, and then 10% of 10 parts of a 5% aqueous solution of potassium persulfate and 20 parts of 1% aqueous solution of anhydrous sodium bisulfite were added, and polymerization was started. An inside of a reaction system was maintained at 60° C. for 5 minutes, and then a remainder of a pre-emulsion, and a remainder of a 5% aqueous solution of potassium persulfate and a 1% aqueous solution of anhydrous sodium bisulfite were dripped for 1.5 hours while an internal temperature was maintained at 60° C., and agitation was further continued for 2 hours. After verifying that an inversion rate exceeds 98% through a measurement of solid content, a temperature was cooled down up to 30° C. Diethylaminoethanol was added to set a pH value to 8.5, and solid content was adjusted to 40% using ion-exchanged water to obtain a resin fine particle water dispersion. The solid content was searched for using a baking residue at 150° C. for 20 minutes. The obtained resin fine particle water dispersion was set to resin fine particle 1.

(Example 1) Manufacture of Dispersing Element and Manufacture of Ink

(65) 34.3 parts of Symuler Super Magenta RGT (manufactured by DIC), which is Pigment Red 122 as a pigment, 42.9 parts of dispersing resin 1, and 37.1 parts of water were preliminarily dispersed by Dispar, and then a main dispersion was performed for 2 hours using DYNO-MILL having a volume of 0.6 L and filled with 1,800 g of zirconia beads having a diameter of 0.5 mm, and a pigment dispersing element was obtained. In this instance, a ratio of a pigment to a non-volatile matter of a dispersing resin is pigment/dispersing resin (non-volatile matter)=4/1.

(66) (Affinity Test of Pigment with Respect to Water)

(67) 1.00% by weight of pigment is added to water, is shaken 50 times, and is left for an hour. Thereafter, an aqueous layer is collected, and is put in a 50 mm angular cell of a turbidimeter (NDH2000, manufactured by NIPPON DENSHOKU INDUSTRIES CO., LTD). A transmittance of an aqueous layer was measured in a result of a measurement using a turbidimeter (NDH2000, manufactured by NIPPON DENSHOKU INDUSTRIES CO., LTD).

(68) (Measurement of Viscosity of Dispersing Element)

(69) A viscosity of a pigment dispersing element was measured using an E-type viscometer (“ELD-type viscometer” manufactured by TOKI SANGYO CO., LTD) at 25° C. on condition of an engine speed 20 rpm.

(70) (Temporal Preservation Stability of Dispersing Element)

(71) A pigment dispersing element was preserved for a week in a constant-temperature oven at 70° C., stimulated over time, and then a viscosity change of the pigment dispersing element was measured before and after the passage of time. A case in which a rate of change of a viscosity before and after the preservation for a week at 70° C. is less than ±10% was indicated by a symbol ∘, a case in which the rate of change is ±10% or more and less than ±20% was indicated by a symbol Δ, and a case in which the rate of change is ±20% or more was indicated by a symbol x.

(72) (Manufacture of Ink)

(73) Further, 20 parts of a pigment dispersing element, 40 parts of triethylene glycol monomethyl ether, 27.5 parts of water, and 12.5 parts of resin fine particle 1 were mixed to manufacture an ink. In this instance, 100 parts of an ink contains 4 parts of a pigment, 1.7 parts of a dispersing resin, and 5 parts of a resin fine particle.

(74) (Measurement of Viscosity of Ink)

(75) A viscosity of an ink was measured using an E-type viscometer (“ELD-type viscometer” manufactured by TOKI SANGYO CO., LTD) at 25° C. on condition of an engine speed 20 rpm.

(76) (Temporal Preservation Stability of Ink)

(77) An ink was preserved for a week in a constant-temperature oven at 70° C., stimulated over time, and then a viscosity change of the ink was measured before and after the passage of time. A case in which a rate of change of a viscosity before and after the preservation for a week at 70° C. is less than ±10% was indicated by a symbol ∘, a case in which the rate of change is ±10% or more and less than ±20% was indicated by a symbol Δ, and a case in which the rate of change is ±20% or more was indicated by a symbol x.

(78) (Adsorption Rate of Resin)

(79) 20 parts of a prepared ink was turned at 30,000 rpm for 4 hours using an ultracentrifuge. Thereafter, a supernatant was collected, and solid content was measured to calculate a concentration of a resin in the supernatant. An adsorption rate was calculated based on the following equation.
Adsorption rate (%)=(Initial amount of input dispersant−Amount of resin of supernatant)×100/Initial amount of input dispersant

(80) (Print Evaluation of Ink)

(81) A cartridge of an inkjet printer (“PM-750C” manufactured by Epson Corp.) was filled with an ink, and printing was performed on coated paper (OK topcoat+manufactured by Oji Paper Co., Ltd., paper weight in gsm 104.7 g/m.sup.2). A printed sample was observed through a magnifying glass, and connection between dots, color unevenness, and the like were evaluated. A significantly excellent printing quality was indicated by a symbol ⊚, an excellent printing quality was indicated by a symbol ∘, a generally satisfactory printing quality was indicated by a symbol Δ, and a poor printing quality was indicated by a symbol x.

(82) (Tolerance Test of Printed Material)

(83) The printed material was rubbed with a cotton swab to which ethanol was transfused, and a tolerance test was conducted. A case in which rubbing was performed 50 times or more until an ink peels off, and a ground is exposed was indicated by ∘, and a case in which the rubbing was performed less than 50 times was indicated by x.

(84) (Weather Resistance Test of Printed Material)

(85) A weather resistance test was conducted using super xenon weather meter SX 75 (manufactured by Suga Test Instruments Co., Ltd.) for 600 hours on a sample printed using PVC as a printing base material on condition of an irradiance 160 W, bp 53° C., 50% RH, irradiation+rainfall cycle mode (1 cycle 120 minutes, within 18 minutes rainfall), and a concentration change before and after the test was evaluated.

(86) ∘: OD value decreasing rate is less than 10%

(87) x: OD value decreasing rate is 10% or more

Examples 2 to 17

(88) A dispersing element was manufactured similarly to Example 1 except that a dispersing resin and a solvent described in Table 2 were used, and an ink was manufactured and evaluated.

Comparative Examples 1 to 5

(89) A dispersing and a manufacture and evaluation of an ink were performed similarly to Example 1 except that a dispersing resin and a solvent described in Table 2 were used.

(90) TABLE-US-00004 TABLE 1 Reaction solvent Dripping mixture Manufacturing Dispersed Triethylene glycol Diethylene glycol 1,2- Behenyl Behenyl Stearyl Stearyl Lauryl Example resin monomethyl ether monohexyl ether butanediol Butanol acrylate methacrylate acrylate methacrylate methacrylate Ex. 1 1 93.4 35 Ex. 2 2 93.4 35 Ex. 3 3 93.4 35 Ex. 4 4 93.4 35 Ex. 5 5 93.4 35 Ex. 6 6 93.4 35 Ex. 7 7 93.4 47 Ex. 8 8 93.4 23 Ex. 9 9 89 35 Ex. 10 10 98.35 35 Ex. 11 11 93.4 35 Ex. 12 12 93.4 50 Ex. 13 13 93.4 50 Ex. 14 14 93.4 35 Ex. 15 15 93.4 40 Ref. Ex. 1 Ref. 1 93.4 70 Ref. Ref. 2 93.4 Ex. 2 3 hours form Dripping mixture completion Manufacturing α-methyl Benzyl of dripping Reaction Example Styrene styrene methacrylate Benzyl acrylate Methacrylic acid Acrylic acid V-601 V-65 V-601 V-65 temperature Ex. 1 35 30 6 0.6 110° C. Ex. 2 35 30 6 0.6 110° C. Ex. 3 35 30 6 0.6 110° C. Ex. 4 35 30 6 0.6 110° C. Ex. 5 35 30 6 0.6 110° C. Ex. 6 35 30 6 0.6 110° C. Ex. 7 47 6 6 0.6 110° C. Ex. 8 23 54 6 0.6 110° C. Ex. 9 35 30 10 1 130° C. Ex. 10 35 30 1.5 0.15 110° C. Ex. 11 35 30 6 0.6 110° C. Ex. 12 20 30 6 0.6 110° C. Ex. 13 20 30 6 0.6 110° C. Ex. 14 35 30 6 0.6 110° C. Ex. 15 20 40 6 0.6 110° C. Ref. Ex. 1 30 6 0.6 110° C. Ref. 70 30 6 0.6 110° C. Ex. 2 Final Neutralization material Theoretical Manufacturing Neutralization Non-volatile acid Example perceptage Dimethylaminoethanol matter value Mw Ex. 1 100% 37.1 20% 234 16000 Ex. 2 100% 37.1 20% 234 16000 Ex. 3 100% 37.1 20% 234 16000 Ex. 4 100% 37.1 20% 234 16000 Ex. 5 100% 37.1 20% 234 16000 Ex. 6 100% 31.1 20% 196 16000 Ex. 7 100% 7.4 20% 47 16000 Ex. 8 100% 66.8 20% 421 16000 Ex. 9 100% 37.1 20% 234 1500 Ex. 10 100% 37.1 20% 234 35000 Ex. 11 100% 37.1 20% 234 16000 Ex. 12 100% 37.1 20% 234 16000 Ex. 13 100% 37.1 20% 234 16000 Ex. 14 100% 37.1 20% 234 16000 Ex. 15 100% 49.5 20% 312 16000 Ref. Ex. 1 100% 37.1 20% 234 16000 Ref. 100% 37.1 20% 234 16000 Ex. 2 V-601: Radical polymerization initiator (manufactured by WAKO PURE CHEMICAL INDUSTRIES, LTD.) V-65: Radical polymerization initiator (manufactured by WAKO PURE CHEMICAL INDUSTRIES, LTD.) MTG: Triethylene glycol monomethyl ether HDG: Diethylene glycol monohexyl ether BDO: 1,2-butanediol

(91) TABLE-US-00005 TABLE 2 Pigment: Pigment Red 122 Dispersed resin Manufacture of ink Dispersed Pigment Dispersing Example resin Composition Mw Types Transmittance element Water MTG BDG HDG PDO BDO Ex. 1 1 VA/St/AA = 35/35/30 16000 Symuler Super 55.75 20 27.5 40 Magenta RGT Part Part Part Ex. 2 1 ↑ 16000 ↑ 55.75 20 35.5 2 30 Part Part Part Part Ex. 3 2 ↑ 16000 ID120 4.75 20 33.5 30 Part Part Part Ex. 4 3 VMA/α- 16000 Symuler Super 55.75 20 32.5 5 30 MeSt/AA = 35/35/30 Magenta RGT Part Part Part Part Ex. 5 4 VA/BzMA/AA = 16000 ↑ 55.75 20 27.5 30 35/35/30 Part Part Part Ex. 6 5 VA/BzA/AA = 35/35/30 16000 ↑ 55.75 20 27.5 40 Part Part Part Ex. 7 6 VA/St/MAA = 35/35/30 16000 ↑ 55.75 20 27.5 40 Part Part Part Ex. 8 7 VA/St/AA = 47/47/6 16000 ↑ 55.75 20 27.5 40 Part Part Part Ex. 9 8 VA/St/AA = 23/23/54 16000 ↑ 55.75 20 27.5 40 Part Part Part Ex. 10 9 VA/St/AA = 35/35/30 1500 ↑ 55.75 20 27.5 40 Part Part Part Ex. 11 10 ↑ 35000 ↑ 55.75 20 27.5 40 Part Part Part Ex. 12 11 STMA/St/AA = 35/35/30 16000 ↑ 55.75 20 27.5 40 Part Part Part Ex. 13 1 VA/St/AA = 35/35/30 16000 ↑ 55.75 20 30 5 45 Part Part Part Part Ex. 14 12 VA/St/AA = 50/20/30 16000 ↑ 55.75 20 33.5 30 Part Part Part Ex. 15 13 LMA/St/AA = 50/20/30 16000 ↑ 55.75 20 32.5 5 30 Part Part Part Part Ex. 16 14 SA/St/AA = 50/20/30 16000 ↑ 55.75 20 27.5 30 Part Part Part Ex. 17 15 VA/St/AA = 40/20/40 16000 ↑ 55.75 20 33.5 30 Part Part Part Ref. 1 VA/St/AA = 35/35/30 16000 ↑ 55.75 20 27.5 Ex. 1 Part Part Ref. Ref. 1 LMA/AA = 70/30 16000 ↑ 55.75 20 27.5 40 Ex. 2 Part Part Part Ref. Ref. 2 St/AA = 70/30 16000 ↑ 55.75 20 27.5 40 Ex. 3 Part Part Part Ref. 1 VA/St/AA = 35/35/30 16000 Quindo Violet 85.25 20 27.5 40 Ex. 4 BH-201(PB19) Part Part Part Ref. 1 ↑ 16000 ↑ 85.25 20 35.5 2 30 Ex. 5 Part Part Part Part Dispersing element Ink Manufacture of ink Temporal Temporal Weather Fixing preservation Adsorption preservation Printing Tolerance resistance Example HDO 2PY Gly resin 1 Viscosity stability rate (%) Viscosity stability quality test test Ex. 1 12.5 16 ◯ 35 7.3 ◯ ◯ ◯ ◯ Part Ex. 2 12.5 ↑ ◯ 36 7.1 ◯ ⊙ ◯ ◯ Part Ex. 3 4 12.5 24.7 ◯ 35 7.1 ◯ ◯ ◯ ◯ Part Part Ex. 4 12.5 22.1 ◯ 33 7.2 ◯ ◯ ◯ ◯ Part Ex. 5 10 12.5 31.2 ◯ 34 7.4 ◯ ◯ ◯ ◯ Part Part Ex. 6 12.5 28.9 ◯ 36 7 ◯ ◯ ◯ ◯ Part Ex. 7 12.5 29.1 ◯ 40 7.5 ◯ ◯ ◯ ◯ Part Ex. 8 12.5 80.9 Δ 75 6.8 Δ ◯ ◯ ◯ Part Ex. 9 12.5 18.1 ◯ 15 7.1 Δ ◯ ◯ ◯ Part Ex. 10 12.5 12.1 Δ 22 6.5 Δ Δ ◯ ◯ Part Ex. 11 12.5 56.6 Δ 24 8.4 Δ ◯ ◯ ◯ Part Ex. 12 12.5 26 ◯ 40 7.1 ◯ ◯ ◯ ◯ Part Ex. 13 26 ◯ 35 7.1 ◯ ◯ Δ ◯ Ex. 14 4 12.5 ↑ ◯ 38 7.6 ◯ ◯ ◯ ◯ Part Part Ex. 15 12.5 ↑ ◯ 25 7.6 ◯ ◯ ◯ ◯ Part Ex. 16 10 12.5 ↑ ◯ 43 7.9 ◯ ◯ ◯ ◯ Part Part Ex. 17 4 12.5 ↑ ◯ 33 8 ◯ ◯ ◯ ◯ Part Part Ref. 40 12.5 ↑ ◯ 35 7.9 ◯ X ◯ ◯ Ex. 1 Part Part Ref. 12.5 31.8 X 23 9.2 X ◯ ◯ ◯ Ex. 2 Part Ref. 12.5 15.4 ◯ 20 7 X ◯ ◯ ◯ Ex. 3 Part Ref. 12.5 18.3 X 6 7.2 X ◯ ◯ X Ex. 4 Part Ref. 12.5 18.4 X 7 7.1 X ◯ ◯ X Ex. 5 Part MTG: Triethylene glycol monomethyl ether BDG: Diethylene glycol monobutyl ether HDG: Diethylene glycol monohexyl ether PDO: 1,2-propanediol BDO: 1,2-butanediol HDO: 2-methyl-2,4-pentanediol 2PY: 2-pyrrolidone Gly: Glycerin ↑: Same as above

Embodiment III

(Manufacturing Example 1) Synthesis of Dispersing Resin 1

(92) 93.4 parts of triethylene glycol monomethyl ether was put in a reaction container including a gas introduction pipe, a thermometer, a condenser, and a stirrer, and replacement by nitrogen gas was performed. An inside of the reaction container was heated to 110° C., a mixture of 35.0 parts of behenyl methacrylate, 35.0 parts of styrene, 30.0 parts of acrylic acid, and 6.0 parts of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was dripped for 2 hours, and a polymerization reaction was conducted. After the dripping was completed, the reaction was further conducted at 110° C. for 3 hours, and then 0.6 parts of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the reaction was further continued at 110° C. for an hour to obtain a solution of dispersing resin 1. A weight-average molecular weight of dispersing resin 1 was about 16,000. Further, cooling was performed up to room temperature, and then 37.1 parts of dimethylaminoethanol was added, and neutralization was conducted. The amount corresponds to an amount at which acrylic acid is 100% neutralized. Further, 200 parts of water was added to form an aqueous solution. 1 g of sample was taken, the sample was heated and dried at 180° C. for 20 minutes to measure a non-volatile matter, and water was added so that a non-volatile matter of the aqueous resin solution corresponds to 20%. In this way, an aqueous solution in which a non-volatile matter corresponds to 20% of dispersing resin 1 was obtained.

(Manufacturing Example 2) Synthesis of Dispersing Resin 2

(93) 93.4 parts of butanol was put in a reaction container including a gas introduction pipe, a thermometer, a condenser, and a stirrer, and replacement by nitrogen gas was performed. An inside of the reaction container was heated to 110° C., a mixture of 35.0 parts of behenyl methacrylate, 35.0 parts of styrene, 30.0 parts of acrylic acid, and 6.0 parts of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was dripped for 2 hours, and a polymerization reaction was conducted. After the dripping was completed, the reaction was further conducted at 110° C. for 3 hours, and then 0.6 parts of V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the reaction was further continued at 110° C. for an hour to obtain a solution of dispersing resin 2. A weight-average molecular weight of dispersing resin 2 was about 16,000.

(94) Further, cooling was performed up to room temperature, and then 37.1 parts of dimethylaminoethanol was added, and neutralization was conducted. The amount corresponds to an amount at which acrylic acid is 100% neutralized. Further, 200 parts of water was added to form an aqueous solution, and then the aqueous solution was heated to 90° C. or more, and azeotropic removal of butanol was conducted from the mixture of butanol and water. In response to an internal temperature reaching 100° C., 1 g of sample was taken, the sample was heated and dried at 180° C. for 20 minutes to measure a non-volatile matter, and water was added so that a non-volatile matter of the aqueous resin solution corresponds to 20%. In this way, an aqueous solution excluding an organic solvent in which a non-volatile matter corresponds to 20% of dispersing resin 2 was obtained.

Manufacturing Examples 3 to 15, and Comparative Manufacturing Examples 1 to 7

(95) Synthesis was performed similarly to Manufacturing Example 1 except that a material, an input amount, and a reaction temperature described in Table 1 were used, and solutions of dispersing resin 3 to 15, and comparative dispersing resins 1 to 7 were obtained. Further, dimethylaminoethanol was added to achieve 100% neutralization, an aqueous solution was formed similarly to Manufacturing Example 1, and aqueous solutions of dispersing resin 3 to 15, and comparative dispersing resins 1 to 7 were obtained.

(96) (Manufacturing Example of Resin Fine Particle)

(97) 40 parts of ion-exchanged water and 0.2 parts of AKUARON KH-10 (manufactured by DAI-ICHI KOGYO SEIYAKU CO., LTD.) as a surfactant were put in a reaction container including an agitator, a thermometer, a dropping funnel, and a reflux apparatus, and 1% of a pre-emulsion in which 10 parts of 2-ethyl hexyl acrylate, 57 parts of methyl methacrylate, 30 parts of styrene, 2 parts of dimethylacrylamide, 1 part of methacrylic acid, 53 parts of ion-exchanged water, and 1.8 parts of AKUARON KH-10 (manufactured by DAI-ICHI KOGYO SEIYAKU CO., LTD.) as a surfactant were mixed in advance was further separately added. An internal temperature was increased to 60° C., replacement by nitrogen gas was sufficiently performed, and then 10% of 10 parts of 5% aqueous solution of potassium persulfate and 20 parts of 1% aqueous solution of anhydrous sodium bisulfite were added, and polymerization was started. An inside of a reaction system was maintained at 60° C. for 5 minutes, and then a remainder of a pre-emulsion, and a remainder of a 5% aqueous solution of potassium persulfate and a 1% aqueous solution of anhydrous sodium bisulfite were dripped for 1.5 hours while an internal temperature was maintained at 60° C., and agitation was further continued for 2 hours. After verifying that an inversion rate exceeds 98% through a measurement of solid content, a temperature was cooled down up to 30° C. Diethylaminoethanol was added to set a pH value to 8.5, and solid content was adjusted to 40% using ion-exchanged water to obtain a resin fine particle water dispersion. The solid content was searched for using a baking residue at 150° C. for 20 minutes. The obtained resin fine particle water dispersion was set to resin fine particle 1. A calculated glass transition point temperature of resin fine particle 1 is 80° C.

(Example 1) Manufacture of Dispersing Element and Manufacture of Ink

(98) 20 parts of Pigment Yellow 150 as a pigment, 20 parts of dispersing resin 1, 60 parts of water were preliminarily dispersed by Dispar, and then a main dispersion was performed for 2 hours using DYNO-MILL having a volume of 0.6 L and filled with 1,800 g of zirconia beads having a diameter of 0.5 mm, and a pigment dispersing element was obtained. In this instance, a ratio of a pigment to a non-volatile matter of a dispersing resin is pigment/dispersing resin (non-volatile matter)=5/1. Further, 20 parts of a pigment dispersing element, 35 parts of triethylene glycol monomethyl ether, 5 parts of diethylene glycol monobutyl ether, and 40 parts of water were mixed, and an ink was manufactured.

Examples 2 to 18, and Comparative Examples 1 to 16

(99) A dispersing element was manufactured similarly to Example 1 except that a dispersing resin, a pigment, and a solvent described in Table 2 were used, and an ink was manufactured and evaluated.

Examples 16 to 31

(100) A dispersing element was prepared similarly to Example 1 using a dispersing resin described in Table 2, and 20 parts of a pigment dispersing element, a solvent described in Table 2, and 20 parts of a resin fine particle were mixed, and an ink was prepared.

(101) (Evaluation of Preservation Stability)

(102) A viscosity of a prepared ink was measured using an E-type viscometer (TVE-20L manufactured by TOKI SANGYO CO., LTD) at 25° C. on condition of an engine speed 50 rpm. The ink was preserved in a constant-temperature oven at 70° C., stimulated over time, and then a viscosity change of the ink was evaluated before and after the passage of time. Evaluation criteria are as below, and evaluations A, B, and C correspond to practicable ranges.

(103) A: A rate of change of a viscosity after preservation for 4 weeks is less than ±10%.

(104) B: A rate of change of a viscosity after preservation for 2 weeks is less than ±10%.

(105) C: A rate of change of a viscosity after preservation for 1 week is less than ±10%.

(106) D: A rate of change of a viscosity after preservation for 1 week is ±10 to 20%.

(107) E: A rate of change of a viscosity after preservation for 1 week is ±20% or more.

(108) (Preparation of Printed Material)

(109) Solvent ink inkjet printer Color Painter 64SPlus manufactured by Seiko I Infotech Inc. was filled with the manufactured inkjet yellow ink under a circumstance of 25° C., and an image was printed while a base material is heated to 50° C. After the ink was applied to the base material, heating and drying was performed at 80° C. for 3 minutes, and a printed material for evaluation was obtained. A weather resistance evaluation, verification of a printing quality, and a tolerance test were conducted using the printed material.

(110) (Discharging Characteristic)

(111) A solid printing of 1 m×1 m was performed by the printer, a nozzle check pattern was printed before and after the printing to count the number of nozzle-outs, and an evaluation was conducted using the number.

(112) ∘: No nozzle-out

(113) Δ: 1 to 10 nozzle-outs

(114) x: 11 or more nozzle-outs

(115) (Weather Resistance)

(116) A weather resistance test was conducted using super xenon weather meter SX 75 (manufactured by Suga Test Instruments Co., Ltd.) for 600 hours on a sample printed using PVC as a printing base material on condition of an irradiance 160 W, bp 53° C., 50% RH, irradiation and rainfall cycle mode (1 cycle 120 minutes, within 18 minutes rainfall), and a concentration change before and after the test was evaluated. A concentration was measured using 528 spectral concentration meter manufactured by X-Rite.

(117) ∘: OD value decreasing rate is less than 10%

(118) x: OD value decreasing rate is 10% or more

(119) (Printing Quality)

(120) A printed sample was observed through a magnifying glass for the base material below, and connection between dots, color unevenness, and the like were evaluated. A significantly excellent printing quality was indicated by a symbol ⊚, an excellent printing quality was indicated by a symbol ∘, a generally satisfactory printing quality was indicated by a symbol Δ, and a poor printing quality was indicated by a symbol x.

(121) Coated paper: OK topcoat+manufactured by Oji Paper Co., Ltd.

(122) PVC: MD-5 manufactured by Metamark

(123) (Tolerance Test)

(124) A sample printed using PVC as a printing base material was rubbed with a cotton swab to which ethanol was transfused, and a tolerance test was conducted. A case in which rubbing was performed 51 times or more until an ink peels off, and a ground is exposed was indicated by ∘, a case in which the rubbing was performed 20 to 50 times was indicated by Δ, and a case in which the rubbing was performed less than 20 times was indicated by x. In Examples, it is possible to obtain an enhanced preservation stability, discharging characteristic, weather resistance, printing quality, and tolerance when a pigment, a dispersed resin, and a solvent within the scope of the claims are used. In Examples 16 to 30, a further enhanced tolerance is achieved by using a resin fine particle 1 as a resin fine particle. In Examples 21 to 26, an enhanced printing quality is achieved even on PVC by adjusting a solvent composition. On the other hand, in Comparative Examples 1 to 7, a dispersed resin is out of the scope of the claims and thus, a stability of an ink may not be maintained, and a discharging characteristic is poor. In Comparative Examples 8 to 13, a weather resistance is low since C.I. Pigment Yellow 150 is not used. In Comparative Examples 14 to 16, a printing quality deteriorates since a solvent composition is out of the scope of the claims. In this way, it is indicated that an ink satisfying all evaluation items, and having a quality withstanding practical use is not manufactured when the ink out of the scope of the invention.

(125) TABLE-US-00006 TABLE 1 Manufacturing Reaction solvent Dripping mixture Example Dispersed resin MTG HDG BOD Butanol VA VMA STA STMA LMA St α-MeSt BzA BzMA AA MAA Ex. 1 1 93.4 35 35 30 Ex. 2 2 93.4 35 35 30 Ex. 3 3 93.4 35 35 30 Ex. 4 4 93.4 35 35 30 Ex. 5 5 93.4 35 35 30 Ex. 6 6 93.4 35 35 30 Ex. 7 7 93.4 47 47 6 Ex. 8 8 93.4 23 23 54 Ex. 9 9 89 35 35 30 Ex. 10 10 98.35 35 35 30 Ex. 11 11 93.4 20 50 30 Ex. 12 12 93.4 50 20 30 Ex. 13 13 93.4 40 20 40 Ex. 14 14 93.4 35 35 30 Ex. 15 15 93.4 35 35 30 Ref. 1 Ref. 1 93.4 70 30 Ref. 2 Ref. 2 93.4 70 30 Ref. 3 Ref. 3 93.4 35 35 30 Ref. 4 Ref. 4 93.4 47 47 6 Ref. 5 Ref. 5 93.4 23 23 54 Ref. 6 Ref. 6 93.4 50 20 30 Ref. 7 Ref. 7 93.4 20 50 30 3 hours from Dripping completion Neutralization Final material Manufacturing mixture of dripping Reaction Neutralization Non-volatile Theoretical acid Example V-601 V-65 V-601 V-65 temperature percentage DMAE matter value Mw Ex. 1 6 0.6 110° C. 100% 37.1 20% 234 16000 Ex. 2 6 0.6 110° C. 100% 37.1 20% 234 16000 Ex. 3 6 0.6 110° C. 100% 37.1 20% 234 16000 Ex. 4 6 0.6 110° C. 100% 37.1 20% 234 16000 Ex. 5 6 0.6 110° C. 100% 37.1 20% 234 16000 Ex. 6 6 0.6 110° C. 100% 37.1 20% 196 16000 Ex. 7 6 0.6 110° C. 100% 7.4 20% 47 16000 Ex. 8 6 0.6 110° C. 100% 66.8 20% 421 16000 Ex. 9 10 1 130° C. 100% 37.1 20% 234 1500 Ex. 10 1.5 0.15 110° C. 100% 37.1 20% 234 35000 Ex. 11 6 0.6 110° C. 100% 37.1 20% 234 16000 Ex. 12 6 0.6 110° C. 100% 37.1 20% 234 16000 Ex. 13 6 0.6 110° C. 100% 49.5 20% 312 16000 Ex. 14 6 0.6 110° C. 100% 37.1 20% 234 16000 Ex. 15 6 0.6 110° C. 100% 37.1 20% 234 16000 Ref. 1 6 0.6 110° C. 100% 37.1 20% 234 16000 Ref. 2 6 0.6 110° C. 100% 37.1 20% 234 16000 Ref. 3 6 0.6 110° C. 100% 37.1 20% 234 16000 Ref. 4 6 0.6 110° C. 100% 7.4 20% 47 16000 Ref. 5 6 0.6 110° C. 100% 66.8 20% 421 16000 Ref. 6 6 0.6 110° C. 100% 37.1 20% 234 16000 Ref. 7 6 0.6 110° C. 100% 37.1 20% 234 16000 VA: Behenyl acrylate VMA: Behenyl methacrylate STA: Stearyl acrylate STMA: Stearyl methacrylate LMA: Lauryl acrylate St: Styrene α-MeSt: α-methyl styrene BzA: Benzyl acrylate BzMA: Benzyl methacrylate AA: Acrylic acid V-601: Radical polymerization initiator (manufacturing by WAKO PURE CHEMICAL INDUSTRIES, LTD.) V-65: Radical polymerization initiator (manufacturing by WAKO PURE CHEMICAL INDUSTRIES, LTD.) MTG: Triethylene glycol monomethyl ether HDG: Diethylene glycol monohexyl ether BDO: 1,2-butanediol

(126) TABLE-US-00007 TABLE 2 Dispersed resin Pigment Dispersed Dispersed Manufacture of ink Example resin Composition Mw Types element MTG BDG HDG DEDG DMTeG PDO BDO HDO Ex. 1 1 VA/St/AA = 35/35/30 16000 Pigment 20% 35% 5% Yellow 150 Ex. 2 2 ↑ 16000 Pigment 20% 35% 5% Yellow 150 Ex. 3 3 VMA/α- 16000 Pigment 20% 35% 5% MeSt/AA = 35/35/30 Yellow 150 Ex. 4 4 VA/BzA/AA = 35/35/30 16000 Pigment 20% 35% 5% Yellow 150 Ex. 5 5 VA/BzMA/AA = 35/35/30 16000 Pigment 20% 35% 5% Yellow 150 Ex. 6 6 VA/St/MAA = 35/35/30 16000 Pigment 20% 35% 5% Yellow 150 Ex. 7 7 VA/St/AA = 47/47/6 16000 Pigment 20% 35% 5% Yellow 150 Ex. 8 8 VA/St/AA = 23/23/54 16000 Pigment 20% 35% 5% Yellow 150 Ex. 9 9 VA/St/AA = 35/35/30  1500 Pigment 20% 35% 5% Yellow 150 Ex. 10 10 ↑ 35000 Pigment 20% 35% 5% Yellow 150 Ex. 11 11 VA/St/AA = 20/50/30 16000 Pigment 20% 35% 5% Yellow 150 Ex. 12 12 VA/St/AA = 50/20/30 16000 Pigment 20% 35% 5% Yellow 150 Ex. 13 13 VA/St/AA = 40/20/40 16000 Pigment 20% 35% 5% Yellow 150 Ex. 14 14 STA/St/AA = 35/35/30 16000 Pigment 20% 35% 5% Yellow 150 Ex. 15 15 STMA/St/AA = 35/35/30 16000 Pigment 20% 35% 5% Yellow 150 Ex. 16 1 ↑ 16000 Pigment 20% 35% 5% Yellow 150 Ex. 17 13 VA/St/AA = 40/20/40 16000 Pigment 20% 35% 5% Yellow 150 Ex. 18 13 ↑ 16000 Pigment 20% 40% Yellow 150 Ex. 19 13 ↑ 16000 Pigment 20% 20% 20% Yellow 150 Ex. 20 13 ↑ 16000 Pigment 20% 10% 30% Yellow 150 Ex. 21 13 ↑ 16000 Pigment 20% 10% 30% Yellow 150 Ex. 22 13 ↑ 16000 Pigment 20% 20% 20% Yellow 150 Ex. 23 13 ↑ 16000 Pigment 20% 10% 25% Yellow 150 Ex. 24 13 ↑ 16000 Pigment 20% 10% 20% 5% Yellow 150 Ex. 25 13 ↑ 16000 Pigment 20% 20% 20% Yellow 150 Ex. 26 13 ↑ 16000 Pigment 20% 35%  5% Yellow 150 Ex. 27 13 ↑ 16000 Pigment 20% 35%  5% Yellow 150 Ex. 28 13 ↑ 16000 Pigment 20% 5% 35% Yellow 150 Ex. 29 13 ↑ 16000 Pigment 20% 40% Yellow 150 Ex. 30 13 ↑ 16000 Pigment 20% 35%  5% Yellow 150 Ex. 31 13 ↑ 16000 Pigment 20% 30% Yellow 150 Ref. Ref. 1 VA/AA = 70/30 16000 Pigment 20% 35% 5% Ex. 1 Yellow 150 Ref. Ex. 2 Ref. 2 St/AA = 70/30 16000 Pigment 20% 35% 5% Yellow 150 Ref. Ref. 3 LMA/St/AA = 35/35/30 16000 Pigment 20% 35% 5% Ex. 3 Yellow 150 Ref. Ex. 4 Ref. 4 LMA/St/AA = 47/47/6 16000 Pigment 20% 35% 5% Yellow 150 Ref. Ref. 5 LMA/St/AA = 23/23/54 16000 Pigment 20% 35% 5% Ex. 5 Yellow 150 Ref. Ex. 6 Ref. 6 LMA/St/AA = 50/20/30 16000 Pigment 20% 35% 5% Yellow 150 Ref. Ref. 7 LMA/St/AA = 20/50/30 16000 Pigment 20% 35% 5% Ex. 7 Yellow 150 Ref. 1 VA/St/AA = /40/20/40 16000 Pigment 20% 35% 5% Ex. 8 Yellow 74 Ref. Ex. 9 1 ↑ 16000 Pigment 20% 35% 5% Yellow 120 Ref. 1 ↑ 16000 Pigment 20% 35% 5% Ex. 10 Yellow 151 Ref. 1 ↑ 16000 Pigment 20% 35% 5% Ex. 11 Yellow 155 Ref. 1 ↑ 16000 Pigment 20% 35% 5% Ex. 12 Yellow 180 Ref. 1 ↑ 16000 Pigment 20% 35% 5% Ex. 13 Yellow 185 Ref. 1 ↑ 16000 Pigment 20% Ex. 14 Yellow 150 Ref. 1 ↑ 16000 Pigment 20% Ex. 15 Yellow 150 Ref. 1 ↑ 16000 Pigment 20% Ex. 16 Yellow 150 Manufacture of ink Preservation Weather Printing quality Printing quality Tolerance Example 2PY Gly Fixing resin 1 Water stability Discharging resistance (Coated paper) (PVC) test Ex. 1 40.0% B ◯ ◯ ◯ Δ Δ Ex. 2 40.0% B ◯ ◯ ◯ Δ Δ Ex. 3 40.0% B ◯ ◯ ◯ Δ Δ Ex. 4 40.0% B ◯ ◯ ◯ Δ Δ Ex. 5 40.0% B ◯ ◯ ◯ Δ Δ Ex. 6 40.0% B ◯ ◯ ◯ Δ Δ Ex. 7 40.0% C Δ ◯ ◯ Δ Δ Ex. 8 40.0% C ◯ ◯ ◯ Δ Δ Ex. 9 40.0% C ◯ ◯ ◯ Δ Δ Ex. 10 40.0% C Δ ◯ ◯ Δ Δ Ex. 11 40.0% C ◯ ◯ ◯ Δ Δ Ex. 12 40.0% A ◯ ◯ ◯ Δ Δ Ex. 13 40.0% A ◯ ◯ ◯ Δ Δ Ex. 14 40.0% C ◯ ◯ ◯ Δ Δ Ex. 15 40.0% C ◯ ◯ ◯ Δ Δ Ex. 16 20% 20.0% C ◯ ◯ ◯ Δ ◯ Ex. 17 20% 20.0% B ◯ ◯ ◯ Δ ◯ Ex. 18 20% 20.0% C ◯ ◯ ⊙ ⊙ ◯ Ex. 19 20% 20.0% B ◯ ◯ ⊙ ⊙ ◯ Ex. 20 20% 20.0% B ◯ ◯ ⊙ ⊙ ◯ Ex. 21 20% 20.0% B ◯ ◯ ⊙ ⊙ ◯ Ex. 22 20% 20.0% B ◯ ◯ ⊙ ⊙ ◯ Ex. 23 5% 20% 20.0% A ◯ ◯ ⊙ ⊙ ◯ Ex. 24 5% 20% 20.0% A ◯ ◯ ⊙ ⊙ ◯ Ex. 25 20% 20.0% B ◯ ◯ ⊙ ◯ ◯ Ex. 26 20% 20.0% A ◯ ◯ ⊙ ◯ ◯ Ex. 27 20% 20.0% A ◯ ◯ ◯ Δ ◯ Ex. 28 20% 20.0% A ◯ ◯ ◯ Δ ◯ Ex. 29 20% 20.0% A ◯ ◯ Δ Δ ◯ Ex. 30 20% 20.0% A ◯ ◯ Δ Δ ◯ Ex. 31 10% 20% 20.0% A ◯ ◯ Δ Δ ◯ Ref. 40.0% D X ◯ ◯ Δ Δ Ex. 1 Ref. Ex. 2 40.0% E X ◯ ◯ Δ X Ref. 40.0% E X ◯ ◯ Δ X Ex. 3 Ref. Ex. 4 40.0% E X ◯ ◯ Δ X Ref. 40.0% E X ◯ ◯ Δ X Ex. 5 Ref. Ex. 6 40.0% D X ◯ ◯ Δ X Ref. 40.0% E X ◯ ◯ Δ X Ex. 7 Ref. 40.0% B ◯ X ◯ Δ Δ Ex. 8 Ref. Ex. 9 40.0% B ◯ X ◯ Δ Δ Ref. 40.0% C ◯ X ◯ Δ Δ Ex. 10 Ref. 40.0% C ◯ X ◯ Δ Δ Ex. 11 Ref. 40.0% C ◯ X ◯ Δ Δ Ex. 12 Ref. 40.0% D X X ◯ Δ Δ Ex. 13 Ref. 30% 50.0% A X ◯ X X Δ Ex. 14 Ref. 30% 50.0% A X ◯ X X Δ Ex. 15 Ref. 20% 10% 50.0% A X ◯ X X Δ Ex. 16 MTG: Triethylene glycol monomethyl ether BDG: Diethylene glycol monobutyl ether HDG: Diethylene glycol monohexyl ether PDO: 1,2-propanediol BDO: 1,2-butanediol HDO: 1,2-hexanediol 2PY: 2-pyrrolidone Gly: Glycerin