The surfactant may be used alone or in combination of two or more thereof.

The wet agent is not particularly limited, and examples thereof include lower alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, and tert-butyl alcohol; amides such as dimethylformamide and dimethylacetamide; ketones such as acetone; keto alcohols such as diacetone alcohol; ethers such as tetrahydrofuran and dioxane; polyethers such as polyalkylene glycol; alkylene glycols; polyhydric alcohols such as glycerin, trimethylolpropane, and trimethylolethane; 2-pyrolidone; N-methyl-2-pyrolidone; and 1,3-dimethyl-2-imidazolidinone. Examples of the polyalkylene glycol include polyethylene glycol and polypropylene glycol. Examples of the alkylene glycol include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol, thiodiglycol, and hexylene glycol. These wet agents may be used alone or in combination of two or more thereof. Among them, polyhydric alcohols such as alkylene glycol and glycerin are preferable.

Examples of the viscosity modifier include polyvinyl alcohol, cellulose, and a water-soluble resin.

Next, an aqueous ink for ink jet recording of the present disclosure (hereinafter, sometimes referred to as an “aqueous ink” or an “ink”) will be described. The aqueous ink of the present disclosure contains the resin composition of the present disclosure and a pigment.

The pigment is not particularly limited, and examples thereof include carbon black, an inorganic pigment, and an organic pigment. Examples of the carbon black include furnace black, lamp black, acetylene black, and channel black. Examples of the inorganic pigment include titanium oxide, iron oxide inorganic pigments, and carbon black inorganic pigments. Examples of the organic pigment include an azo pigment such as azo lake, an insoluble azo pigment, a condensed azo pigment, and a chelate azo pigment; a polycyclic pigment such as a phthalocyanine pigment, a perylene and perinone pigment, an anthraquinone pigment, a quinacridone pigment, a dioxazine pigment, a thioindigo pigment, an isoindolinone pigment, and a quinophthalone pigment; a dye lake pigment such as a basic dye lake pigment and an acid dye lake pigment; a nitro pigment; a nitroso pigment; and an aniline black daylight fluorescent pigment. Another pigment may be used as long as the pigment can be dispersed in an aqueous phase. Specific examples of these pigments include C.I. Pigment Black 1, 6, and 7; C.I. Pigment Yellow 1, 2, 3, 12, 13, 14, 15, 16, 17, 55, 74, 78, 150, 151, 154, 180, 185, and 194; C.I. Pigment Orange 31 and 43; C.I. Pigment Red 2, 3, 5, 6, 7, 12, 15, 16, 48, 48:1, 53:1, 57, 57:1, 112, 122, 123, 139, 144, 146, 149, 150, 166, 168, 175, 176, 177, 178, 184, 185, 190, 202, 209, 221, 222, 224, and 238; C.I. Pigment Violet 19 and 196; C.I. Pigment Blue 1, 2, 3, 15, 15:1, 15:2, 15:3, 15:4, 16, 22, and 60; C.I. Pigment Green 7 and 36; and solid solutions of the pigments.

The pigment may be dispersed in a solvent with a resin dispersant (also referred to as a resin dispersing pigment). As the resin dispersant, for example, a general high molecular weight dispersant (also referred to as a pigment dispersing resin or a resin dispersant) may be used, and the resin dispersant may be self-prepared. Further, in the aqueous ink of the present disclosure, the pigment may be encapsulated with a polymer. As the resin dispersant, for example, those containing at least one of methacrylic acid and acrylic acid as a monomer can be used, and for example, a commercially available product may be used. The resin dispersant may be, for example, a block copolymer, a graft copolymer, or a random copolymer formed by hydrophobic monomers such as styrene, styrene derivatives, vinylnaphthalene, vinylnaphthalene derivatives, aliphatic alcohol esters of α,β-ethylenically unsaturated carboxylic acids or two or more monomers selected from the group consisting of acrylic acid, acrylic acid derivatives, maleic acid, maleic acid derivatives, itaconic acid, itaconic acid derivatives, fumaric acid, and fumaric acid derivatives, or a salt thereof. Examples of the commercially available product include “Joncryl (registered trademark) 611”, “Joncryl (registered trademark) 60”, “Joncryl (registered trademark) 586”, “Joncryl (registered trademark) 687”, “Joncryl (registered trademark) 63”, and “Joncryl (registered trademark) HPD296” manufactured by Johnson Polymer Co., Ltd.; “Disperbyk 190” and “Disperbyk 191” manufactured by Bicchemy Japan Co., Ltd.; and “Solsperse 20000” and “Solsperse 27000” manufactured by Zeneca Corp.

Examples of a method for dispersing the pigment using the pigment dispersing resin include dispersing the pigment using a dispersing device. The dispersing device used for dispersing the pigment is not particularly limited as long as the dispersing device is a general disperser, and examples thereof include a ball mill, a roll mill, and a sand mill (for example, a high-speed type sand mill).

The pigment may be a self-dispersing pigment. The self-dispersing pigment can be dispersed in water without using a dispersant, for example, by introducing at least one of a hydrophilic functional group such as a carbonyl group, a hydroxyl group, a carboxylic acid group, a sulfonic acid group, and a phosphate group, and a salt thereof into pigment particles through chemical bonding, either directly or through other groups. As the self-dispersing pigment, for example, pigments treated by methods described in JPH08-003498A, JP2000-513396A, JP2008-524400A, JP2009-515007A, and JP2011-515535A can be used. As a raw material of the self-dispersing pigment, either an inorganic pigment or an organic pigment can be used. Further, examples of the pigment suitable for the treatment include carbon black such as “MA8” and “MA100” manufactured by Mitsubishi Chemical Corporation. The self-dispersing pigment may be, for example, a commercially available product. Examples of the commercially available product include “CAB-O-JET (registered trademark) 200”, “CAB-O-JET (registered trademark) 250C”, “CAB-O-JET (registered trademark) 260M”, “CAB-O-JET (registered trademark) 270Y”, “CAB-O-JET (registered trademark) 300”, “CAB-O-JET (registered trademark) 400”, “CAB-O-JET (registered trademark) 450C”, “CAB-O-JET (registered trademark) 465M”, and “CAB-O-JET (registered trademark) 470Y” manufactured by Cabot Corporation; “BONJET (registered trademark) BLACK CW-2” and “BONJET (registered trademark) BLACK CW-3” manufactured by Orient Chemical Company; and “LIOJET (registered trademark) WD BLACK 002C” manufactured by TOYO INK CO., LTD.

A concentration of the pigment is not particularly limited, and may be, for example, 2% by weight or more, 4% by weight or more, or 6% by weight or more, and may be, for example, 6% by weight or less, 4% by weight or less, or 2% by weight or less.

The aqueous ink of the present disclosure may further contain a fixing agent as an additive. The fixing agent is used for fixing the colorant to a recording medium. The recording medium is not particularly limited, and examples thereof include a non-absorbent base material and a recording sheet.

Next, a screening method for the second solvent and the resin particles used in the resin composition of the present disclosure or the aqueous ink of the present disclosure will be described. The screening method includes: a step of calculating the relative energy difference (RED); and a step of selecting the second solvent and the resin particles having a relationship in which the RED is less than 3. The calculation method of RED is the same as the calculation method of RED described in the resin composition of the present disclosure.

Next, an ink jet recording device and an ink jet recording method of the present disclosure will be described.

The ink jet recording device of the present disclosure includes a flow path and an applying unit, in which the resin composition or the aqueous ink supplied to the flow path is applied to an object by the applying unit, the resin composition is the resin composition of the present disclosure, and the aqueous ink is the aqueous ink for ink jet recording of the present disclosure.

FIGURE shows a configuration of an example of the ink jet recording device. As shown in the FIGURE, an ink jet recording device 1 includes four ink storage units (ink cartridges 2), an ink discharging unit (ink jet head) 3, a head unit 4, a carriage 5, a drive unit 6, a platen roller 7, and a purge device 8 as main components.

The four ink cartridges 2 storage, for example, four aqueous inks, that is, a yellow ink, a magenta ink, a cyan ink, and a black ink, respectively. For example, at least one of the four aqueous inks is an aqueous ink of the present disclosure. Further, for example, at least one of the aqueous inks may be used as the resin composition of the present disclosure. In this example, a set of four ink cartridges 2 is shown, but instead of this, for example, an integrated ink cartridge which is partitioned so as to form an aqueous yellow ink storage unit, an aqueous magenta ink storage unit, an aqueous cyan ink storage unit, and an aqueous black ink storage unit therein may be used. As a main body of the ink cartridge, for example, a known ink cartridge aqueous in the related art can be used.

The ink jet head 3 provided in the head unit 4 performs recording on a recording medium (for example, a non-absorbent base material) P. The four ink cartridges 2 and the head unit 4 are mounted on the carriage 5. The drive unit 6 reciprocates the carriage 5 in a linear direction. As the drive unit 6, for example, a known drive unit in the related art can be used (for example, see JP2008-246821A). The platen roller 7 extends in a reciprocating direction of the carriage 5 and is disposed in a manner of facing the ink jet head 3.

The ink jet head 3 is formed by stacking a plurality of thin metal plates, for example. A through hole is formed in the thin plates. By stacking the plurality of thin plates in which the through hole is formed, the flow path for passing the aqueous ink is formed. The thin plates are bonded by, for example, an adhesive.

The purge device 8 suctions a defective ink containing air bubbles and the like accumulated inside the ink jet head 3. As the purge device 8, for example, a known purge device in the related art can be used (for example, see JP2008-246821A).

A wiper member 20 is disposed adjacent to the purge device 8 on a platen roller 7 side of the purge device 8. The wiper member 20 is formed in a spatula shape and wipes a nozzle forming surface of the ink jet head 3 as the carriage 5 moves. In FIGURE, a cap 18 covers a plurality of nozzles of the ink jet head 3 to be returned to a reset position when recording is completed in order to prevent drying of the aqueous ink.

In the ink jet recording device 1 of the present embodiment, the four ink cartridges 2 are mounted on one carriage 5 together with the head unit 4. However, the present disclosure is not limited thereto. In the ink jet recording device 1, each of the four ink cartridges 2 may be mounted on a carriage different from the head unit 4. Each of the four ink cartridges 2 may be disposed and fixed in the ink jet recording device 1 without being mounted on the carriage 5. In these aspects, for example, each of the four ink cartridges 2 and the head unit 4 mounted on the carriage 5 are connected by a tube or the like, and the aqueous ink is supplied from each of the four ink cartridges 2 to the head unit 4. Further, in these aspects, four ink bottles each having a bottle shape may be used instead of the four ink cartridges 2. In this case, it is preferable that the ink bottle is provided with an injection port for injecting the ink from an outside to an inside.

Ink jet recording using the ink jet recording device 1 is performed as follows, for example. First, the recording sheet P is fed from a sheet feeding cassette (not shown) provided on a lateral side or a lower side of the ink jet recording device 1. The recording sheet P is introduced between the ink jet head 3 and the platen roller 7. Predetermined recording is performed on the introduced recording sheet P with the aqueous ink discharged from the ink jet head 3. This discharge may be performed, for example, at a first discharge amount as described above, or may be performed at a second discharge amount when a specific condition is satisfied. The recording sheet P after the recording is ejected from the ink jet recording device 1. In FIGURE, a sheet feeding mechanism and a sheet ejecting mechanism of the recording sheet P are not shown.

In the device shown in FIGURE, a serial type ink jet head is used, but the present disclosure is not limited thereto. The ink jet recording device may be a device using a line type ink jet head or roll-to-roll. The serial type ink jet head is an ink jet head that performs printing while reciprocating the ink jet head in a width direction of the recording medium. The line type ink jet head is an ink jet head that covers of the recording medium in the entire width direction. The roll-to-roll is a method for sending out and printing the recording medium in a roll shape, and winding the recording medium in a roll shape again.

The ink jet recording method of the present disclosure includes a recording step of applying the resin composition of the present disclosure or the aqueous ink of the present disclosure to the recording medium by an ink jet method to perform recording. The recording step can be carried out using, for example, the ink jet recording device shown in FIGURE.

The ink jet recording method of the present disclosure may further include, for example, a drying step of heating a recording portion of the recording medium. The drying step is not particularly limited except that the resin composition or the aqueous ink applied to the recording medium, or the solvent (water and solution) contained in the resin composition or the aqueous ink, is removed by evaporation, and can be appropriately selected from a warm wind, a heat platen, a heat press, and the like according to a purpose.

A lower limit value of a drying temperature in the drying step is, for example, 90° C. or more, preferably 100° C. or more, and more preferably 110° C. or more. When the drying temperature is lower than 90° C., volatilization of the water is slow. As a result, for example, since a ratio of the solvent contained in the resin composition or the aqueous ink does not become rich after the application, a film forming effect becomes weaker, and the coating performance deteriorates. On the other hand, when the drying temperature is 90° C. or more, the volatilization of the water is accelerated. As a result, the ratio of the solvent contained in the resin composition or the aqueous ink after the application tends to be rich, the film forming effect becomes stronger, and the coating performance is improved. Therefore, the drying temperature is preferably 90° C. or more. Further, an upper limit value of the drying temperature in the drying step is, for example, a temperature at which abnormal deformation such as wrinkles or burning does not occur in the base material (recording medium), and varies depending on the base material to be used. The upper limit value of the drying temperature may be, for example, 120° C. or less in a case of Scotch Cal graphic film IJ1220 manufactured by 3M Company, and 140° C. or less in a case of “OK Top Coat+” manufactured by OJI PAPER CO., LTD.

The lower limit value of the drying temperature is determined according to the resin composition or the aqueous ink to be used, but in relation to the resin composition or the aqueous ink to be used, the higher the upper limit value of the drying temperature, the better the coating performance tends to be. On the other hand, the higher the drying temperature, the more likely the base material is altered. Therefore, in the present disclosure, the upper limit value of the drying temperature is not particularly limited in relation to the resin composition or the aqueous ink, and is determined by the base material on which the resin composition or the aqueous ink lands.

A lower limit value of the drying time in the drying step is, for example, 1 minute or more, 2 minutes or more, or 3 minutes or more, and an upper limit thereof is, for example, 10 minutes or less, 5 minutes or less, or 4 minutes or less. Drying conditions are preferably such that the drying temperature is 90° C. or more and the drying time is 1 minute or more, and more preferably such that the drying temperature is 110° C. or more and the drying time is 1 minute or more.

EXAMPLES

Next, Examples of the present disclosure will be described together with Comparative Examples. The present disclosure is not limited or restricted by the following Examples and Comparative Examples. In the following description, “parts” and “%” are based on mass unless otherwise specified. Further, various physical properties are measured according to a measurement method to be described later.

[Preparation of Resin Composition and Aqueous Ink] (Examples 1 to 19 and Comparative Examples 1 to 10)

The first solvent, the second solvent, and the resin particles in each of composition tables (Tables 1 to 5) were uniformly mixed to obtain a resin composition. When the resin composition contains a color material, the color material described in each of Tables 1 to 5 were added to the resin composition and uniformly mixed. An obtained mixture was filtered through a cellulose acetate type membrane filter (pore diameter: 3.00 m) manufactured by Toyo Roshi Kaisha, Ltd. to obtain a resin composition and an aqueous ink for ink jet recording in each of Examples 1 to 19 and Comparative Examples 1 to 10 shown in Tables 1 to 5.

[Calculation of RED]

The relative energy difference RED described in Tables 1 to 5 was calculated by the following procedure. First, 1 g of each second solvent described in Tables 1 to 5 or a solvent other than each second solvent was sufficiently mixed with 1 g of a polymer. After the solvent and the polymer were sufficiently stirred, a property of the mixture were observed and classified into three types: “gelling,” “white-clouding,” and “no change.” Next, HSP values of the second solvent and the solvent other than the second solvent were calculated using HSP value calculation software (HSPiP, manufactured by Pirika.com). Next, a sphere (Hansen sphere) containing all the solvents obtained by “gelling” and “white-clouding” the polymer was prepared using the software, and a HSP value of each polymer was calculated from a center of the Hansen sphere. Next, an HSP distance (R_a) between the solvent and the resin was calculated from the HSP values of the second solvent and the solvent other than the second solvent and the HSP values of the respective polymers. The HSP distance (R_a) was obtained from Calculation Formula (1) described in the above embodiment. Further, the relative energy difference RED (R_a/R₀) was calculated from a radius (R₀) of the Hansen sphere and the HSP distance (R_a).

[Evaluation of Physical Properties]

With respect to the aqueous inks of Examples 1 to 19 and Comparative Examples 1 to 10, (a) surface tackiness immediately after drying, (b) drying unevenness, (c) storage stability (room temperature), (d) an OD value, and (e) solvent resistance were evaluated by the following methods.

In evaluation of the following coating films, the coating films were prepared as follows. First, each of the aqueous inks of Examples 1 to 19 and Comparative Examples 1 to 10 was applied onto a base material (PVC sheeting, product number: Scotch Cal graphic film IJ1220, manufactured by 3M Company) using a bar coater (manufactured by OSG SYSTEM PRODUCTS Co., Ltd., depth: 9 m). This was dried using a warm air dryer at 110° C. for 1 min to obtain a coating film.

(a) Surface Tackiness Immediately after Drying

The surface tackiness immediately after the drying was evaluated by touching the coating film immediately after the preparation with a glove (material: natural rubber, product number: ASPURE Latex Glove, manufactured by AS ONE CORPORATION) for 1 second, and then visually checking transfer of the coating film to the glove and marks left on a coating film surface.

Surface Tackiness Immediately after Drying Evaluation Standard

A: There was no transfer to the glove or any marks left on the coating film surface.

B: There was a transfer to the glove or a mark left on the coating film surface.

(b) Drying Unevenness

The coating film immediately after the preparation was visually observed from an angle of 45 degrees at a distance of about 5 cm from the coating film under irradiation with a fluorescent lamp (product number: FL20SNEDL, manufactured by PANASONIC Co., Ltd.), and the drying unevenness was evaluated from uniformity of the film.

Drying Unevenness Evaluation Standard A: A striped pattern due to the drying was not observed, and the coating film was uniformly formed. B: A striped pattern due to the drying was observed, and a uniform coating film was not formed.

(c) Storage Stability (Room Temperature)

The prepared aqueous ink of each of Examples and Comparative Examples was placed in a sealed container and stored for 5 days in a room temperature environment. The stored ink was observed using a microscope (product number: LV100ND POL/DS, manufactured by Nikon Corporation) at a magnification of 200 times under transmitted light for the presence or absence of aggregation of ink components to evaluate the storage stability in the room temperature environment.

Storage Stability (Room Temperature): Evaluation Standard ∘: No aggregation of the ink was observed. x: Aggregation of the ink was observed.

(d) OD Value

Optical density (OD value) of the prepared coating film was measured using a spectral colorimeter exact (filter: M0 (No), light source: D20, viewing angle: 2°, ISO status T) manufactured by X-Rite, Inc., and optical density (OD value) of each of color materials, that is, Mg, Cy, Bk, and Ye materials was evaluated according to the following evaluation standard.

OD Value Evaluation Standard A: Mg: 1.0 or more, Cy: 1.7 or more, Bk: 1.4 or more, and Ye: 1.6 or more; and B: Mg: less than 1.0, Cy: less than 1.7, Bk: less than 1.4, and Ye: less than 1.6

(e) Solvent Resistance

A cloth for evaluation (canequim No. 3) impregnated with 300 μL of 70% ethanol was set in a gakushin-type rubbing fastness tester (AB-301, manufactured by TESTER SANGYO CO., LTD.), and a surface of the prepared coating film was rubbed under conditions of a load of 200 g, 3.6 m/min, and five reciprocating movements to evaluate the solvent resistance of the coating film. In a solvent resistance test, a coating film was prepared under the same conditions as described above except that the drying conditions were changed to the conditions described in each of Tables 1 to 5. Specifically, the solvent resistance of Examples and Comparative Examples was evaluated under the drying conditions of “110° C. and 1 min”. Further, in order to check the solvent resistance under a lower temperature drying condition, representative Examples 1 to 2, 7, and 11 to 15 were also evaluated under drying conditions of “90° C. and 1 min”.

Solvent Resistance Evaluation Standard A: An area of coating film peeling due to rubbing was less than 30%. B: An area of coating film peeling due to rubbing was 30% or more and less than 70%. C: An area of coating film peeling due to rubbing was 70% or more.

An aqueous ink composition and an evaluation result of the aqueous ink of each of Examples 1 to 19 and Comparative Examples 1 to 10 are shown in Tables 1 to 5.

TABLE 1

Boiling
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-
Exam-

point
ple 1
ple 2
ple 3
ple 4
ple 5
ple 6
ple 7

Solvent
Dipropylene glycol methyl ether (DPM)
188

Propylene glycol (PG)
188

1,3-propanediol
214
12.0
13.0
13.0
18.0
12.0
15.0
13.0

1,2-hexanediol
223

Dipropylene glycol n-butyl ether (DPnB)
230

Polyethylene glycol 400 (PEG 400)
250

2-pyrolidone
251

Tripropylene glycol (TPG)
270
12.0

12.0

15.0

Tripropylene glycol n-butyl ether (TPnB)
274

9.0

Triethylene glycol (TEG)
276

Triethylene glycol monobutyl ether (BTG)
278

9.0
7.0

Glycerin (Gly)
290

Polyethylene glycol monomethyl ether
300

10.0

Polymer R
Mowinyl ® 6969D (*1)
8.4
8.4
8.1
8.0
8.0
7.9
8.2

*Solid content
Mowinyl ® 6899D (*2)

concentration
JE-1056 (*3)

Vinyblan ® 715S (*4)

Surfactant
Olfine ® E1004 (*5)
1.0
1.0
1.0
1.0
1.0
1.0
1.0

Color material
Pigment dispersion A (*6)
3.1

2.5

*Solid content
Pigment dispersion B (*7)

3.0

concentration
Pigment dispersion C (*8)

3.2

3.0

Pigment dispersion D (*9)

4.0

Water
Balance
Balance
Balance
Balance
Balance
Balance
Balance

First solvent
S1
12.0
13.0
13.0
18.0
12.0
15.0
13.0

Second
Solvent having boiling point of 250° C. or more
Pres-
Pres-
Pres-
Pres-
Pres-
Pres-
Pres-

solvent

ence
ence
ence
ence
ence
ence
ence

Relative energy difference (Ra/Ro) RED calculated
2.6
1.0
1.0
1.0
2.6
1.6
2.6

from HSP distance (Ra) between solvent having

boiling point of 250° C. or more and resin particles

and Hansen sphere radius (Ro)

S2
12.0
9.0
7.0
9.0
12.0
10.0
15.0

S2/R
1.43
1.07
0.86
1.13
1.50
1.27
1.83

S2/S1
1.00
0.69
0.54
0.50
1.00
0.67
1.15

S1 + S2
24
22
20
27
24
25
28

Surface tackiness immediately after drying
A
A
A
A
A
A
A

Drying unevenness
A
A
A
A
A
A
A

Storage stability (room temperature)
∘
∘
∘
∘
∘
∘
∘

Solvent resistance
120° C. × 1 min
A
A
—
—
—
—
A

110° C. × 1 min
A
A
B
A
A
A
A

90° C. × 1 min
B
B
—
—
—
—
B

(*1): Acrylic resin emulsion, manufactured by Japan Coating Resin Corp.

(*2): Acrylic resin emulsion, manufactured by Japan Coating Resin Corp.

(*3): Acrylic resin emulsion, manufactured by SEIKO PMC CORPORATION

(*4): Vinyl chloride-acrylic copolymer emulsion, manufactured by Nissin Chemical Industry Co., Ltd.

(*5): Acetylene glycol-based surfactant (ethylene oxide of diol (10 mol)) adduct, manufactured by Nissin Chemical Industry Co., Ltd., active ingredient = 100%

(*6): Aqueous dispersion of C.I. Pigment Red 122 (containing resin dispersant): numerical values in table indicate pigment solid blending amount.

(*7): Aqueous dispersion of C.I. Pigment Blue 15:3 (containing resin dispersant): numerical values in table indicate pigment solid blending amount.

(*8): Aqueous dispersion of carbon black: numerical values in table indicate pigment solid blending amount.

(*9): Aqueous dispersion of C.I. Pigment Yellow 155 (containing resin dispersant): numerical values in table indicate pigment solid blending amount.

TABLE 2

Boiling
Example
Example
Example
Example
Example
Example

point
8
9
10
11
12
13

Solvent
Dipropylene glycol methyl ether (DPM)
188

Propylene glycol (PG)
188

13.0

1,3-propanediol
214
23.0
33.0
3.0

13.0

1,2-hexanediol
223

12.0

Dipropylene glycol n-butyl ether (DPnB)
230

Polyethylene glycol 400 (PEG 400)
250

2-pyrolidone
251

Tripropylene glycol (TPG)
270
10.0
9.0
12.0
10.0
10.0

Tripropylene glycol n-butyl ether (TPnB)
274

Triethylene glycol (TEG)
276

Triethylene glycol monobutyl ether (BTG)
278

10.0

Glycerin (Gly)
290

Polyethylene glycol monomethyl ether
300

Polymer R
Mowinyl ® 6969D (*1)
6.8
6.9
7.5
9.0
7.6

*Solid content
Mowinyl ® 6899D (*2)

8.4

concentration
JE-1056 (*3)

Vinyblan ® 715S (*4)

Surfactant
Olfine ® E1004 (*5)
1.0
1.0
1.0
1.0
1.0
1.0

Color material
Pigment dispersion A (*6)

2.6
4.1

*Solid content
Pigment dispersion B (*7)
2.8

2.7

concentration
Pigment dispersion C (*8)

2.5

Pigment dispersion D (*9)

3.2

Water
Balance
Balance
Balance
Balance
Balance
Balance

First solvent
S1
23.0
33.0
3.0
12.0
13.0
13.0

Second solvent
Solvent having boiling point of 250° C. or more
Presence
Presence
Presence
Presence
Presence
Presence

Relative energy difference (Ra/Ro) RED calculated
2.6
2.6
2.6
2.6
2.6
0.6

from HSP distance (Ra) between solvent having boiling

point of 250° C. or more and resin particles and Hansen

sphere radius (Ro)

S2
10.0
9.0
12.0
10.0
10.0
10.0

S2/R
1.47
1.30
1.60
1.11
1.32
1.19

S2/S1
0.43
0.27
4.00
0.83
0.77
0.77

S1 + S2
33
42
15
22
23
23

Surface tackiness immediately after drying
A
A
A
A
A
A

Drying unevenness
A
B
B
A
A
A

Storage stability (room temperature)
∘
∘
∘
∘
∘
∘

Solvent resistance
120° C. × 1 min
—
—
—
A
A
A

110° C. × 1 min
B
B
B
A
A
A

90° C. × 1 min
—
—
—
A
B
B

(*1): Acrylic resin emulsion, manufactured by Japan Coating Resin Corp.

(*2): Acrylic resin emulsion, manufactured by Japan Coating Resin Corp.

(*3): Acrylic resin emulsion, manufactured by SEIKO PMC CORPORATION

(*4): Vinyl chloride-acrylic copolymer emulsion, manufactured by Nissin Chemical Industry Co., Ltd.

(*5): Acetylene glycol-based surfactant (ethylene oxide of diol (10 mol)) adduct, manufactured by Nissin Chemical Industry Co., Ltd., active ingredient = 100%

(*6): Aqueous dispersion of C.I. Pigment Red 122 (containing resin dispersant): numerical values in table indicate pigment solid blending amount.

(*7): Aqueous dispersion of C.I. Pigment Blue 15:3 (containing resin dispersant): numerical values in table indicate pigment solid blending amount.

(*8): Aqueous dispersion of carbon black: numerical values in table indicate pigment solid blending amount.

(*9): Aqueous dispersion of C.I. Pigment Yellow 155 (containing resin dispersant): numerical values in table indicate pigment solid blending amount.

TABLE 3

Boiling
Example
Example
Example
Example
Example
Example

point
14
15
16
17
18
19

Solvent
Dipropylene glycol methyl ether (DPM)
188

Propylene glycol (PG)
188

1,3-propanediol
214
13.0
13.0
13.0
13.0
13.0
13.0

1,2-hexanediol
223

Dipropylene glycol n-butyl ether (DPnB)
230

Polyethylene glycol 400 (PEG 400)
250

2-pyrolidone
251

Tripropylene glycol (TPG)
270

10.0

Tripropylene glycol n-butyl ether (TPnB)
274
10.0

9.0

Triethylene glycol (TEG)
276

Triethylene glycol monobutyl ether (BTG)
278

9.0

9.0

Glycerin (Gly)
290

Polyethylene glycol monomethyl ether
300

9.0

Polymer R
Mowinyl ® 6969D (*1)

8.4
8.4

*Solid content
Mowinyl ® 6899D (*2)

concentration
JE-1056 (*3)
8.4
8.4
9.0

Vinyblan ® 715S (*4)

8.0

Surfactant
Olfine ® E1004 (*5)
1.0
1.0
1.0
1.0
1.0
1.0

Color material
Pigment dispersion A (*6)
3.0

1.5
5.0

*Solid content
Pigment dispersion B (*7)

3.2

concentration
Pigment dispersion C (*8)

Pigment dispersion D (*9)

2.9

2.8

Water
Balance
Balance
Balance
Balance
Balance
Balance

First solvent
S1
13.0
13.0
13.0
13.0
13.0
13.0

Second solvent
Solvent having boiling point of 250° C. or more
Presence
Presence
Presence
Presence
Presence
Presence

Relative energy difference (Ra/Ro) RED calculated
1.0
0.8
1.0
1.0
2.6
1.0

from HSP distance (Ra) between solvent having boiling

point of 250° C. or more and resin particles and Hansen

sphere radius (Ro)

S2
10.0
9.0
9.0
9.0
10.0
9.0

S2/R
1.19
1.07
1.00
1.13
1.19
1.07

S2/S1
0.77
0.69
0.69
0.69
0.77
0.69

S1 + S2
23
22
22
22
23
22

Surface tackiness immediately after drying
A
A
A
A
A
A

Drying unevenness
A
A
A
A
A
A

Storage stability (room temperature)
∘
∘
∘
∘
∘
∘

Solvent resistance
120° C. × 1 min
A
A
—
—
—
—

110° C. × 1 min
A
A
A
A
A
A

90° C. × 1 min
A
A
—
—
—
—

(*1): Acrylic resin emulsion, manufactured by Japan Coating Resin Corp.

(*2): Acrylic resin emulsion, manufactured by Japan Coating Resin Corp.

(*3): Acrylic resin emulsion, manufactured by SEIKO PMC CORPORATION

(*4): Vinyl chloride-acrylic copolymer emulsion, manufactured by Nissin Chemical Industry Co., Ltd.

(*5): Acetylene glycol-based surfactant (ethylene oxide of diol (10 mol) adduct, manufactured by Nissin Chemical Industry Co., Ltd., active ingredient = 100%

(*6): Aqueous dispersion of C.I. Pigment Red 122 (containing resin dispersant): numerical values in table indicate pigment solid blending amount.

(*7): Aqueous dispersion of C.I. Pigment Blue 15:3 (containing resin dispersant): numerical values in table indicate pigment solid blending amount.

(*8): Aqueous dispersion of carbon black: numerical values in table indicate pigment solid blending amount.

(*9): Aqueous dispersion of C.I. Pigment Yellow 155 (containing resin dispersant): numerical values in table indicate pigment solid blending amount.

TABLE 4

Boiling
Comparative
Comparative
Comparative
Comparative
Comparative

point
Example 1
Example 2
Example 3
Example 4
Example 5

Solvent
Dipropylene glycol methyl ether (DPM)
188

11.0

Propylene glycol (PG)
188

1,3-propanediol
214

13.0
12.0
14.0
15.0

1,2-hexanediol
223

Dipropylene glycol n-butyl ether (DPnB)
230

9.0

Polyethylene glycol 400 (PEG 400)
250

2-pyrolidone
251

8.0

Tripropylene glycol (TPG)
270
10.0

Tripropylene glycol n-butyl ether (TPnB)
274

Triethylene glycol (TEG)
276
13.0

Triethylene glycol monobutyl ether (BTG)
278

Glycerin (Gly)
290

10.0

Polyethylene glycol monomethyl ether
300

Polymer R
MowinyI@ 6969D (*1)
8.4
8.4
8.4
8.4
8.4

*Solid content
MowinyI ® 6899D (*2)

concentration
JE-1056 (*3)

Vinyblan@ 715S (*4)

Surfactant
Olfine ® E1004 (*5)
1.0
1.0
1.0
1.0
1.0

Color material
Pigment dispersion A (*6)
3.1

2.5

*Solid content
Pigment dispersion B (*7)

concentration
Pigment dispersion C (*8)

3.2

3.0

Pigment dispersion D (*9)

4.0

Water
Balance
Balance
Balance
Balance
Balance

First solvent
S1
0.0
13.0
12.0
23.0
26.0

Second solvent
Solvent having boiling point of 250° C. or more
Presence
Presence
Presence
Absent
Absent

Relative energy difference (Ra/Ro) RED calculated from
2.6
10.5
4.4
—
—

HSP distance (Ra) between solvent having boiling point of

250° C. or more and resin particles and Hansen sphere

radius (Ro)

S2
10.0
—
—
—
—

S2/R
1.19
—
—
—
—

S2/S1
—
—
—
—
—

S1 + S2
10
—
—
—
—

Surface tackiness immediately after drying
C
C
A
A
A

Drying unevenness
A
A
A
A
A

Storage stability (room temperature)
∘
∘
∘
∘
∘

Solvent resistance
120° C. × 1 min
—
—
—
—
—

110° C. × 1 min
C
C
C
C
C

90° C. × 1 min
—
—
—
—
—

(*1): Acrylic resin emulsion, manufactured by Japan Coating Resin Corp.

(*2): Acrylic resin emulsion, manufactured by Japan Coating Resin Corp.

(*3): Acrylic resin emulsion, manufactured by SEIKO PMC CORPORATION

(*4): Vinyl chloride-acrylic copolymer emulsion, manufactured by Nissin Chemical Industry Co., Ltd.

(*5): Acetylene glycol-based surfactant (ethylene oxide of diol (10 mol)) adduct, manufactured by Nissin Chemical Industry Co., Ltd., active ingredient = 100%

(*6): Aqueous dispersion of C.I. Pigment Red 122 (containing resin dispersant): numerical values in table indicate pigment solid blending amount.

(*7): Aqueous dispersion of C.I. Pigment Blue 15:3 (containing resin dispersant): numerical values in table indicate pigment solid blending amount.

(*8): Aqueous dispersion of carbon black: numerical values in table indicate pigment solid blending amount.

(*9): Aqueous dispersion of C.I. Pigment Yellow 155 (containing resin dispersant): numerical values in table indicate pigment solid blending amount.

TABLE 5

Boiling
Comparative
Comparative
Comparative
Comparative
Comparative

point
Example 6
Example 7
Example 8
Example 9
Example 10

Solvent
Dipropylene glycol methyl ether (DPM)
188

Propylene glycol (PG)
188

29.5
25.0

1,3-propanediol
214
23.0
13.0
13.0

1,2-hexanediol
223

Dipropylene glycol n-butyl ether (DPnB)
230

Polyethylene glycol 400 (PEG 400)
250

2-pyrolidone
251

Tripropylene glycol (TPG)
270

5.0
15.0
1.0

Tripropylene glycol n-butyl ether (TPnB)
274

Triethylene glycol (TEG)
276

Triethylene glycol monobutyl ether (BTG)
278

3.0

Glycerin (Gly)
290

Polyethylene glycol monomethyl ether
300

Polymer R
Mowinyl ® 6969D (*1)
8.4
8.4
6.0
4.0
5.0

*Solid content
Mowinyl ® 6899D (*2)

concentration
JE-1056 (*3)

Vinyblan ® 715S (*4)

Surfactant
Olfine ® E1004 (*5)
1.0
1.0
1.0
2.0
1.0

Color material
Pigment dispersion A (*6)

2.6

2.5

*Solid content
Pigment dispersion B (*7)
2.8

concentration
Pigment dispersion C (*8)

Pigment dispersion D (*9)

3.2

4.0