AU2018373095B2 - Aqueous liquid ink and printed article - Google Patents

Abstract

The present invention addresses the problem of providing an aqueous liquid ink which exhibits fundamental characteristics as an aqueous liquid ink (adhesion to a base material, blocking resistance, a high printing density, and the like), and which also exhibits high water resistance (boil retort properties) and solvent resistance. This aqueous liquid ink includes a colouring agent (A), a binder (B) having acid groups, a basic compound (C), and an aqueous medium (D). The binder (B) having acid groups includes a urethane resin (B1) which is a reaction product of a polyisocyanate (b2), and a polyol (b1) including at least one from among a polyol (b1-1) having acid groups, a polyester polyol (b1-2), and a polycarbonate polyol (b1-3). The content of alicyclic structures in the urethane resin (B1) is at least 1,000 mmol/kg. The basic compound (C) includes at least one from among a basic metal compound (C1) and an organic amine (C2).

Description

DESCRIPTION

Title: AQUEOUS LIQUID INK AND PRINTED ARTICLE

Technical Field

[0001]

The present disclosure relates to an aqueous liquid ink

that can be used for water-based printing, and to a printed

article printed using an aqueous liquid ink.

Background

[0002]

Gravure printing and flexography are widely used to

give esthetics and functionality to printed material. In

recent years, the printing ink industry has faced a growing

demand for a turn to aqueous printing inks as they are

viewed as a solution to problems with solvent-based printing

inks, such as environmental issues including air pollution,

occupational health and safety concerns including organic

solvent poisoning, and dangers including ignition and

explosion, and also from the perspectives of operational

safety and hygiene, environmental protection, the reduction

of residual solvents in packaging, etc. Indeed, aqueous

printing inks have been increasingly used in commercial

printing, for example of wrapping paper and paper-made

containers such as cardboard boxes.

[0003]

As an example of such an aqueous printing ink, a

surface-printing water-based ink for packaging has been

proposed. This ink contains, as a binder, a water-based

polyurethane resin obtained by reacting an isocyanate

containing polymer with a polyhydrazide compound and a

polyamine compound other than the polyhydrazide compound and

making the resulting polyurethane resin water-soluble by

neutralizing an organic solution of the resin with a

deionized water containing aqueous ammonia (e.g., see PTL 1:

Japanese Unexamined Patent Application Publication No. 8

53641)

[0004]

Also proposed is a water-based printing ink composition

for lamination. This ink composition is made with a water

based polyurethane resin obtained by reacting an organic

diisocyanate compound with a polymeric diol compound

containing a particular polycarbonate diol and with a chain

extender and making the resulting resin water-based by

adding water and trimethylamine (e.g., see PTL 2: Japanese

Unexamined Patent Application Publication No. 5-171091).

Citation List

Patent Literature

[00051

PTL 1: Japanese Unexamined Patent Application

Publication No. 8-53641

PTL 2: Japanese Unexamined Patent Application

Publication No. 5-171091

[0005a] Any discussion of documents, acts, materials, devices,

articles or the like which has been included in the present

specification is not to be taken as an admission that any or

all of these matters form part of the prior art base or were

common general knowledge in the field relevant to the present

disclosure as it existed before the priority date of each of

the appended claims.

[0005b]

Throughout this specification the word "comprise", or

variations such as "comprises" or "comprising", will be

understood to imply the inclusion of a stated element, integer

or step, or group of elements, integers or steps, but not the

exclusion of any other element, integer or step, or group of

elements, integers or steps.

Summary

[00061

Aqueous printing inks, however, are slow to dry

compared with solvent-based inks. Besides the essential

performance attributes of adhesion to plastic substrates and freedom from blocking, requirements include, for example, good dispersion of pigment(s) therein, and it is difficult to improve print density while fulfilling all of these. For example, the surface-printing water-based ink for packaging described in PTL 1 and the water-based printing ink composition for lamination described in PTL 2 may be lacking in essential performance for use as aqueous liquid inks.

Moreover, the water-based printing ink composition for

lamination described in PTL 2, occasionally but notably, is

by no means one that can withstand long-run printing.

[0007]

An aim of at least a preferred embodiment of the

present disclosure is to provide an aqueous liquid ink that

meets essential performance requirements for use as an

aqueous liquid ink (adhesion to substrates, freedom from

blocking, high print density, etc.) and also combines high

waterproofness (boilability/retortability) and resistance to

solvents. By virtue of combining these performance

attributes, the ink can provide, when used as an aqueous

liquid ink (in particular, an aqueous liquid ink for

printing on laminated packaging materials), a printed

article that can withstand even boiling and retort

treatment.

[0008]

The present disclosure provides the use of a binder for water-based flexo inks that contains a urethane resin that has an acid group neutralized with basic compounds including a basic metal compound and an organic amine.

[00091

That is, the present disclosure relates to an aqueous

liquid ink that contains a colorant (A), a binder having an

acid group (B), at least one basic compound (C), and an

aqueous medium (D). The binder having an acid group (B)

contains a urethane resin (B1) that is a product of reaction

between polyols (bl) including at least one selected from

the group consisting of a polyol having an acid group (bl-1)

and a polyester polyol (bl-2) and a polycarbonate polyol

(bl-3) and a polyisocyanate (b2), and the alicyclic

structure content of the urethane resin (B1) is 1,000

mmol/kg or more in the total amount of the urethane resin

(B1). The basic compound (C) includes at least one selected

from the group consisting of a basic metal compound (Cl) and

an organic amine (C2).

[0010]

The present disclosure provides an aqueous liquid ink

that not only has essential performance attributes for use

as an aqueous liquid ink (adhesiveness, anti-blocking

properties, high print density, etc.) but also combines high

waterproofness (boilability/retortability) and high

resistance to solvents.

[0010a]

In one aspect the present disclosure provides an

aqueous liquid ink comprising a colorant (A), a binder

having an acid group (B), at least one basic compound (C),

and an aqueous medium (D), wherein:

the binder having an acid group (B) contains a urethane

resin (B1) that is a product of reaction between polyols

(b1) and at least one polyisocyanate (b2);

the polyols (b1) include: a polyol having an acid group

(bl-1), at least one selected from the group consisting of a

polyester polyol (bl-2) and a polycarbonate polyol (bl-3),

and a polyol having an alicyclic structure (bl-4);

the total percentage of the polyol having an acid

group (bl-1), the polyester polyol (bl-2), the polycarbonate

polyol (bl-3), and the polyol having an alicyclic structure

(bl-4) is 70% by mass or more in the polyols (b1);

a percentage of the polyol having an alicyclic

structure (bl-4) is 20% by mass or less in a total amount of

the polyols (b1);

the polyisocyanate (b2) includes a polyisocyanate

having an alicyclic structure;

an alicyclic structure content of the urethane resin

(B1) is 1,000 mmol/kg or more and 5,000 mmol/kg or less in a

total amount of the urethane resin (B1); and

the basic compound (C) includes at least one selected from the group consisting of a basic metal compound (Cl) and an organic amine (C2).

Description of Embodiments

[0011]

An aqueous liquid ink according to the present

disclosure contains at least one colorant (A), a binder

having an acid group (B), at least one basic compound (C),

and at least one aqueous medium (D).

[0012]

The colorant (A) can be one or two or more colorants.

Examples include pigments, such as organic or inorganic

pigments, and dyes. Colorants used in, for example, inks,

paints, and recording agents are preferred.

Examples of organic pigments include pigments such as

azo, phthalocyanine, anthraquinone, perylene, perinone,

quinacridone, thioindigo, dioxazine, isoindolinone,

quinophthalone, azomethine-azo, diketopyrrolopyrrole, and

isoindoline pigments.

[0013]

Examples of inorganic pigments include carbon black,

titanium oxide, zinc oxide, zinc sulfide, barium sulfate,

calcium carbonate, chromium oxide, silica, red iron oxide,

aluminum, and mica. Shiny pigments produced by coating

glass flakes or lump flakes as a base material with a metal or metal oxide (Metashine; Nippon Sheet Glass Co., Ltd.) can also be used.

[0014]

By color index name, examples include:

C.I. Pigment Yellow 1, 3, 12, 13, 14, 17, 42, 74, and

83;

C.I. Pigment Orange 16;

C.I. Pigment Red 5, 22, 38, 48:1, 48:2, 48:4, 49:1,

53:1, 57:1, 63:1, 81, and 101;

C.I. Pigment Violet 19 and 23;

C.I. Pigment Blue 23, 15:1, 15:3, 15:4, 17:1, 18, 27,

and 29

C.I. Pigment Green 7, 36, 58, and 59;

C.I. Pigment Black 7; and

C.I. Pigment White 4, 6, and 18.

[0015]

For cyan ink, C.I. Pigment Blue 15:3 (copper

phthalocyanine) is preferred. For yellow ink, C.I. Pigment

Yellow 83 is preferred in terms of cost and light fastness.

For magenta ink, C.I. Pigment Red 57:1 is preferred. For

white, black, gold/silver, and pearl inks, titanium oxide,

carbon black, aluminum, and mica, respectively, are

preferred in terms of cost and tinctorial strength.

Aluminum is in powder or paste form, but preferably is used

in paste form for the sake of ease of handling and safety.

As for which type of aluminum to use, leafing or non

leafing, an appropriate type is selected considering

brightness felt and density.

[0016]

To ensure sufficient density and tinctorial strength of

the ink, the total percentage of the pigment(s) is

preferably 1% by mass or more in the total amount of the

ink, preferably 50% by mass or less.

[0017]

The binder having an acid group (B) contains a urethane

resin (B1) that is a product of reaction between polyols

(bl) including at least one selected from the group

consisting of at least one polyol having an acid group (bl

1) and at least one polyether polyol (bl-2) and at least one

polycarbonate polyol (bl-3) and at least one polyisocyanate

(b2).

[0018]

The acid value of the urethane resin (B1) is preferably

3 mg KOH/g or more, more preferably 5 mg KOH/g or more,

preferably 40 mg KOH/g or less, more preferably 30 mg KOH/g

or less. As used herein, an acid value refers to a

theoretical calculation based on the amount of, for example,

acid group-containing compounds used to produce the urethane

resin (B1), such as the polyol having an acid group (bl-1).

[0019]

The urethane resin (B1), moreover, contains an

alicyclic structure. By virtue of containing an alicyclic

structure, the urethane resin (B1) helps reduce blocking of

printed articles. Examples of alicyclic structures include

saturated C3 to C10 (preferably C4 to C8) monocyclic

structures, such as the cyclobutyl ring, the cyclopentyl

ring, the cyclohexyl ring, the cycloheptyl ring, the

cyclooctyl ring, and the propylcyclohexyl ring; and

saturated C5 to C20 (preferably C7 to C12) bridged cyclic

structures, such as the tricyclo[5.2.1.0.2.6]decyl

structure, the bicyclo[4.3.0]nonyl structure, the

tricyclo[5.3.1.1]dodecyl structure, the

propyltricyclo[5.3.1.1]dodecyl structure, the norbornyl

structure, the isobornyl structure, the dicyclopentanyl

structure, and the adamantyl structure. Of these, saturated

monocyclic structures are particularly preferred, and the

cyclohexyl ring structure is more preferred.

[0020]

The alicyclic structure content of the urethane resin

(B1) is 1,000 mmol/kg or more in the total amount of the

urethane resin (B1), preferably 1,200 mmol/kg or more, more

preferably 1,500 mmol/kg or more, preferably 5,000 mmol/kg

or less, more preferably 3,000 mmol/kg or less, even more

preferably 2,500 mmol/kg or less.

As mentioned herein, the proportion of alicyclic structures in the urethane resin (B1) is a calculation based on the total mass of the polyols (b1), polyisocyanate (b2), and all other raw materials used to produce the urethane resin (B1) and the amount of substance of alicyclic structures in the compound(s) containing an alicyclic structure used to produce the urethane resin (A) (polyol(s) having an alicyclic structure (bl-3) and/or polyisocyanate(s) having an alicyclic structure).

[0021]

The urethane resin (B1), furthermore, may contain an

aromatic ring. If the urethane resin (B1) contains an

aromatic ring, its amount is preferably 0 mmol/kg or more in

the total amount of the urethane resin (B1), more preferably

500 mmol/kg or more, even more preferably 1,000 mmol/kg or

more, preferably 4,000 mmol/kg or less, more preferably

3,000 mmol/kg or less, even more preferably 2,500 mmol/kg or

less.

[0022]

The alicyclic structure may be contained in the polyols

(b1) or may be contained in the polyisocyanate (b2). The

ratio between the alicyclic structure content, by the number

of moles, derived from the polyisocyanate (b2) and that from

the polyols (b1) is 0 or more, preferably 0.05 or more, more

preferably 0.1 or more, even more preferably 0.2 or more,

preferably 10 or less, more preferably 8 or less, even more preferably 5 or less.

[0023]

The acid group in the polyol having an acid group (bl

1) can be, for example, a carboxy or sulfonic acid group.

The polyol having an acid group (bl-1) can be, for example,

at least one polyol having a carboxy group or at least one

polyol having a sulfonic acid group.

[0024]

The polyol having a carboxy group can be one or two or

more of such polyols. Examples include hydroxy acids, such

as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic

acid, and 2,2-dimethylolvaleric acid; and polyester polyols

having a carboxy group. Polyester polyols having a carboxy

group can be obtained by reacting a hydroxy acid with

polycarboxylic acids.

[0025]

The polyol having a sulfonic acid group can be one or

two or more of such polyols. Examples include polyester

polyols that are products of reaction between a dicarboxylic

acid having a sulfonic acid group or its salt and a low

molecular-weight polyol (e.g., with a molecular weight of

100 or more and 1000 or less). Examples of dicarboxylic

acids having a sulfonic acid group include 5

sulfoisophthalic acid, sulfoterephthalic acid, 4

sulfophthalic acid, and 5-(4-sulfophenoxy)isophthalic acid.

Examples of low-molecular-weight polyols include C1-10

alkanediols, such as ethylene glycol, propylene glycol, 1,4

butanediol, 1,6-hexanediol, and neopentyl glycol; and C2-10

polyether polyols, such as diethylene glycol.

[0026]

The number-average molecular weight of the polyol

having an acid group (bl-1) is preferably 100 or more,

preferably 2000 or less, more preferably 1000 or less.

As mentioned herein, number-average and weight-average

molecular weights are polystyrene-equivalent values measured

by gel permeation chromatography (GPC).

[0027]

The polyester polyol (bl-2) can be, for example,

polyester polyol(s) resulting from esterification of a low

molecular-weight polyol (e.g., a polyol having a molecular

weight of 50 or more and 300 or less) and a polycarboxylic

acid; polyester polyol(s) resulting from ring-opening

polymerization of a cyclic ester compound, such as e

caprolactone; and/or polyester polyol(s) that is

copolymer(s) thereof.

[0028]

Examples of low-molecular-weight polyols include

polyols having a relatively low molecular weight (e.g., a

molecular weight of 50 or more and 300 or less), such as

ethylene glycol, diethylene glycol, 1,2-propylene glycol, dipropylene glycol, neopentyl glycol, 2-butyl-2-ethyl-1,3 propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5 pentanediol, 1,4-cyclohexanediol, 1,6-hexanediol, and cyclohexanedimethanol.

[0029]

Examples of polycarboxylic acids include aliphatic

polycarboxylic acids, such as succinic acid, adipic acid,

sebacic acid, and dodecanedicarboxylic acid; aromatic

polycarboxylic acids, such as terephthalic acid, isophthalic

acid, phthalic acid, and naphthalenedicarboxylic acid; and

anhydrides or ester-forming derivatives of such aliphatic

and aromatic polycarboxylic acids.

[0030]

For the sake of compatibility with, for example,

pigments, the number-average molecular weight of the

polyester polyol (bl-2) is preferably 500 or more, more

preferably 1,000 or more, preferably 4,000 or less, more

preferably 3,000 or less.

[0031]

The polycarbonate polyol (bl-3) can be, for example,

product(s) of reaction between a carbonate and a polyol;

and/or product(s) of reaction between phosgene and a polyol

or similar compound.

[0032]

Examples of carbonates include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonates, and diphenyl carbonate.

[00331

Examples of polyols that can react with carbonates and

phosgene include the polyols listed above as examples of

low-molecular-weight polyols; and high-molecular-weight

polyols (with a weight-average molecular weight of 500 or

more and 5,000 or less), such as polyether polyols (e.g.,

polyethylene glycol and polypropylene glycol) and polyester

polyols (e.g., polyhexamethylene adipate). In particular,

polyols containing an aromatic ring are preferred.

[0034]

For the sake of compatibility with, for example,

pigments, the number-average molecular weight of the

polycarbonate polyol (bl-3) is preferably 500 or more, more

preferably 1,000 or more, preferably 4,000 or less, more

preferably 3,000 or less.

[00351

In the polyols (bl), the percentage of the

polycarbonate polyol (bl-3) in the total of the polyester

polyol (bl-2) and polycarbonate polyol (bl-3) is preferably

% by mass or more, more preferably 10% by mass or more,

even more preferably 20% by mass or more, preferably 100% by

mass or less, more preferably 90% by mass or less, even more

preferably 80% by mass or less.

[0036]

Preferably, the polyols (b1) include at least a

polycarbonate polyol (bl-3). In the polyols (b1), the

percentage of the polycarbonate polyol (bl-3) is preferably

% by mass or more, more preferably 5% by mass or more, even

more preferably 10% by mass or more,

preferably 100% by mass or less, more preferably 90% by mass

or less, even more preferably 80% by mass or less.

[0037]

The total percentage of the polyol having an acid group

(bl-1), polyester polyol (bl-2), and polycarbonate polyol

(bl-3) is preferably 60% by mass or more in the polyols

(b1), more preferably 75% by mass or more, more preferably

% by mass or more, even more preferably 90% by mass or

more and may be 95% by mass or less.

[00381

Preferably, the polyols (b1) further include at least

one polyol having an alicyclic structure (bl-4).

The polyol having an alicyclic structure (bl-4) can be

one or two or more of such polyols. Examples include

saturated diols having an alicyclic structure, such as

cyclobutanediol, cyclopentanediol, 1,4-cyclohexanediol,

cycloheptanediol, cyclooctanediol, butylcyclohexanediol,

cyclohexanedimethanol, hydroxypropylcyclohexanol,

dicyclohexanediol, hydrogenated bisphenol A, and 1,3- adamantanediol; unsaturated diols having an alicyclic structure, such as 1,1'-bicyclohexylidenediol; and saturated trials having an alicyclic structure, such as cyclohexanetriol. The number-average molecular weight of the polyol having an alicyclic structure (bl-4) is preferably 100 or more and 500 or less.

[00391

If a polyol having an alicyclic structure (bl-4) is

used, its percentage is preferably 0% by mass or more in the

total amount of the polyols (bl) for reduced blocking of

printed articles, more preferably 5% by mass or more,

preferably 40% by mass or less, preferably 25% by mass or

less, more preferably 20% by mass or less, even more

preferably 10% by mass or less.

[0040]

The total percentage of the polyol having an acid group

(bl-1), polyester polyol (bl-2), polycarbonate polyol (bl

3), and polyol having an alicyclic structure (bl-4) is

preferably 70% by mass or more in the polyols (bl), more

preferably 80% by mass or more, even more preferably 90% by

mass or more.

[0041]

The polyols (bl) may include extra polyols (bl-5).

Examples of extra polyols include polyether polyols, low

molecular-weight polyols (e.g., with a molecular weight of or more and 300 or less), and polyolefin polyols.

[0042]

Examples of polyether polyols (bl-2) include polymers

produced by addition polymerization of an alkylene oxide

performed using one or two or more compounds having two or

more groups bearing an active hydrogen atom (-NH- or -OH) as

initiator(s).

[0043]

Examples of initiators include compounds having two

hydroxyl groups, such as ethylene glycol, diethylene glycol,

triethylene glycol, propylene glycol, trimethylene glycol,

1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, and

bisphenol A; and compounds having three hydroxyl groups,

such as glycerol, trimethylolethane, and trimethylolpropane.

[0044]

Examples of alkylene oxides include epoxide compounds,

such as ethylene oxide, propylene oxide, butylene oxide,

styrene oxide, and epichlorohydrin; and C4 or larger

(preferably C4-6, in particular C4) cyclic ethers, such as

tetrahydrofuran.

[0045]

For the sake of compatibility with, for example,

pigments, the number-average molecular weight of a polyether

polyol is preferably 500 or more, more preferably 1,000 or

more, preferably 4,000 or less, more preferably 3,000 or less.

As mentioned herein, number-average molecular weights

represent values measured by gel permeation chromatography

(GPC).

[0046]

Low-molecular-weight polyols can be polyols having a

molecular weight of roughly 50 or more and 300 or less.

Examples include C2 to C6 aliphatic polyols, such as

ethylene glycol, propylene glycol, 1,4-butanediol, 1,5

pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol,

diethylene glycol, dipropylene glycol, neopentyl glycol, and

1,3-butanediol; polyols containing an alicyclic structure,

such as 1,4-cyclohexanediol and cyclohexanedimethanol; and

polyols containing an aromatic structure, such as bisphenol

compounds, e.g., bisphenol A and bisphenol F, and their

alkylene oxide adducts.

[0047]

Examples of polyolefin polyols include polyisobutene

polyols, hydrogenated polybutadiene polyols, and

hydrogenated polyisoprene polyols.

[0048]

The percentage of extra polyols (bl-5) is preferably

% by mass or less in the polyols (bl), more preferably 40%

by mass or less, even more preferably 30% by mass or less,

further preferably 20% by mass or less, in particular 10% by mass or less.

[0049]

The polyisocyanate (b2) can be one or two or more

polyisocyanates. Examples include aromatic polyisocyanates,

such as 4,4'-diphenylmethane diisocyanate, 2,4'

diphenylmethane diisocyanate, carbodiimide-modified

diphenylmethane diisocyanate, crude diphenylmethane

diisocyanate, phenylene diisocyanate, tolylene diisocyanate,

naphthalene diisocyanate, xylylene diisocyanate, and

tetramethylxylylene diisocyanate; aliphatic polyisocyanates,

such as hexamethylene diisocyanate and lysine diisocyanate;

and polyisocyanates having an alicyclic structure, such as

cyclohexane diisocyanate, hydrogenated xylylene

diisocyanate, isophorone diisocyanate, and

dicyclohexylmethane diisocyanate.

[0050]

Preferably, the polyisocyanate (b2) includes a

polyisocyanate having an alicyclic structure. The

percentage of the polyisocyanate having an alicyclic

structure is preferably 50% by mass or more in the

polyisocyanate (b2), more preferably 80% by mass or more,

even more preferably 90% by mass or more, preferably 100% by

mass or less.

[0051]

The proportion of the number of equivalents, by the number of moles, of isocyanate groups in the polyisocyanate

(b2) to that of hydroxyl groups in the polyols (b1)

[isocyanate groups/hydroxyl groups] is preferably 0.8 or

more, more preferably 0.9 or more, preferably 2.5 or less,

more preferably 2.0 or less, even more preferably 1.5 or

less.

[0052]

In the production of the urethane resin (B1), at least

one chain extender may optionally be used.

[0053]

The chain extender can be one or two or more extenders.

Examples include polyamines, hydrazine compounds, and other

compounds having an active hydrogen atom.

[0054]

Examples of polyamines include diamines, such as

ethylenediamine, 1,2-propanediamine, 1,6

hexamethylenediamine, piperazine, 2,5-dimethylpiperazine,

isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'

dimethyl-4,4'-dicyclohexylmethanediamine, 1,4

cyclohexanediamine, N-ethylaminoethylamine, and N

methylaminopropylamine; diamines having a hydroxy group,

such as N-hydroxymethylaminoethylamine, N

hydroxyethylaminoethylamine, and N

hydroxypropylaminopropylamine; triamines, such as

diethylenetriamine and dipropylenetriamine; and tetramines, such as triethylenetetramine. Of these, ethylenediamine is particularly preferred.

[00551

Examples of hydrazine compounds include hydrazine,

N,N'-dimethylhydrazine, 1,6-hexamethylenebishydrazine,

succinic dihydrazide, adipic dihydrazide, glutaric

dihydrazide, sebacic dihydrazide, isophthalic dihydrazide,

$-semicarbazidopropionic hydrazide, 3 semicarbazidopropyl

carbazate, and semicarbazido-3-semicarbazidomethyl-3,5,5

trimethylcyclohexane.

[00561

Examples of other compounds having an active hydrogen

include glycols, such as ethylene glycol, diethylene glycol,

triethylene glycol, propylene glycol, 1,3-propanediol, 1,3

butanediol, 1,4-butanediol, hexamethylene glycol,

saccharose, methylene glycol, glycerol, and sorbitol;

phenols, such as bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'

dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone,

hydrogenated bisphenol A, and hydroquinone, and water.

[0057]

If the chain extender is, for example, polyamine(s),

the ratio between the number of equivalents of amino groups

and that of isocyanate groups in the polyamine(s) [amino

groups/isocyanate groups] is preferably 1.2 or less, more

preferably in the range of 0.3 or more and 1 or less.

[0058]

For improved durability of printed articles, the

weight-average molecular weight of the urethane resin (A) is

preferably 5,000 or more, more preferably 10,000 or more,

even more preferably 20,000 or more, preferably 500,000 or

less, more preferably 200,000 or less, even more preferably

100,000 or less. Increasing the weight-average molecular

weight not only helps improve the durability of printed

articles, but also helps reduce, for example, blocking

caused by incomplete drying. Ensuring the weight-average

molecular weight is moderately small helps reduce, for

example, incomplete transfer and resolubility of the ink.

[00591

The urethane resin (B1) can be produced by reacting the

polyols (b1) and the polyisocyanate (b2), optionally with

chain extender(s). The reaction between the polyols (b1)

and the polyisocyanate (b2) may be done in the presence of

at least one organic solvent. Preferably, the polyols (b1)

and the polyisocyanate (b2) are allowed to react at a

temperature of 500C or more and 1500C or less.

[00601

The organic solvent can be one or two or more solvents.

Examples include ketone solvents, such as acetone and methyl

ethyl ketone; ether solvents, such as tetrahydrofuran and

dioxane; ester solvents, such as ethyl acetate and butyl acetate; nitrile solvents, such as acetonitrile; and amide solvents, such as dimethylformamide and N-methylpyrrolidone.

[0061]

As an attempt at safety and/or reducing environmental

burdens, the organic solvent may be partially or completely

removed, for example by vacuum distillation, during or after

the production of the urethane resin (B1).

[0062]

The percentage of the urethane resin (B1) is preferably

% by mass or more in the binder having an acid group (B),

more preferably 95% by mass or more, even more preferably

99% by mass or more, in particular 100% by mass.

[0063]

The binder having an acid group (B) may be dispersed

beforehand in the aqueous medium (D), described later

herein. An example of a method for dispersing the urethane

resin (B1) in the aqueous medium (D) (making the ink water

based) is to prepare the binder having an acid group (B)

(binder (B) preparation step), mix the resulting binder

having an acid group (B) with at least a subset of the basic

compound (C), described later herein (neutralization step),

and mix the resulting mixture with the aqueous medium (D) to

make a liquid dispersion (dispersion step).

If chain extender(s) is used, the chain extender(s) may

be added in the binder (B) preparation step or may be added after the dispersion step.

[0064]

For the sake of resolubility of the aqueous ink,

reduced blocking of printed articles, improved print

density, and adhesion to substrates, the percentage of the

binder having an acid group (B) is preferably 10% by mass or

more in the liquid dispersion, more preferably 20% by mass

or more, preferably 50% by mass or less, more preferably 40%

by mass or less.

[0065]

During the process of making the ink water-based, an

emulsifier may optionally be used. During the aqueous

dissolution or aqueous dispersion, a homogenizer or similar

machinery may optionally be used.

Examples of emulsifiers include nonionic emulsifiers,

such as polyoxyethylene nonyl phenyl ether, polyoxyethylene

lauryl ether, polyoxyethylene styryl phenyl ether,

polyoxyethylene sorbitol tetraoleate, and polyoxyethylene

polyoxypropylene copolymers; anionic emulsifiers, such as

sodium oleate and other fatty acid salts, alkyl sulfates,

alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene

sulfonate, polyoxyethylenealkyl sulfates, sodium

alkanesulfonates, and sodium salts of alkyl diphenyl ether

sulfonic acids; and cationic emulsifiers, such as salts of

alkylamines, alkyltrimethylammonium salts, and alkyldimethylbenzylammonium salts. In particular, anionic or nonionic emulsifiers are preferred in terms of storage stability.

[00661

The basic compound (C) includes at least one selected

from the group consisting of a basic metal compound (Cl) and

an organic amine (C2).

Examples of basic metal compounds (Cl) include metal

hydroxides, such as sodium hydroxide, potassium hydroxide,

lithium hydroxide, calcium hydroxide, and magnesium

hydroxide; metal chlorides, such as sodium chloride and

potassium chloride; and metal sulfates, such as copper

sulfate.

[0067]

Examples of organic amines (C2) include ammonia;

primary amines, such as monoethanolamine; tertiary amines,

such as triethylamine and diethylethanolamine; and cyclic

amines, such as morpholine.

Preferably, the basic compound (C) includes at least an

organic amine (C2).

[00681

The proportion represented by the formula below is

preferably 0.001 or more, more preferably 0.01 or more, even

more preferably 0.05 or more and is 0.3 or less, preferably

0.25 or less, more preferably 0.2 or less, even more preferably 0.15 or less. Ensuring this proportion is in these ranges leads to good boilability/retortability.

The number of moles of the basic metal compound (Cl) x

the valency of the basic metal compound (Cl) / {(the number

of moles of the organic amine (C2) x the valency of the

organic amine (C2) + (the number of moles of the basic metal

compound (Cl) x the valency of the basic metal compound

(Cl))

[00691

The basic metal compound (Cl) and organic amine (C2)

may be in salt form with the acid group in the binder having

an acid group (B) in the aqueous liquid ink. Neutralization

of the acid group in the binder having an acid group by the

basic compound (Cl) and organic amine (Cl) helps improve the

aqueous dispersibility of the binder.

[0070]

The basic compound (C) content is preferably 0.01 parts

by mass or more per 100 parts by mass of the binder having

an acid group (B), more preferably 0.05 parts by mass or

more, even more preferably 0.1 parts by mass or more,

preferably 10 parts by mass or less, more preferably 7 parts

by mass or less, even more preferably 4 parts by mass or

less.

[0071]

For the aqueous medium (D), examples include water; at least one hydrophilic organic solvent; and a mixture of water and at least one hydrophilic organic solvent. In terms of safety and addition to the environment, water or a mixture of water and at least one hydrophilic organic solvent is preferred.

The hydrophilic organic solvent can be one or two or

more of such solvents, preferably water-miscible one(s).

Examples include alcohol solvents, such as methanol,

ethanol, n-propanol, and 2-propanol; ketone solvents, such

as acetone and methyl ethyl ketone; polyhydric alcohol

solvents, such as ethylene glycol, diethylene glycol,

propylene glycol, polyalkylene glycols, and glycerol; ether

solvents, such as propylene glycol monomethyl ether,

propylene glycol monoethyl ether, propylene glycol mono-n

propyl ether, and ethyl carbitol; and amide solvents, such

as N-methyl-2-pyrrolidone.

[0072]

If the aqueous medium (D) includes water and

hydrophilic organic solvent(s), the percentage of water is

preferably 80% by mass or more in the aqueous medium (D),

more preferably 85% by mass or more, even more preferably

% by mass or more. For example, the percentage of water

may be 100% by mass or less, and even a percentage of 95% by

mass or less is acceptable.

[0073]

The aqueous liquid ink according to the present

disclosure may further contain auxiliaries. The auxiliaries

may alternatively be the following ones, which are used on

an as-needed basis: waxes for imparting, for example,

abrasion resistance and sliding smoothness, such as paraffin

waxes, polyethylene waxes, and carnauba wax; fatty acid

amide compounds, such as oleic acid amide, stearic acid

amide, and erucic acid amide; silicone or non-silicone

antifoams for controlling foaming during printing;

dispersants, etc.

[0074]

For dispersants, nonionic dispersants are preferred.

The acid value of a dispersant is preferably 30 mg

KOH/g or less, more preferably 25 mg KOH/g or less, even

more preferably 20 mg KOH/g or less. For example, the acid

value may be 1 mg KOH/g or more, or may even be 3 mg KOH/g

or more.

Preferably, the acid value of the dispersant is smaller

than that of the binder having an acid group (B). The

difference between the acid value of the binder having an

acid group (B) and that of the dispersant is, for example, 1

mg KOH/g or more, more preferably 3 mg KOH/g or more,

preferably 30 mg KOH/g or less, more preferably 20 mg KOH/g

or less.

[0075]

The dispersant content is preferably 40 parts by mass

or more per 100 parts by mass of the colorant (A), more

preferably 50 parts by mass or more, even more preferably 60

parts by mass or more, preferably 100 parts by mass or less,

more preferably 80 parts by mass or less, even more

preferably 75 parts by mass or less.

The dispersant content is preferably 10 parts by mass

or more per 100 parts by mass of the binder having an acid

group (B), more preferably 20 parts by mass or more, even

more preferably 30 parts by mass or more, preferably 100

parts by mass or less, more preferably 80 parts by mass or

less, even more preferably 60 parts by mass or less.

[0076]

The viscosity of the aqueous liquid ink is preferably 7

seconds or more as a measurement taken at 250C using a Rigo

Zahn cup #4, more preferably 10 seconds or more, preferably

seconds or less, more preferably 20 seconds or less.

In millipascal-seconds, the viscosity is preferably 70

(mPa-s) or more at 250C, more preferably 100 (mPa-s) or more,

preferably 350 (mPa-s) or less, more preferably 250 (mPa-s)

or less.

[0077]

The surface tension of the aqueous liquid ink is

preferably 25 mN/m or more, more preferably 33 mN/m or more,

preferably 50 mN/m or less, more preferably 43 mN/m or less.

Ensuring the surface tension of the ink is moderately high

helps reduce dot bridging (type of dirt on the print surface

that occurs when adjacent dots in halftone-dot areas join

together) while maintaining wettability of the ink on

substrates. Ensuring the surface tension of the ink is

moderately small helps increase the wettability of the ink

on substrates and thereby reduce repellence.

[0078]

The aqueous liquid ink according to the present

disclosure can be produced using equipment that is common in

the production of gravure and flexographic inks, such as an

Eiger mill, a sand mill, a gamma mill, or an attritor.

[0079]

In the preparation of the aqueous liquid ink according

to the present disclosure, a precursory composition (milled

base ink) may be prepared to ensure uniformity. The

precursory composition is prepared by mixing together the

colorant (A), at least part of the binder having an acid

group (B), at least a subset or part of the basic compound

(C), a dispersant as described above, and at least a subset

or part of the aqueous medium (D).

[0080]

The aqueous liquid ink according to the present

disclsoure is superior in adhesion to different substrates;

can be used for printing on paper, synthetic paper, thermoplastic resin films, plastic products, sheet steel, etc.; is a useful ink for gravure printing, in which an electronically engraved or similar gravure plate is used, or for flexography, in which a resin or similar flexographic plate is used; and, at the same time, is not an ink for inkjet printing, in which ink is ejected from inkjet nozzles without using a plate. That is, with an inkjet ink, ink droplets ejected from nozzles adhere directly to a substrate and form a printed article. With the aqueous liquid ink according to the present disclosure, the printing ink is once attached/transferred to a printing plate or printing pattern, and then only the ink is attached again, to a substrate this time, optionally followed by drying, to make a printed article.

The thickness of a film of printing ink formed by

gravure printing or flexography using the aqueous liquid ink

according to the present disclosure is, for example, 10 pm

or less, preferably 5 pm or less.

[0081]

Examples of substrates include films of thermoplastic

resins, such as polyamide resins, e.g., nylon 6, nylon 66,

and nylon 46, polyester resins, e.g., polyethylene

terephthalate (PET), polyethylene naphthalate,

polytrimethylene terephthalate, polytrimethylene

naphthalate, polybutylene terephthalate, and polybutylene naphthalate, polyhydroxycarboxylic acids, e.g., polylactic acid, biodegradable resins, e.g., poly(ethylene succinate), poly(butylene succinate), and other aliphatic polyester resins, polyolefin resins, e.g., PP and polyethylene, polyimide resins, polyarylate resins, and mixtures thereof as well as a stack of such films, but in particular, polyester, polyamide, polyethylene, and polypropylene films are suitable for use. These substrate films may be non oriented films or oriented films and are not limited to a particular production process. The thickness of the substrate film is not critical either, but usually it only needs to be in the range of 1 to 500 pm.

Preferably, the print surface of the substrate film has

been treated with a corona discharge. There may be a

deposited coating of silica or alumina, for example, on the

print surface.

EXAMPLES

[00821

The following describes the present disclosure in

detail by examples and comparative examples.

[00831

(Synthesis Examples 1 to 10 and Comparative Synthesis

Examples 1 to 3: Preparation of Binders (1) to (13))

In a nitrogen-purged vessel equipped with a thermometer, a nitrogen inlet tube, and a stirrer, the polyols (bl) specified in Table 1 and the polyisocyanate

(b2) specified in Table 1 were allowed to react in methyl

ethyl ketone to give an organic solution of a urethane

prepolymer having a terminal isocyanate group (binder having

an acid group).

Then the basic compound (C) or aqueous solution of a

basic compound (C) specified in Table 1 was added to

neutralize some or all of the carboxy groups in the urethane

prepolymer, and the mixture was stirred thoroughly with

water and the aqueous solution of a chain extender specified

in Table 1, giving an aqueous dispersion of urethane resin.

Then the dispersion was aged, and the solvent was

eliminated. In this way, binders (1) to (13) were obtained

with a non-volatile content of 40% by mass.

For the binders (1) to (13) obtained, the alicyclic

structure content and aromatic ring content of the urethane

resin and the acid value are presented in Table 1.

[00841

[Table 1] Syntesi ExapleCornparative SynthesisExample Synthesis Example 1 2 3 4 5 6 7 8 9 10 1 2 3 Binder No. (1) (2) (3) (4) (5) (6) (7) (8) (9) (10) (11) (12) (13) (bl-1) 2,2-Dimethylolpropionic acid 15 13 19 20 9 16 25 17 13 17 27 19 32 231 197 125 (b1-2) Polyester polyol 1 Polyester polyol 2 228 224 92 Polycarbonate polyol 1 290 280 250 166 184 279 258 Polyols (b1) (b1-3) Polycarbonate polyol 2 218 (b1-4) 1,4-Cyclohexanedimethanol 35 41 18 14 15 12 13 23 4 8 29 7 3 (b1-5) Neopentylglycol Polyether polyol 1 198 Polyisocyanate Isophorone diisocyanate 119 148 135 141 86 93 145 110 92 100 147 96 107 (b2) Basic metal 50% by mass aqueous solution 17 45 compound (Cl) of potassium hydroxide Basiccompoun rganicamine25% by mass aqueous ammonia 13 11 18 (C) O Dimethylethanolamine 19 8 23 22 27 31 83 Triethylamine Chain extender 80% by mass aqueous solution of hydrazine 4 4 6 2 3 6 3 6 5 9 6 5 Alicyclic structure content (mmol/kg) 40 40 40 40 40 40 40 40 40 40 40 40 40 Aromatic ring content (mmol/kg) 19182181 1787 1747 1170 1218 1659 1485 1016 1157 2120 1182 990 Acid value (mg KOH/g) 16 14 20 21 10 16 26 18 14 18 28 20 34 Unit: parts by mass

[0085]

In Table 1, polyester polyol 1 represents an aliphatic

polyester polyol (Daicel Corporation "L212AL"; number

average molecular weight, 1,250), polyester polyol 2

represents an aromatic polyester polyol (an aromatic

polyester polyol produced by reacting 13.1 parts by mass of

ethylene glycol, 22.0 parts by mass of neopentyl glycol,

18.5 parts by mass of terephthalic acid, 18.5 parts by mass

of isophthalic acid, and 7.9 parts by mass of acrylic acid

in the presence of 0.03 parts by mass of monobutyltin oxide;

number-average molecular weight, 1,000), polycarbonate

polyol 1 represents a polycarbonate polyol (Ube Industries,

Ltd. "ETERNACOLL UH-200"; number-average molecular weight,

2,000), polycarbonate polyol 2 represents a polycarbonate

polyol (Ube Industries, Ltd. "ETERNACOLL UH-100"; number

average molecular weight, 1000), and polyether polyol 1

represents a polytetraethylene glycol (number-average

molecular weight, 2,000).

[00861

Examples 1 to 10 and Comparative Examples 1 to 3

Binders (1) to (13), obtained in the Synthesis Examples

and Comparative Synthesis Examples, were each stirred and

mixed well in accordance with the formula below. The

resulting mixtures were milled in a bead mill to give milled

base inks. The resulting milled base inks were respectively mixed with another 10 parts by mass of binders (1) to (13) and another 4 parts by mass of water, giving aqueous blue printing inks. The viscosity of the resulting printing inks was adjusted with water to be 16 seconds (250C) as measured with a Zahn cup #4 (Rigo). The inks obtained were respectively named aqueous liquid inks of Examples 1 to 10 and Comparative Examples 1 to 3.

[0087]

The surface tension of the resulting aqueous liquid

inks was checked by measuring their surface tension at 25°C.

The measurement of the surface tension was based on the

Wilhelmy method and performed using Kyowa Interface Science

Co., Ltd. DY-300 automatic surface tensiometer.

[0088]

[Formula of the Milled Base Inks]

FASTOGEN BLUE LA5380 cyan pigment (DIC) 15 parts by

mass

Binder for aqueous flexographic inks 40 parts by mass

Nonionic pigment dispersant (BYK)10 parts by mass

Isopropyl alcohol 3 parts by mass

Water 8 parts by mass

Silicone antifoam (BYK) 0.2 parts by mass

[0089]

[Total Amounts in the Aqueous Liquid Inks (blue) (excluding

water for viscosity adjustment)]

FASTOGEN BLUE LA5380 cyan pigment (DIC) 15 parts by

mass

Binder for aqueous flexographic inks 50 parts by mass

Nonionic pigment dispersant (BYK)10 parts by mass

Isopropyl alcohol 3 parts by mass

Water 12 parts by mass

Silicone antifoam (BYK) 0.2 parts by mass

[00901

The aqueous liquid inks of the Examples and Comparative

Examples were applied to the corona-treated polyethylene

terephthalate (PET) film (Toyobo Co., Ltd. ESTER E5102;

thickness, 12 pm) and corona-treated biaxially oriented

polypropylene (OPP) film (Toyobo Co., Ltd. PYLEN P2161;

thickness, 20 pm) specified in Table 1 using Flexiproof 100

test printer (Testing Machines, Inc.) to print a 240-mm long

by 80-mm wide solid image. The printed image was dried

using a hair dryer, giving printed articles.

[0091]

The resulting printed articles were tested for

boilability/retortability, resistance to solvents, freedom

from blocking, and adhesion to substrate for each type of

film. The ink transfer was checked on the basis of print

density.

[0092]

[Test Item 1: Boilability/Retortability (resistance to hot water)]

The ink side of the printed article made with a corona

treated polyethylene terephthalate (PET) film was coated

with DICDRY LX-500/KW-75 urethane-based dry-lamination

adhesive (DIC) to a coating density of 3.5 g/m 2 , dried, and

then laminated with aluminum foil (hereinafter AL; Toyo

Aluminum Kogyo K.K., Aluminum Foil C, 15 pm) using a dry

laminator (DIC Engineering), giving two-layer laminate 1.

Then the AL of laminate 1 was likewise coated with the

adhesive, cast polypropylene film (hereinafter R-CPP; Toray

Plastic Films ZK-75, 50 pm) was placed thereon, and the

resulting stack was aged at 400C for 5 days, giving three

layer composite laminate 2.

The resulting laminate 2 was shaped into a 120 mm x 120

mm pouch, and 70 g of simulated food, a mixture of vinegar,

salad oil, and Bolognese meat sauce in a 1:1:1 weight ratio,

was sealed in the pouch. After 30 minutes of retort

sterilization of the pouch with steam at 135°C, the

delamination of the ink coating was evaluated in four

grades.

0: No signs of delamination.

0: Only a very few small delamination blisters.

A: Medium-sized delamination blisters are observed in

part.

x: Signs of delamination, whether large or small, are observed throughout.

[0093]

[Test Item 2: Resistance to Solvents]

The printed article prepared was rubbed ten times with

a cotton swab soaked in ethanol, and the erasure of the

print was graded. A commercially available laminate with a

best-before date inkjet-printed thereon was used as a

reference standard. The criteria for grading were as

follows.

0: A good result; none of the print was erased.

0: A good result; 80% or more of the print was left.

A: 50% of the print was erased.

x: 100% of the print was erased.

[0094]

[Test Item 3: Freedom from Blocking]

The film was cut to a 4 cm x 4 cm size, and the cut

pieces were put on top of one another with the printed side

of the printed article on the non-printed side. The stack

was left under 400C conditions for 12 hours under a load of

2 Kgf/cm , then the pieces of film were separated, and the

ink transfer (setoff) to the non-printed side was visually

assessed on the basis of the percentage area (%) of setoff.

0: No transfer to the non-printed side.

0: Setoff transfer is observed, although as small as

less than 5%.

A: 5% or more to less than 20% setoff transfer is

observed.

x: 20% or more setoff transfer is observed.

[0095]

[Test Item 4: Adhesion to the Substrate]

Adhesive tape (Nichiban, 12-mm wide) was attached to

the printed side of a printed article that had been aged for

one day. An end of the tape was pulled off at right angles

to the surface of the print, and the appearance was visually

assessed on the basis of the percentage of the remaining

print coating.

0: No print coating is removed.

0: 80% or more and less than 90% of the print coating

remained on the film.

A: 50% or more and less than 80% of the print coating

remained on the film.

x: Only less than 50% of the print coating remained on

the film.

[0096]

[Test Item 5: Ink Transfer]

Ink transfer was graded on the basis of the solid

density of the printed article measured using X-Rite

SpectroEye densitometer.

0: Ink transfer is good; the cyan density of the

printed article is 1.9 or more.

A: Ink transfer is intermediate; the cyan density of

the printed article is 1.6 or more and less than 1.9.

x: Ink transfer is poor; the cyan density of the

printed article is less than 1.6.

[0097]

By using the aqueous liquid ink according to the

present disclosure, one can provide an aqueous liquid ink

that meets essential performance requirements for use as an

aqueous liquid ink (adhesion to substrates, freedom from

blocking, high print density, etc.) and also combines high

waterproofness (boilability/retortability) and resistance to

solvents. By virtue of combining these performance

attributes, the ink can provide a printed article that can

withstand even boiling and retort treatment.

[Table 2]

Example Comparative Example 1 2 3 4 5 6 7 8 9 10 1 2 3 Surface tension (mN/m) 32 34 27 28 43 32 30 32 37 30 23 24 Boilability/Retortability 0 0 0 0 0 0 0 0 0 0 x x Ethanol 0 0 0 0 0 0 0 0 0 0 x 0 Resistance to solvents AO Alkali 0 0 0 0 0 0 0 0 0 0 X n A () PET 0 0 0 0 0 0 0 0 0 0 0 x Freedom from blocking ® ® ® ® ® ® ® ® 0 0 0 A

PET 0 0 0 0 0 0 0 0 0 0 0 0 Adhesion to substrate AhsotosbtaeOPP P 0 ___ __ 0 ___ 0 ___ 0 0 ____O 0 0 0 0 0 O 0 O 9 0 FF PET 0 0 0 0 0 0 0 0 0 0 0 0 Ink transfer P O O O O O O O O O O O O

Claims (6)

1. [Claim 1]

   An aqueous liquid ink comprising a colorant (A), a

   binder having an acid group (B), at least one basic

   compound (C), and an aqueous medium (D), wherein:

   the binder having an acid group (B) contains a

   urethane resin (B1) that is a product of reaction between

   polyols (b1) and at least one polyisocyanate (b2);

   the polyols (b1) include:

   a polyol having an acid group (bl-1),

   at least one selected from the group consisting

   of a polyester polyol (bl-2) and a polycarbonate

   polyol (bl-3), and

   a polyol having an alicyclic structure (bl-4);

   the total percentage of the polyol having an acid

   group (bl-1), the polyester polyol (bl-2), the

   polycarbonate polyol (bl-3), and the polyol having an

   alicyclic structure (bl-4) is 70% by mass or more in the

   polyols (b1);

   a percentage of the polyol having an alicyclic

   structure (bl-4) is 20% by mass or less in a total amount

   of the polyols (b1);

   the polyisocyanate (b2) includes a polyisocyanate

   having an alicyclic structure;

   an alicyclic structure content of the urethane resin

   (B1) is 1,000 mmol/kg or more and 5,000 mmol/kg or less in a total amount of the urethane resin (B1); and the basic compound (C) includes at least one selected from the group consisting of a basic metal compound (Cl) and an organic amine (C2).
2. [Claim 2]

   The aqueous liquid ink according to Claim 1, wherein

   the percentage of the polyol having an alicyclic structure

   (bl-4) is 5% by mass or more and 20% by mass or less in a

   total amount of the polyols (bl).
3. [Claim 3]

   The aqueous liquid ink according to Claim 1 or 2,

   wherein an acid value of the binder having an acid group

   (B) is 3 mg KOH/g or more and 40 mg KOH/g or less.
4. [Claim 4]

   The aqueous liquid ink according to any one of Claims

   1 to 3, wherein the ink has a surface tension of 25 mN/m or

   more and 50 mN/m or less at 25°C.
5. [Claim 5]

   The aqueous liquid ink according to any one of Claims

   1 to 4, wherein the ink is an aqueous gravure ink or

   aqueous flexographic ink.
6. [Claim 6]

   A printed article comprising a print made using an

   aqueous liquid ink according to any one of Claims 1 to 5.