AU2020240710B2 - Resin composition for aqueous coating materials, and coating film - Google Patents

Abstract

The present invention provides a resin composition for aqueous coating materials, which enables the production of an aqueous coating material that is capable of forming a coating film that has excellent initial gloss, initial water resistance and gloss retainability. A resin composition for aqueous coating materials according to the present invention is characterized by containing a copolymer which contains a styrene monomer unit, an acrylic monomer unit and an unsaturated fatty acid salt unit, while having a glass transition temperature of from -4°C to 40°C; and this resin composition for aqueous coating materials enables the production of an aqueous coating material that is capable of forming a coating film that has excellent initial gloss, initial water resistance and gloss retainability.

Description

PCT/JP2020/11949 (Y-283)

DESCRIPTION

Title of Invention: RESIN COMPOSITION FOR AQUEOUS COATING

MATERIAL AND COATING FILM

Technical Field

[0001] The present invention relates to a resin

composition for an aqueous coating material and a coating

film.

Background Art

[0002] Conventionally, solvent-based coating materials

have been widely used for coating surfaces of building

materials such as exterior materials used for construction of

buildings. As solvent-based resins used in solvent-based

coating materials, styrene-(meth)acrylate copolymers with

styrene and (meth)acrylate serving as main monomer units are

generally used because of its excellent initial gloss and

initial water resistance.

[0003] On the other hand, in recent years, also in the

field of coating materials, in order to improve the burden on

the use environment and the global environment caused by

volatile organic compounds, a transition from solvent-based

coating materials including organic solvents to aqueous

coating materials including aqueous solvents has been rapidly

accelerated. Although development of resins for aqueous

coating materials has been advanced with this transition to

aqueous coating materials, a problem regarding resins for

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aqueous coating materials exists in that initial gloss and

initial water resistance are inferior to those of solvent

based resins such as styrene-(meth)acrylate copolymers.

[0004] Accordingly, Patent Literature 1 discloses a resin

composition for a coating material including a resin emulsion

obtained by emulsion polymerization of monomer components. The

resin composition uses a plurality of emulsifiers when the

monomer components are subjected to emulsion polymerization.

Citation List

Patent Literature

[0005] Patent Literature 1: Japanese Patent Application

Laid-Open No. 2017-125219

Summary of Invention

Technical Problem

[0006] However, coating films of aqueous coating materials

produced using the above-mentioned resin compositions for

coating material have a problem in which the initial gloss is

still insufficient.

[0007] In addition, the coating films of aqueous coating

materials produced using the above-mentioned resin

compositions for coating material has a problem in which the

gloss deteriorates with time due to adhesion of water or the

like (meaning that its initial water resistance is

insufficient).

[00081 The present invention provides a resin composition

PCT/JP2020/11949 (Y-283)

for an aqueous coating material that can be used for producing

an aqueous coating material capable of forming a coating film

which has excellent initial gloss and initial water

resistance.

Solution to Problem

[00091 A resin composition for an aqueous coating material

of the present invention includes a copolymer that includes a

styrene-based monomer unit, an acrylic monomer unit, and an

unsaturated fatty acid salt unit, and has a glass transition

temperature of -4 to 400 C.

[0010] A coating film of the present invention is a

solidified product of an applied layer of the above-mentioned

resin composition for an aqueous coating material on an object

to be coated.

Advantageous Effects of Invention

[00111 The resin composition for an aqueous coating

material of the present invention can produce an aqueous

coating material capable of forming a coating film which has

excellent initial gloss and excellent initial water

resistance.

Description of Embodiments

[0012] The resin composition for an aqueous coating

material of the present invention includes a copolymer that

includes a styrene-based monomer unit, an acrylic monomer unit,

and an unsaturated fatty acid salt unit, and has a glass

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transition temperature of -4 to 400 C.

[0013] The resin composition for an aqueous coating

material includes a copolymer that includes a styrene-based

monomer, an acrylic monomer unit, and an unsaturated fatty

acid salt unit.

[0014] Examples of the styrene-based monomer constituting

the copolymer include, but are not particularly limited to,

styrene, a-methylstyrene, p-methylstyrene, methylstyrene,

tert-butylstyrene, chlorostyrene, and vinyltoluene. Styrene is

preferably used from the viewpoint of the initial gloss of the

coating film formed from the resin composition for an aqueous

coating material. Note that the styrene-based monomers may be

used alone, or two or more kinds thereof may be used in

combination.

[0015] A benzene ring of the styrene-based monomer may

have a functional group such as an alkyl group such as a

methyl group and a tert-butyl group, a nitro group, a nitrile

group, an alkoxyl group, an acyl group, a sulfone group, a

hydroxyl group and a halogen atom.

[0016] The content of the styrene-based monomer unit in

the copolymer is preferably 5% by mass or more, more

preferably 10% by mass or more, still more preferably 15% by

mass or more, still more preferably 20% by mass or more, and

particularly preferably 25% by mass or more, from the

viewpoint of the initial gloss of the coating film formed from

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the resin composition for an aqueous coating material. The

content of the styrene-based monomer unit in the copolymer is

preferably 50% by mass or less, more preferably 45% by mass or

less, still more preferably 40% by mass or less, and

particularly preferably 35% by mass or less, from the

viewpoint of the weather resistance of the coating film formed

from the resin composition for an aqueous coating material.

[00171 Examples of the acrylic monomer that constitutes

the copolymer include, but are not particularly limited to, an

alkyl (meth)acrylate such as methyl (meth)acrylate, ethyl

(meth)acrylate, n-propyl (meth)acrylate, isopropyl

(meth)acrylate, n-butyl (meth)acrylate, isobutyl

(meth)acrylate, tert-butyl (meth)acrylate, sec-butyl

(meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl

(meth)acrylate, tridecyl (meth)acrylate, n-lauryl

(meth)acrylate, dodecyl (meth)acrylate, and stearyl

(meth)acrylate; an alicyclic (meth)acrylate such as cyclohexyl

(meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl

(meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate,

dicyclopentanyl (meth)acrylate, and adamantanyl

(meth)acrylate, a nitrogen-containing (meth)acrylic monomer

such as (meth)acrylonitrile, (meth)acrylamide, and diacetone

(meth)acrylamide, acrylic acid, methacrylic acid, itaconic

acid, crotonic acid, rheic acid, fumaric acid, citraconic

acid, maleic acid (anhydride), and citraconic acid

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(anhydride).

[0018] The acrylic monomer is preferably an alkyl

(meth)acrylate or (meth)acrylic acid, more preferably includes

an alkyl (meth)acrylate and methacrylic acid, and particularly

preferably includes an alkylacrylate, an alkyl methacrylate,

and methacrylic acid. Note that the acrylic monomer may be

used alone, or two or more kinds thereof may be used in

combination. (Meth)acrylate means acrylate or methacrylate.

(Meth)acrylic acid means acrylic acid or methacrylic acid.

[0019] The content of the acrylic monomer unit in the

copolymer is preferably 30% by mass or more, more preferably

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

more, and particularly preferably 55% by mass or more, from

the viewpoint of the weather resistance of the coating film

formed from the resin composition for an aqueous coating

material. The content of the acrylic monomer unit in the

copolymer is preferably 80% by mass or less, more preferably

75% by mass or less, and particularly preferably 70% by mass

or less, from the viewpoint of the initial gloss of the

coating film formed from the resin composition for an aqueous

coating material.

[0020] The number of carbon atoms of the alkyl group in

the alkyl (meth)acrylate is preferably 1 or more, more

preferably 2 or more, and particularly preferably 3 or more,

from the viewpoint of the initial gloss of the coating film

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formed from the resin composition for an aqueous coating

material. The number of carbon atoms of the alkyl group in the

alkyl (meth)acrylate is preferably 15 or less, more preferably

12 or less, and particularly preferably 10 or less, from the

viewpoint of the drying property of the aqueous coating

material formed from the resin composition for an aqueous

coating material.

[0021] The alkyl (meth)acrylate preferably includes methyl

(meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl

LO (meth)acrylate, and n-butyl (meth)acrylate, and more

preferably includes methyl methacrylate, isobutyl

methacrylate, 2-ethylhexyl acrylate, and n-butylacrylate.

[0022] The content of the alkyl (meth)acrylate unit in the

copolymer is preferably 30% by mass or more, more preferably

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

more, and particularly preferably 55% by mass or more, from

the viewpoint of the weather resistance of the coating film

formed from the resin composition for an aqueous coating

material. The content of the alkyl (meth)acrylate unit in the

copolymer is preferably 80% by mass or less, more preferably

75% by mass or less, and particularly preferably 70% by mass

or less, from the viewpoint of the initial gloss of the

coating film formed from the resin composition for an aqueous

coating material.

[0023] The content of the (meth)acrylic acid unit in the

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copolymer is preferably 0.01% by mass or more, more preferably

0.05% by mass or more, and particularly preferably 0.1% by

mass or more, from the viewpoint of the stability of the

emulsion particles in the aqueous coating material. The

content of the (meth)acrylic acid unit in the copolymer is

preferably 4% by mass or less, more preferably 3% by mass or

less, still more preferably 2% by mass or less, and

particularly preferably 1% by mass or less, from the viewpoint

of the initial water resistance of the coating film formed

LO from the resin composition for an aqueous coating material.

[0024] The content of the methacrylic acid unit in the

copolymer is preferably 0.01% by mass or more, more preferably

0.05% by mass or more, and particularly preferably 0.1% by

mass or more, from the viewpoint of the stability of the

.5 emulsion particles in the aqueous coating material. The

content of the methacrylic acid unit in the copolymer is

preferably 4% by mass or less, more preferably 3% by mass or

less, still more preferably 2% by mass or less, and

particularly preferably 1% by mass or less, from the viewpoint

of the initial water resistance of the coating film formed

from the resin composition for an aqueous coating material.

[0025] The unsaturated fatty acid salt constituting the

copolymer is a reactive emulsifier. The reactive emulsifier

has an emulsifying property. The unsaturated fatty acid salt

is a salt of a monocarboxylic acid represented by RCOOH,

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wherein the substituent represented by R includes at least one

unsaturated bond. The unsaturated fatty acid salt is

incorporated into the polymer chain of the copolymer by

radical polymerization with the unsaturated bonds. The

unsaturated fatty acid salts may be used alone, and two or

more kinds thereof may be used in combination.

[0026] Since the copolymer includes the unsaturated fatty

acid salt unit, the copolymer has a hydrophobic moiety and a

hydrophilic moiety. The copolymer can take a micellar

structure in which the hydrophobic moiety is located inside

and the hydrophilic moiety is located outside, so that the

copolymer can be dispersed in an aqueous medium to constitute

an aqueous coating material. Note that the aqueous medium is

not particularly limited, and examples thereof include water,

an alcohol-based solvent (e.g., methanol, ethanol, propanol,

isopropanol, butanol, and the like), and a glycol ether-based

solvent (e.g., an ethylene glycol monoethyl ether, a propylene

glycol monomethyl ether, a butyl diglycol, and the like).

Among these, water is preferable.

[0027] The unsaturated fatty acid salt includes an

unsaturated bond in the substituent R. The substituent R takes

a bent structure in the unsaturated bond moiety. The

substituent R with the bent structure can cause the copolymer

to be brought into a state in which the copolymer is

accommodated into the micelle in place while the hydrophobic

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moiety thereof is bent, so that the dispersibility of the

copolymer in an aqueous medium is improved.

[0028] The unsaturated bond in the substituent R is not

particularly limited, but is preferably an ethylenically

unsaturated bond such as an ethylenically unsaturated double

bond (carbon-carbon double bond) and an ethylenically

unsaturated triple bond (carbon-carbon triple bond), and is

more preferably an ethylenically unsaturated double bond.

Although the ethylenically unsaturated double bond can be a

cis-double bond or a trans-double bond, a cis-double bond is

preferable because it can cause the copolymer to be brought

into a state in which the copolymer is accommodated into the

micelle in place while the hydrophobic moiety thereof is

encapsulated.

[0029] The number of the unsaturated bonds in the

substituent R is preferably 1 to 6, more preferably 1 to 5,

and particularly preferably 1 to 4. When the number of carbon

atoms of the substituent R is 11 or more, it is preferable to

have the unsaturated bond between carbon atoms at the third or

subsequent positions counted from the carbon atom at the

terminal of the substituent R (the terminal of the longest

chain in the substituent R). It is more preferable to have the

unsaturated bond between carbon atoms at the fifth or

subsequent positions counted from the carbon atom at the

terminal of the substituent R, and it is particularly

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preferable to have the unsaturated bond between carbon atoms

at the sixth or subsequent positions counted from the carbon

atom at the terminal of the substituent R.

[0030] The number of carbon atoms of the unsaturated fatty

acid salt (the total number of carbon atoms possessed by the

unsaturated fatty acid salt) is preferably 4 or more, more

preferably 12 or more, and particularly preferably 16 or more,

from the viewpoint of the stability of the emulsion particles

in the aqueous coating material. The number of carbon atoms of

the unsaturated fatty acid salt (the total number of carbon

atoms possessed by the unsaturated fatty acid salt) is

preferably 30 or less, more preferably 28 or less, and

particularly preferably 26 or less, from the viewpoint of the

water solubility of the unsaturated fatty acid salt.

[0031] The unsaturated fatty acid (named according to

IUPAC) used as a raw material for the unsaturated fatty acid

salt is not particularly limited. Examples thereof include

butenoic acid (C4), pentenoic acid (CS), hexenoic acid (C6),

heptenoic acid (C7), octenoic acid (C8), nonenoic acid (C9),

decenoic acid (C1o), undecenoic acid (C11), dodecenoic acid

(C12), tridecenoic acid (C13), tetradecenoic acid (C14),

pentadecenoic acid (C15), hexadecenoic acid (C16),

heptadecenoic acid (C17), octadecenoic acid (C18),

nonadecenoic acid (C19), icosenoic acid (C20), henicosenoic

acid (C21), docosenoic acid (C22), tricosenoic acid (C23),

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tetracosenoic acid (C24), pentacosenoic acid (C25),

hexacosenoic acid (C26), heptacosenoic acid (C27),

octacosenoic acid (C28), nonacosenoic acid (C29), and

triacontenoic acid (C30). Among these, it is preferable to

include octadecenoic acid. Note that the symbol in parentheses

represents the total number of carbon atoms possessed by each

unsaturated fatty acid.

[0032] Specific examples (trivial names) of the

unsaturated fatty acid used as a raw material of the

L0 unsaturated fatty acid salt include myristoleic acid (C14, 1

bond, B5), palmitoleic acid (C16, 1 bond, B7), stearidonic

acid (C18, 4 bonds, B3, 6, 9, 12), vaccenic acid (C18, 1 bond,

B7), oleic acid (C18, 1 bond, B9), elaidic acid (C18, 1 bond,

B9), linoleic acid (C18, 2 bonds, B6, 9), a-linolenic acid

(C18, 3 bonds, B3, 6, 9), y-linolenic acid (C18, 3 bonds, B6,

9, 12), gadoleic acid (C20, 1 bond, B11), eicosenoic acid

(C20, 1 bond, B11), eicosadienoic acid (C20, 2 bonds, B6, 9),

arachidonic acid (C20, 3 bonds, B6, 9, 12), eicosapentaenoic

acid (C20, 5 bonds, B3, 6, 9, 12, 15), erucic acid (C22, 1

bond, B9), docosahexaenoic acid (C22, 6 bonds, B3, 6, 9, 12,

15, 18), and nervonic acid (C24, 1 bond, B9). Among these, it

is preferable to include palmitoleic acid, oleic acid and

linoleic acid, more preferable to include oleic acid and

linoleic acid, and particularly preferable to include oleic

acid. Note that the symbols in parentheses represent, in

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order, the total number of carbon atoms, the number of

ethylenically unsaturated double bonds, and the position of

the ethylenically unsaturated double bond(s). The symbols of

Bn , m, .. , p indicates that the unsaturated fatty acid has

an ethylenically unsaturated double bond(s) between carbon

atoms at the nth position and (n+l)th position, at the mth

position and (m+l)th position, ... , and the pth position and

(p+l)th position counted from the carbon atom at the terminal

of the substituent R.

[00331 As described above, the unsaturated fatty acid salt

may be used alone, and two or more kinds thereof may be used

in combination. A salt of an animal or vegetable oil fatty

acid containing a plurality of kinds of unsaturated fatty

acids may be used.

[0034] Examples of the animal or vegetable oil fatty acid

salts include a soybean oil fatty acid salt, a cottonseed oil

fatty acid salt, a tall oil fatty acid salt (a salt of a

mixture of palmitic acid, stearic acid, oleic acid, and

linoleic acid), a corn oil fatty acid salt, a rice bran oil

fatty acid salt, a safflower oil fatty acid salt, a sunflower

oil fatty acid salt, a linseed oil fatty acid salt, a fish oil

fatty acid salt, a dehydrated castor oil fatty acid salt, a

palm oil fatty acid salt, a beef fat acid salts, a rapeseed

oil fatty acid salt, and an olive oil fatty acid salt. Among

these, a tall oil fatty acid salt is preferable.

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[0035] The unsaturated fatty acid salt may be a derivative

thereof. The derivative of the unsaturated fatty acid salt is

not particularly limited, and examples thereof include a

polymerized fatty acid salt, a salt of an unsaturated

carboxylic acid adduct, a salt of an epoxidized unsaturated

fatty acid, a salt of a hydroxylated unsaturated fatty acid, a

salt of an epoxidized and hydroxylated unsaturated fatty acid,

and a salt of a sulfonated unsaturated fatty acid. Among

these, a polymerized fatty acid salt is preferable, a dimer

acid salt and a trimer acid salt are more preferable, and a

dimer acid salt is particularly preferable. Note that

derivatives of unsaturated fatty acid salts need to have an

unsaturated bond in its molecule.

[0036] The polymerized fatty acid salt is a salt of a

compound obtained by polymerizing an unsaturated fatty acid,

as necessary, in the presence of a catalyst such as clay.

Examples thereof include a dimer acid salt (a salt of a dimer

of an unsaturated fatty acid), a trimer acid (a salt of a

trimer of an unsaturated fatty acid), and a tetramer acid (a

salt of a tetramer of an unsaturated fatty acid). Among these,

a dimer acid salt and a trimer acid salt are preferable. It is

preferable to include a dimer acid salt and a trimer acid salt.

Note that the polymerized fatty acid salts may be used alone,

and two or more kinds thereof may be used in combination.

[0037] The polymerized fatty acid salt may be partially

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hydrogenated, but it is necessary that the polymerized fatty

acid salt still have an unsaturated bond.

[0038] Examples of the salt of the unsaturated carboxylic

acid adduct include a salt of a compound obtained by

subjecting an unsaturated bond of the above-mentioned

unsaturated fatty acid to an addition reaction with an a,p

unsaturated carboxylic acid. Specific examples thereof include

a salt of an adduct of maleic acid or an anhydride thereof

with an unsaturated fatty acid, and a salt of an acrylic acid

adduct with an unsaturated fatty acid. It is necessary that

the salt of the unsaturated carboxylic acid adduct still have

an unsaturated bond.

[0039] The salt of the epoxidized unsaturated fatty acid

is a salt of a compound obtained by subjecting an unsaturated

bond of an unsaturated fatty acid to an epoxidation reaction

with, for example, peracetic acid or hydrogen peroxide. The

salt of the hydroxylated unsaturated fatty acid is one

obtained by hydrolyzing a salt of an epoxidized unsaturated

fatty acid, which may lead to introduce two hydroxyl groups.

The salt of the sulfonated unsaturated fatty acid is a salt of

a compound obtained by subjecting an unsaturated bond of an

unsaturated fatty acid to a sulfonation reaction with a

sulfuric acid or the like. It is necessary that the salt of

the epoxidized unsaturated fatty acid, the salt of the

hydroxylated unsaturated fatty acid, and the salt of the

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sulfonated unsaturated fatty acid still have an unsaturated

bond.

[0040] The content of the unsaturated fatty acid salt unit

in the copolymer is preferably 0.5% by mass or more, more

preferably 0.7% by mass or more, and particularly preferably

1.0% by mass or more, because of the stability of the emulsion

particles in the aqueous coating material. The content of the

unsaturated fatty acid salt unit in the copolymer is

preferably 5.0% by mass or less, and more preferably 4.5% by

mass or less, from the viewpoint of the initial water

resistance of the coating film formed from the resin

composition for an aqueous coating material.

[0041] In the polymerized fatty acid salt, the content of

the dimmer acid salt is preferably 5% by mass or more, more

preferably 15% by mass or more, more preferably 40% by mass or

more, more preferably 60% by mass or more, more preferably 70%

by mass or more, and particularly preferably 80% by mass or

more, from the viewpoint of the initial water resistance of

the coating film formed from the resin composition for an

aqueous coating material.

[0042] In the polymerized fatty acid salt, the content of

the dimer acid salt is preferably 99% by mass or less, more

preferably 97% by mass or less, more preferably 95% by mass or

less, and particularly preferably 87% by mass or less, from

the viewpoint of the initial gloss of the coating film formed

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from the resin composition for an aqueous coating material.

[0043] In the polymerized fatty acid salt, the content of

the trimer acid salt is preferably 1% by mass or more, more

preferably 3% by mass or more, more preferably 5% by mass or

more, more preferably 7% by mass or more, more preferably 10%

by mass or more, and particularly preferably 13% by mass or

more, from the viewpoint of the initial water resistance of

the coating film formed from the resin composition for an

aqueous coating material.

[00441 In the polymerized fatty acid salt, the content of

the trimer acid salt is preferably 95% by mass or less, more

preferably 85% by mass or less, more preferably 40% by mass or

less, more preferably 30% by mass or less, and particularly

preferably 20% by mass or less, from the viewpoint of the

initial gloss of the coating film formed from the resin

composition for an aqueous coating material.

[00451 It is preferable that the unsaturated fatty acid

salt include a monomer unsaturated fatty acid salt (monomer

acid salt), a dimer acid salt, and a trimer acid salt. Note

that the "monomer unsaturated fatty acid salt (monomer acid

salt)" refers to an unsaturated fatty acid salt which has not

been polymerized.

[0046] When the unsaturated fatty acid salt includes a

monomer acid salt, a dimer acid salt, and a trimer acid salt,

the content of the monomer acid salt in the unsaturated fatty

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acid salt is preferably 0.5% by mass or more, more preferably

1% by mass or more, more preferably 2% by mass or more, and

particularly preferably 3% by mass or more, from the viewpoint

of the initial gloss of the coating film formed from the resin

composition for an aqueous coating material. The content of

the monomer acid salt in the unsaturated fatty acid salt is

preferably 10% by mass or less, more preferably 8% by mass or

less, more preferably 6% by mass or less, and particularly

preferably 5% by mass or less, from the viewpoint of the

initial water resistance of the coating film formed from the

resin composition for an aqueous coating material.

[0047] When the unsaturated fatty acid salt includes a

monomer acid salt, a dimer acid salt, and a trimer acid salt,

the content of the dimer acid salt in the unsaturated fatty

acid salt is preferably 10% by mass or more, more preferably

20% by mass or more, more preferably 50% by mass or more, and

particularly preferably 70% by mass or more, from the

viewpoint of the initial water resistance of the coating film

formed from the resin composition for an aqueous coating

material. The content of the dimer acid salt in the

unsaturated fatty acid salt is preferably 95% by mass or less,

more preferably 90% by mass or less, and particularly

preferably 85% by mass or less, from the viewpoint of the

initial gloss of the coating film formed from the resin

composition for an aqueous coating material.

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[0048] When the unsaturated fatty acid salt includes a

monomer acid salt, a dimer acid salt, and a trimer acid salt,

the content of the trimer acid salt in the unsaturated fatty

acid salt is preferably 0.5% by mass or more, more preferably

1% by mass or more, more preferably 10% by mass or more, and

particularly preferably 70% by mass or more, from the

viewpoint of the initial water resistance of the coating film

formed from the resin composition for an aqueous coating

material. The content of the trimer acid salt in the

unsaturated fatty acid salt is preferably 90% by mass or less,

more preferably 85% by mass or less, and particularly

preferably 80% by mass or less, from the viewpoint of the

initial gloss of the coating film formed from the resin

composition for an aqueous coating material.

[0049] The copolymer may include a reactive emulsifier

other than the unsaturated fatty acid salt as a monomer unit.

The reactive emulsifier other than the unsaturated fatty acid

salt has an emulsifying property. The reactive emulsifier

other than the unsaturated fatty acid salt has at least one

unsaturated bond in its molecule, and is incorporated into the

copolymer by radical polymerization with an unsaturated bond.

[0050] The unsaturated bond is not particularly limited,

but is preferably an ethylenically unsaturated bond such as an

ethylenically unsaturated double bond (carbon-carbon double

bond, C=C) and an ethylenically unsaturated triple bond

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(carbon-carbon triple bond), and is more preferably an

ethylenically unsaturated double bond. The unsaturated bond

may be included in multiple in the molecule.

[0051] The ethylenically unsaturated double bond is an

unsaturated bond included in a functional group such as an

alkenyl group, a (meth)allyloxyalkyl group, or a

(meth)acryloyl group, for example. Note that (meth)allyl means

allyl or methallyl, and (meth)acryloyl means acryloyl or

methacryloyl.

[0052] Examples of the alkenyl group include a vinyl

group, a (meth)allyl group, a 1-propenyl group, a 2-methyl-1

propenyl group, and an isopropenyl group.

[0053] The reactive emulsifier other than the unsaturated

fatty acid salt is not particularly limited, and examples

thereof include a sulfate ester salt of a polyoxyalkylene

phenyl ether which has at least one functional group including

an ethylenically unsaturated double bond in its molecule, a

sulfosuccinate ester salt of a polyoxyethylene alkyl ether

which has at least one functional group including an

ethylenically unsaturated double bond in its molecule (ester

sodium salt, ester ammonium salt, and the like), a sulfate

ester salt of a polyoxyethylene alkyl ether which has at least

one functional group including an ethylenically unsaturated

double bond in its molecule (ester sodium salt, ester ammonium

salt, and the like), a sulfosuccinate ester salt of a

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polyoxyethylene alkyl phenyl ether which has at least one

functional group including an ethylenically unsaturated double

bond in its molecule (ester sodium salt, ester ammonium salt,

and the like), a sulfate ester salt of a polyoxyalkylene ether

which has at least one functional group including an

ethylenically unsaturated double bond in its molecule (ester

sodium salt, ester ammonium salt, and the like), a sulfate

ester salt of a polyoxyalkylene alkyl phenyl ether which has

at least one functional group including an ethylenically

.0 unsaturated double bond in its molecule (ester sodium salt,

ester ammonium salt, and the like), and an acidic phosphoric

acid (meth)acrylic acid ester-based dispersant which has at

least one functional group including an ethylenically

unsaturated double bond in the molecule. Note that the

reactive emulsifier other than the unsaturated fatty acid salt

may be used alone, and two or more kinds thereof may be used

in combination.

[0054] It is preferable that the reactive emulsifier other

than the unsaturated fatty acid salt have an ethylenically

unsaturated double bond in the vicinity of the molecular

terminal. The phrase "the vicinity of the molecular terminal"

refers to a carbon-carbon bond moiety formed by a terminal

carbon atom and second and third carbon atoms counted from the

terminal carbon atom (first) in a molecular chain composed of

bonded carbon atoms. It is preferable that the reactive

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emulsifier other than the unsaturated fatty acid salt have an

ethylenically unsaturated double bond between the terminal

carbon atom (first carbon atom) and the carbon atom (second

carbon atom) bonded to the terminal carbon atom. It is

preferable that the reactive emulsifier other than the

unsaturated fatty acid salt have an ethylenically unsaturated

double bond between the second and the third carbon atoms

counted from the terminal carbon atom.

[0055] The reactive emulsifier other than the unsaturated

LO fatty acid salt is preferably a sulfate ester salt of a

polyoxyalkylene phenyl ether which has at least one functional

group including an ethylenically unsaturated double bond in

its molecule, more preferably a sulfate ester ammonium salt of

a polyoxyalkylene phenyl ether which has at least one

.5 functional group including an ethylenically unsaturated double

bond in its molecule, and more preferably a sulfate ester

ammonium salt of a polyoxyethylene phenyl ether which has at

least one functional group including an ethylenically

unsaturated double bond in its molecule.

[0056] The sulfate ester salt of a polyoxyalkylene phenyl

ether which has at least one functional group including an

ethylenically unsaturated double bond in its molecule is

preferably a polyoxyethylene styrenated propenyl phenyl ether

sulfate ammonium salt, a polyoxyethylene styrenated propenyl

phenyl ether sulfate sodium salt, a polyoxyethylene propenyl

PCT/JP2020/11949 (Y-283)

phenyl ether sulfate ammonium salt, or a polyoxyethylene

propenyl phenyl ether sulfate sodium salt. It is more

preferably a polyoxyethylene styrenated propenyl phenyl ether

sulfate ammonium salt, and a polyoxyethylene styrenated

propenyl phenyl ether sulfate sodium salt.

[0057] Examples of the reactive emulsifier other than the

unsaturated fatty acid salt include acid anhydride modified

products of rosin glycidyl ester acrylate (Japanese Patent

Application Laid-Open No. Hei. 4-256429), dispersants

described in Japanese Patent Application Laid-Open No. Sho.

63-23725, dispersants described in Japanese Patent Application

Laid-Open No. Sho. 63-240931, and dispersants described in

Japanese Patent Application Laid-Open No. Sho. 62-104802.

[0058] The reactive emulsifier can also be procured as

commercially available products. Examples of such commercially

available products include KAYAMER PM-1 (manufactured by

Nippon Kayaku Co., Ltd.), KAYAMER PM-2 (manufactured by Nippon

Kayaku Co., Ltd.), KAYAMER PM-21 (manufactured by Nippon

Kayaku Co., Ltd.), SE-10N (manufactured by ADEKA Corporation),

NE-10 (manufactured by ADEKA Corporation), NE-20 (manufactured

by ADEKA Corporation), NE-30 (manufactured by ADEKA

Corporation), New Frontier A229E (manufactured by DKS Co.,

Ltd.), New Frontier N-117E (manufactured by DKS Co., Ltd.),

New Frontier N250Z (manufactured by DKS Co., Ltd.), AQUALON

RN-20 (manufactured by DKS Co., Ltd.), AQUALON RN-2025

PCT/JP2020/11949 (Y-283)

(manufactured by DKS Co., Ltd.), AQUALON BC-1025 (manufactured

by DKS Co., Ltd.), AQUALON AR-1025 (manufactured by DKS Co.,

Ltd.), AQUALON HS-10 (manufactured by DKS Co., Ltd.), AQUALON

KH-1025 (manufactured by DKS Co., Ltd.), EMINOL JS-2

(manufactured by Sanyo Chemical Industries, Ltd.), LATEMUL K

180 (manufactured by Kao Corporation), and LATEMUL PD-104

(manufactured by Kao Corporation). The reactive emulsifier is

preferably AQUALON AR-1025 (manufactured by DKS Co., Ltd.).

[0059] In the emulsifier component of the copolymer, the

content of the monomer unit derived from the reactive

emulsifier other than the unsaturated fatty acid salt is

preferably 0 to 70% by mass, more preferably 0 to 50% by mass,

and particularly preferably 0 to 30% by mass, because of the

improvement in the initial water resistance of the coating

film formed from the resin composition for an aqueous coating

material. Note that "0% by mass" means that no monomer unit

derived from the reactive emulsifier other than the

unsaturated fatty acid salt is included in the copolymer.

[0060] When the copolymer includes the reactive

emulsifiers that include the unsaturated fatty acid salt and a

compound other than the unsaturated fatty acid salt as monomer

units, the content of the monomer unit derived from all the

reactive emulsifiers in the copolymer is preferably 0.5% by

mass or more from the viewpoint of the stability of the

emulsion particles in the aqueous coating material. When the

PCT/JP2020/11949 (Y-283)

copolymer includes the reactive emulsifiers that include the

unsaturated fatty acid salt and the compound other than the

unsaturated fatty acid salt as monomer units, the content of

the monomer unit is preferably 4% by mass or less, more

preferably 2% by mass or less, and more preferably 1% by mass

or less, from the viewpoint of the initial water resistance of

the coating film formed from the resin composition for an

aqueous coating material.

[0061] When the copolymer includes the reactive

emulsifiers that include the unsaturated fatty acid salt and a

compound other than the unsaturated fatty acid salt as monomer

units, the ratio (total amount of compound other than

unsaturated fatty acid salt / unsaturated fatty acid salt) of

the total amount of the compound other than the unsaturated

fatty acid salt to the total amount of the unsaturated fatty

acid salt in the reactive emulsifier is preferably 0.2 or

more. The ratio (total amount of compound other than

unsaturated fatty acid salt / unsaturated fatty acid salt) of

the total amount of the compound other than the unsaturated

fatty acid salt to the total amount of the unsaturated fatty

acid salt in the reactive emulsifier is preferably 3 or less,

more preferably 2 or less, more preferably 1.5 or less, and

more preferably 0.5 or less. The ratio of the total amount of

the compound other than the unsaturated fatty acid salt to the

total amount of the unsaturated fatty acid salt being 0.2 or

PCT/JP2020/11949 (Y-283)

more improves the stability of the emulsion particles in the

aqueous coating material, which is preferable. The ratio of

the total amount of the compound other than the unsaturated

fatty acid salt to the total amount of the unsaturated fatty

acid salt being 3 or less improves the initial gloss and the

initial water resistance of the coating film formed from the

resin composition for an aqueous coating material, which is

preferable.

[0062] The copolymer may include a fatty acid-modified

monomer unit. The fatty acid-modified monomer is a compound

obtained by reacting a drying oil fatty acid and/or a semi

drying oil fatty acid with an epoxy group-containing

polymerizable unsaturated monomer by a known method. In place

of the drying oil fatty acid and the semi-drying oil fatty

acid, or in combination with the drying oil fatty acid and/or

the semi-drying oil fatty acid, an unsaturated fatty acid

(not-polymerized unsaturated fatty acid) may be used. The

unsaturated fatty acid may be used alone, and two or more

kinds thereof may be used in combination.

[0063] The content of the fatty acid-modified monomer unit

in the copolymer is preferably 1% by mass or more, more

preferably 2% by mass or more, and particularly preferably 3%

by mass or more, because of the improvement in the initial

water resistance of the coating film formed from the resin

composition for an aqueous coating material. The content of

PCT/JP2020/11949 (Y-283)

the fatty acid-modified monomer unit in the copolymer is

preferably 10% by mass or less, more preferably 8% by mass or

less, and particularly preferably 6% by mass or less, from the

viewpoint of the stability of the emulsion particles in the

aqueous coating material.

[0064] The drying oil fatty acid and the semi-drying oil

fatty acid are fatty acids which have a polymerizable

unsaturated group of an oxidation curable type. Examples of

the drying oil fatty acid and the semi-drying oil fatty acid

include a fish oil fatty acid, a dehydrated castor oil fatty

acid, a safflower oil fatty acid, a linseed oil fatty acid, a

soybean oil fatty acid, a sesame oil fatty acid, a poppy oil

fatty acid, a perilla oil fatty acid, a hemp seed oil fatty

acid, a grape kernel oil fatty acid, a corn oil fatty acid, a

tall oil fatty acid, a sunflower oil fatty acid, a cottonseed

oil fatty acid, a walnut oil fatty acid, and a rubber seed oil

fatty acid, among which a tall oil fatty acid is preferable.

[0065] The drying oil fatty acid and/or the semi-drying

oil fatty acid may be used, as necessary, in combination with,

for example, a non-drying oil fatty acid such as a coconut oil

fatty acid, a hydrogenated coconut oil fatty acid, and a palm

oil fatty acid; caproic acid, capric acid, lauric acid,

myristic acid, palmitic acid, stearic acid, and the like.

[0066] Examples of the epoxy group-containing

polymerizable unsaturated monomer include glycidyl

PCT/JP2020/11949 (Y-283)

(meth)acrylate, -methylglycidyl (meth)acrylate, 3,4

epoxycyclohexylmethyl (meth)acrylate, 3,4

epoxycyclohexylpropyl (meth)acrylate, and allylglycidyl ether.

Among these, glycidyl (meth)acrylate is preferable, and

glycidyl methacrylate is more preferable.

[0067] The salts of the unsaturated fatty acid salts are

not particularly limited, and examples thereof include an

alkali metal salt such as sodium, potassium, and lithium; an

alkaline earth metal salt such as calcium and barium; an

L0 organic amine salt such as an alkanolamine such as

monoethanolamine, diethanolamine, and triethanolamine, and

triethylamine; and an ammonium salt. Among these, an alkali

metal salt and an alkaline earth metal salt are preferable, an

alkali metal salt is more preferable, sodium and potassium

salts are more preferable, and a potassium salt is

particularly preferable.

[00681 The glass transition temperature Tg of the

copolymer constituting the resin composition for an aqueous

coating material is preferably -4°C or higher, more preferably

1°C or higher, and particularly preferably 6°C or higher,

because of the improvement in the initial water resistance and

the gloss retention property of the coating film formed from

the resin composition for an aqueous coating material. The

glass transition temperature Tg of the copolymer constituting

the resin composition for an aqueous coating material is

PCT/JP2020/11949 (Y-283)

preferably 40°C or lower, more preferably 35°C or lower, more

preferably 25°C or lower, more preferably 23°C or lower, and

particularly preferably 19°C or lower, because of the

improvement in the initial gloss of the coating film formed

from the resin composition for an aqueous coating material.

[0069] The glass transition temperature (Tg) of the

copolymer refers to a temperature measured using a

differential scanning calorimetry (DSC) device according to

JTS K7121-1987.

[0070] The method for producing the copolymer constituting

the resin composition for an aqueous coating material is not

particularly limited, and examples thereof include (1) a

production method in which the copolymer is produced by

emulsion polymerization of a monomer composition including the

styrene-based monomer, the acrylic monomer, and the

unsaturated fatty acid salt, which serves as the reactive

emulsifier, in an aqueous medium in the presence of a general

purpose radical polymerization initiator, and (2) a production

method in which the copolymer is produced by radical

polymerization of a monomer composition including the styrene

based monomer, the acrylic monomer, and the unsaturated fatty

acid salt in an organic solvent (e.g., xylene, toluene, methyl

isobutyl ketone, and the like) in the presence of a general

purpose radical polymerization initiator. From the viewpoint

of the remaining amount of solvent, the production method (1)

PCT/JP2020/11949 (Y-283)

is preferable. When the copolymer is produced by the above

production method (2), the obtained copolymer may be isolated,

and the isolated copolymer may be dispersed in an aqueous

medium using a disperser which has a high energy shearing

ability, as necessary. Examples of the radical polymerization

initiator include an azo-based compound, a peroxide-based

compound, sulfides, sulfines, and a diazo compound.

[0071] An aqueous coating material can be produced by

dispersing the resin composition for an aqueous coating

material in an aqueous medium. In the aqueous coating

material, the content (content of solid content) of the

copolymer constituting the resin composition for an aqueous

coating material is preferably 10 to 90% by mass, more

preferably 15 to 80% by mass, and particularly preferably 20

to 60% by mass.

[0072] Then, since the copolymer constituting the resin

composition for an aqueous coating material includes the

unsaturated fatty acid salt, which is the reactive emulsifier,

as a monomer unit thereof, it is possible to satisfactorily

emulsify and disperse the copolymer in an aqueous medium to

form a substantially homogeneous aqueous coating material. In

addition, dispersing the resin composition for an aqueous

coating material in an aqueous medium can be performed without

using an emulsifier, however if used, the use amount of the

emulsifier can be reduced.

PCT/JP2020/11949 (Y-283)

[0073] The aqueous coating material may include, as

necessary, general-purpose additives such as a non-reactive

emulsifier, a pigment, a film forming aid, a defoaming agent,

a thickener, an antiseptic, an antifungal agent, a pH

adjusting agent, and a metal dryer, for example.

[00741 Examples of the non-reactive emulsifier include an

anionic emulsifier, a cationic emulsifier, and a nonionic

emulsifier. Among these, an anionic emulsifier is preferable.

The non-reactive emulsifier may be used alone, and two or more

kinds thereof may be used in combination.

[00751 Examples of the anionic emulsifier include sodium

lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzene

sulfonate, sodium polyoxyethylene alkyl ether sulfate, sodium

polyoxyethylene alkyl phenyl ether sulfate, ammonium

polyoxyethylene alkyl phenyl ether sulfate, sodium

polyoxyethylene alkyl sulfosuccinate, polyoxyalkylene

polycyclic phenyl ether sulfate ester salts (e.g.,

polyoxyethylene polycyclic phenyl ether sulfate ester sodium,

polyoxyethylene polycyclic phenyl ether sulfate ester

ammonium, polyoxypropylene polycyclic phenyl ether sulfate

ester sodium, polyoxypropylene polycyclic phenyl ether sulfate

ester ammonium salt, and the like). The anionic emulsifier is

preferably a polyoxyalkylene polycyclic phenyl ether sulfate

ester salt, preferably a polyoxyethylene polycyclic phenyl

ether sulfate ester salt, and more preferably polyoxyethylene

PCT/JP2020/11949 (Y-283)

polycyclic phenyl ether sulfate ester ester ammonium.

[0076] Examples of the cationic emulsifier include an

alkyltrimethylammonium chloride.

[0077] Examples of the nonionic emulsifier include a

polyoxyethylene alkyl ether, a polyoxyethylene alkyl phenyl

ether, a polyoxyethylene fatty acid ester, and a

polyoxyethylene polyoxypropylene block polymer. These may be

used alone, and two or more kinds thereof may be used in

combination.

LO [00781 The content of the non-reactive emulsifier in the

aqueous coating material is preferably 0 to 5 parts by mass,

more preferably 0 to 3 parts by mass, and more preferably 0 to

2 parts by mass, relative to 100 parts by mass of the

copolymer. Note that "0 parts by mass" means that no non

.5 reactive emulsifier is included in the aqueous coating

material.

[0079] In order to coat the surface of an object to be

coated (e.g., a building material such as an exterior material

used for constructing a building) with the obtained aqueous

coating material, the aqueous coating material is applied onto

a surface of an object to be coated to form an applied layer,

and the aqueous medium in the applied layer is then evaporated

and removed, which will lead to solidification of the applied

film to form a coating film. This coating film can coat the

surface of the object to be coated.

PCT/JP2020/11949 (Y-283)

[0080] Herein, as described above, the copolymer

constituting the resin composition for an aqueous coating

material includes the unsaturated fatty acid salt unit, which

is a reactive emulsifier, as a monomer unit in its molecule.

The unsaturated fatty acid salt with unsaturated bonds in the

molecule is bonded and incorporated in the copolymer by a

copolymerization reaction. In addition to this, it has an

aliphatic group, so it is possible to prevent elution of the

coating film component when the coating film formed from the

resin composition for an aqueous coating material is exposed

to water. Therefore, in the coating film formed from the

aqueous coating material, the unsaturated fatty acid salt unit

constituting the copolymer is not released from the copolymer

and never bleeds out on the surface of the coating film.

[0081] In addition, in preparing an aqueous coating

material by dispersing the resin composition for an aqueous

coating material in an aqueous medium, as described above, it

is possible to eliminate the use of an emulsifier or to reduce

the amount of an emulsifier to be used.

[00821 Accordingly, the amount of the free emulsifier in

the coating film formed from the aqueous coating material is

extremely reduced, and voids caused by bleed-out of the

emulsifier, which forms on the surface of the coating film

when exposed to water during or after the formation of the

coating film, are reduced or suppressed.

PCT/JP2020/11949 (Y-283)

[0083] Therefore, penetration of moisture into the

interior of the coating film through voids on the surface of

the coating film is reduced or suppressed, and the coating

film has excellent initial water resistance. In addition, the

leveling property is improved at the time of coating film

formation by the unsaturated fatty acid salt unit in the

copolymer, and the coating film also excels in the initial

gloss.

[Examples]

LO [0084] [Synthesis of fatty acid-modified monomer]

The compounds shown below were fed into a reaction

vessel, and were reacted with stirring in the reaction vessel

at 160 0 C. Thus, a tall oil fatty acid and glycidyl

methacrylate were subjected to an addition reaction for about

90 minutes to obtain a fatty acid-modified monomer. After

completion of the reaction, 0.08 parts by mass of hydroquinone

was fed into the reaction vessel. The tall oil fatty acid

included 2% by mass of palmitic acid and 2% by mass of stearic

acid as saturated fatty acids, and 46% by mass of oleic acid

and 41% by mass of linoleic acid as unsaturated fatty acids.

Note that the addition reaction between the epoxy group of

glycidyl methacrylate and the carboxy group of the tall oil

fatty acid was monitored by measuring the amount of the

remaining acid component.

Tall oil fatty acid: 260.00 parts by mass

PCT/JP2020/11949 (Y-283)

Glycidyl methacrylate: 136.00 parts by mass

p-Methoxyphenol: 0.70 parts by mass

Tetrabutylphosphonium bromide: 0.40 parts by mass

Triphenylphosphine: 0.40 parts by mass

[00851 [Emulsifier]

(Synthesis 1 of unsaturated fatty acid salt)

First, 344.92 parts by mass of distilled water and 44.73

parts by mass of 48% by mass of an aqueous potassium hydroxide

solution were fed into a reaction vessel and maintained at 95 0 C

for about 1 hour with stirring. Next, 110.35 parts by mass of

an unsaturated fatty acid shown below was fed into the

reaction vessel and reacted for 3 hours at 95 0C with stirring

to obtain a potassium salt (reactive emulsifier) of the

unsaturated fatty acid which had a solid concentration of 25%

by mass. In Table 1, each potassium salt of the obtained

unsaturated fatty acids was represented by adding "K salt" to

the end of the trade name of the reactive emulsifier that

serves as a raw material. In the following, "potassium salt"

is shown as "K salt".

Unsaturated fatty acid 1: trade name "HARIDIMER 200 (DA

200)" manufactured by Harima Chemical Co., Ltd.

Unsaturated fatty acid 2: trade name "TSUNODYME 395"

manufactured by TSUNO FOOD INDUSTRIAL CO., LTD.

Unsaturated fatty acid 3 : trade name "TSUNODYME 228"

manufactured by TSUNO FOOD INDUSTRIAL CO., LTD.

PCT/JP2020/11949 (Y-283)

[0086] (Synthesis 2 of unsaturated fatty acid salt)

The addition reaction of the unsaturated fatty acid in a

tall oil fatty acid with maleic anhydride gave an adduct. This

adduct was subjected to the same treatment as that according

to the method of Synthesis 1 of unsaturated fatty acid salt to

obtain a potassium salt of the unsaturated fatty acid with a

solid content of 25% by mass (BK-73B K salt, potassium salt of

oleic acid) (reactive emulsifier).

[0087] The tall oil fatty acid included 2% by mass of

palmitic acid and 2% by mass of stearic acid as saturated

fatty acids, and 46% by mass of oleic acid and 41% by mass of

linoleic acid as unsaturated fatty acids.

[00881 (Synthesis 3 of unsaturated fatty acid salt)

A reactant obtained by reacting an unsaturated fatty acid

(trade name "HARIDIMER 200 (DA-200)" manufactured by Harima

Chemical Co., Ltd.) with N,N-dimethylaminoethanol was

subjected to the same treatment as that according to the

method of Synthesis 1 of unsaturated fatty acid salt to obtain

a potassium salt of the unsaturated fatty acid with a solid

content of 25% by mass (DA-200Mabs salt) (reactive

emulsifier).

[0089] (Synthesis 4 of unsaturated fatty acid salt)

First, 471.91 parts by mass of distilled water and 47.38

parts by mass of 48% by mass of an aqueous potassium hydroxide

solution were fed into a reaction vessel and maintained at 95 0 C

PCT/JP2020/11949 (Y-283)

for about 1 hour with stirring. Next, 110.08 parts by mass of

a tall oil fatty acid (trade name "HARTALL FA-1" manufactured

by Harima Chemical Co., Ltd.) was fed into the reaction vessel

and reacted for 3 hours at 95 0C with stirring to obtain a

potassium salt of the tall oil fatty acid with a solid

concentration of 19.4% by mass (FA-1 K salt) (reactive

emulsifier). The potassium salt of the tall oil fatty acid

included a potassium salt of oleic acid and a potassium salt

of linoleic acid.

LO [0090] The tall oil fatty acid included 2% by mass of

palmitic acid and 2% by mass of stearic acid as saturated

fatty acids, and 46% by mass of oleic acid and 41% by mass of

linoleic acid as unsaturated fatty acids.

[0091] (Synthesis 1 of saturated fatty acid salt)

First, 676.89 parts by mass of distilled water and 46.83

parts by mass of 48% by mass of an aqueous potassium hydroxide

solution were fed into a reaction vessel and maintained at 95 0 C

for about 1 hour with stirring. Next, 109.67 parts by mass of

stearic acid, which is a saturated fatty acid, was fed into

the reaction vessel and reacted for 3 hours at 950 C with

stirring to obtain a potassium salt of stearic acid with a

solid concentration of 15% by mass (Stearic Acid K salt) (non

reactive emulsifier).

[00921 (Other emulsifiers)

trade name "AQUALON AR-1025" manufactured by DKS Co., Ltd.

PCT/JP2020/11949 (Y-283)

(reactive emulsifier, polyoxyethylene styrenated propenyl

phenyl ether sulfate ammonium salt)

CH=CHCH3

4 (CH2CH20).-SO3NH Q CH CH3m

[0093]

Polyoxyethylene polycyclic phenyl ether sulfate ester salt

trade name "NEWCOL 707-SF" manufactured by NIPPON

NYUKAZAI CO., LTD. (non-reactive emulsifier)

f-O-(CH 2 CH 2 0)n-SO 3 X

f: Polycyclic phenyl group, X: Na or NH 4

[0094]

trade name "HITENOL LA-12" manufactured by DKS Co., Ltd.

(non-reactive emulsifier)

Polyoxyethylene lauryl ether sulfate ester ammonium

[0095] As to the above-described emulsifiers, the contents

of the monomer acid potassium salt (monomer acid K salt), the

dimer acid potassium salt (dimer acid K salt) and the trimer

acid potassium salt (trimer acid K salt), and the iodine

values thereof (solid) are shown in Table 1.

[0096] [Monomer composition]

Monomer compositions 1 to 16 each including styrene,

methyl methacrylate, isobutyl methacrylate, 2-ethylhexyl

acrylate, n-butyl acrylate, cyclohexyl methacrylate, fatty

acid-modified monomer, diacetone acrylamide, and methacrylic

PCT/JP2020/11949 (Y-283)

acid in respective predetermined amounts shown in Table 2 were

prepared.

[0097] [Examples 1 to 25, Comparative Examples 1 to 7]

(Production of resin composition for aqueous coating

material)

An emulsifier which had the composition (% by mass) shown

in each of Tables 3 to 5 was prepared. An amount of half of

the predetermined fed amount of the emulsifier shown in Tables

3 to 5 and 91.5 parts by mass of distilled water were fed to a

.0 reaction vessel. Nitrogen gas was fed into the reaction vessel

to substitute the inside are with the nitrogen gas while

stirring the content in the reaction vessel, and water

including the emulsifier in the reaction vessel was heated to

90 0 C and maintained.

[0098] Next, to a mixture of 100 parts by mass of the

monomer composition shown in Tables 3 to 5 and the remaining

half of the above-mentioned emulsifier, 55.2 parts by mass of

distilled water and 0.74 parts by mass of ammonium persulfate

were added. The mixture was emulsified by stirring at a high

speed using a high speed disperser to prepare a monomer

emulsion.

[0099] The monomer emulsion was dripped into the reaction

vessel over a period of 3 hours. A radical polymerization

reaction was performed by maintaining the reaction solution in

the reaction vessel at 90°C for 2 hours to synthesize a

PCT/JP2020/11949 (Y-283)

copolymer. After that, the reaction solution in the reaction

vessel was cooled to 40 0 C or lower, and then adjusted with 28%

by mass of aqueous ammonia so that the pH of the reaction

solution became 9, to obtain a resin composition for an

aqueous coating material with a solid content (copolymer)

concentration of 40% by mass.

[0100] Note that the content (% by mass) and the fed

amount (parts by mass) of the emulsifier shown in Tables 3 to

5 indicate the amount of solid content.

[0101] (Production of aqueous coating material)

First, 8.55 parts by mass of water, 17.09 parts by mass

of a pigment (titanium oxide), 0.70 parts by mass of a pigment

dispersant (trade name "DISPERBYK-190" manufactured by Byk

Chemie Co., Ltd.), and 0.09 parts by mass of a defoaming agent

(trade name "SN DEFOAMER 777" manufactured by San Nopco Co.,

Ltd.) were uniformly mixed to prepare a coating raw material

liquid.

[0102] Next, 26.43 parts by mass of the above-mentioned

coating raw material liquid, 1.81 parts by mass of an

emulsifier (trade name "NEWCOL 707-SF" manufactured by NIPPON

NYUKAZAI CO., LTD.), 27.00 parts by mass (solid content) of a

resin composition for an aqueous coating material, 40.50 parts

by mass of water, 2.20 parts by mass of a film forming aid

(butyl diglycol), 0.10 parts by mass of a defoaming agent

(trade name "SN DEFOAMER 777" manufactured by San Nopco Co.,

PCT/JP2020/11949 (Y-283)

Ltd.), 0.40 parts by mass of a thickener (trade name "PRIMAL

RM-12W" manufactured by Dow Chemical Japan Co., Ltd.), 1.46

parts by mass of a metal dryer (trade name "DICNATE3111TL"

manufactured by DIC Corporation), and 0.10 parts by mass of an

adjuvant (adipic acid dihydrazide) were uniformly mixed to

prepare an aqueous coating. Note that the amount of the resin

composition for an aqueous coating material is a solid

content.

[01031 Regarding the obtained aqueous coating material,

the initial gloss and the gloss retention property as an

evaluation criterion of the initial water resistance were

measured as described below, and the results are shown in

Tables 3 to 5. Note that the aqueous coating material of

Comparative Example 4 could not be evaluated because it had

been gelled.

[01041 (Initial gloss)

The aqueous coating material was applied to a stainless

steel plate (length: 150 mm x width: 70 mm x thickness: 0.8 mm)

(manufactured by Taiyu Kizai Co., Ltd.) by using a film

applicator (trade name "AP100" manufactured by Taiyu Kizai

Co., Ltd.). Thus, an applied layer is formed.

[01051 The applied layer on the stainless steel sheet was

dried in a room at 23 0 C and 50% relative humidity for 16 hours

to evaporate and remove moisture included in the applied layer

to form a coating film. The 200 specular reflectance (20°G) of

PCT/JP2020/11949 (Y-283)

the resulting coating film was measured. The measured values

were converted to specular gloss according to JIS Z8741. The

obtained specular gloss was regarded as "initial specular

gloss" and used as evaluation criterion of the initial gloss.

[0106] (Initial water resistance)

The coating film was formed in the same manner as that

for the initial gloss, and the initial specular gloss of the

coating film was measured as described above.

[0107] A polyvinyl chloride pipe with an inner diameter of

43 mm was prepared, and a silicone grease was applied to the

entire end surface of the first opening of the pipe. The pipe

was brought into intimate contact with the coating film. Note

that the entire applied surface of the silicone grease of the

pipe was made to be in intimate contact with the coating film.

[0108] After 15 g of distilled water was fed into the

pipe, the second opening of the pipe was closed with a

synthetic resin film so that the distilled water in the pipe

was not allowed to evaporate in order to prepare a test body.

The test body was allowed to stand for 24 hours in a room at

0 23 C and 50% relative humidity.

[0109] Next, after removing the distilled water in the

pipe, the pipe was removed from the coating film, and the

moisture on the coating film was sufficiently wiped off. The

coating film was then left to stand for 1 hour in a room at

23°C and 50% relative humidity.

PCT/JP2020/11949 (Y-283)

[0110] The specular gloss of the coating film after the

water resistance test (specular gloss after the water

resistance test) was measured in the same manner as that for

the initial specular gloss. The gloss retention rate was

calculated on the basis of the following formula. The higher

the gloss retention rate, the better the initial water

resistance.

Gloss retention rate (%) = 100 x Specular gloss after

water resistance test/Initial specular gloss

.0 [0111]

[Table 1]

PCT/JP2020/11949 (Y-283)

LU (CR

-j

00

LU0

-0 -v

co, Cl

co 0

-H LL

Coo

Coj Ccc c-4

COi~~ C cca

m C

LU)

CD - 0 a) Co

PCT/JP2020/11949 (Y-283)

[0112]

[Table 2]

=0 Co Co 0; 0Cm,

C C:, C CDo

0D 0 C 0 C

C~ ~~c) o Co-

C0 Co CoC 0 C

0 > Co Co 0. C

Lo c>

-~ ~c 0 o0-ou

0 _. 6 0 o Co - Cow

Co - oo - R oo

0 0 o 0 04C

PCT/JP2020/11949 (Y-283)

[0113]

[Table 3]

0. co000C)( 00 0 C) c> c:. C: : n n = c

c~m 00- - o

00 00 0) 0) 0) 0D 0 0 C', -=1~

c- C:. 0: 0> 0> 0z: 0> 0 0 0 cq

0 ) 0 0 0 0 0 0 0 CD C> C'j C>c Ct

L, C)CD C: tO c) c) C> c> "' to0 0.

U-)~~ ~( tOto-z

. C)) C: c'J 0:)D D C C t:o

0~ ~ ~~~. 0 000 0C. -~~

0 0 0 0 0 0 C'' - CD. <D 'to C, C :

0n to CO 0 '

0 0 0 0 00 C, C CCD to tot-.O

C> C)to LO r

4-' LO 0o 4 cu ~ 4-'

- 0) "' - C6(V( ca CI) C'] (V 4,' '

m- >- m m a0 IF 0: 0D C C,> 0> E (V wV mE Il I ' > 4' 0 i 0 -0 0

- -e cu t C) + 0 (

0D U.. C'.4 0 4 _ V) - = - c (V

4VC (V C - L cu (V-4. ~ 0cu 0 - . C( -1 C. U (VCW E coJ0

w 4(V - LU -0 0 0 r- m. U 4-o

o. C s0 E4-( C 0C) 0.0 (V

5- - (Vcz E 0(10 -'0 LL ca CL ( (

46-C .

PCT/JP2020/11949 (Y-283)

[0114]

[Table 4]

C: > C > > C c C) IC -(q 0L

0 0) c0 CD 0> 0, 0 0D c> C:

c') C>2 C> C) C C ) C co to r- qr

C40 0 0 0 0 e'JU t10

C'4 C> C> C ) D Co C CI C

m C4 LO LO o It t

0mD C> 0> 0= 0) : c) C' I= ' ( 0

0 0 0 C) C1 000 CNJ

LU - C ->> C D c > ' ---------------- ---------------- co

Co ) C> C= c c) C: c>j 0) c0 (0

( -(0 C> CU) cr-,.C> t ('>(

LO to -zi C)- o

(0, LI) C:) c0 o , c > C)

0 0to U0 000 I) (

-o 4-o

e 4-'+14

-0i 4 (/ U-0m (

C> C) C) C > 4- E co -cc (/2- (0- _sz LU~~ ' - LU)>(2 41(

41 - o CL to04 c> 0 >- 4> 4-M

----------------------- 1 C/) 4-

- -1 I :I t, I- -,

CD ~ 0 C 0 Co C/ CD 4- )C 4

co~~4 o E ('40-( U 0 4-0U w C(UCUCU~~~ ~Li-/2E-~ Li o -' 0 LU-4'C , '

(/

wU E) CUCC 5- CU

E 0- 41 0 LUJ a- (0-u

0> 115E

PCT/JP2020/11949 (Y-283)

[Table 5]

2~~~ 10 0- 0 000000 1JCl (D

a) D C) C > C D < ) (0' ~ l

(DVC > -,I 0 0 0 CD C) 0 0 > 0C: C'D -> (NJD

0

Cli~ ~ r-. C:. C> CC ) 6C'C0CJ 1 L - 0 0 0 0 0 0 0 "I C0 Cl)

( +JJ 41

CI 0) (N - C)(

Ca C" i ) c ) C41 Ca~ ( C) C) 0 0

0 0 0 0CD ~ M ('D CD ~ C CO CO eVO 2'- ~ 2 4-' C14 Z=~ r- (:N4 - 0 W' 0I I IO I >1. (V -0 c C/) -P I) 4-) - 'n C.. MN C' (V. 4.( C/) - Ci) - _0 '- ( 4 aOr- 0 -4- 0 U)C) 4-).- 0 CD .J a C =0 0 Ca0( r 0 - C 4- C < I .J4-) 0J 0: (V 41-0 C0 LIU (V 4-' C O( CO 4- .3 1-- CD 0a - 0 (VO =(V M 0 LIi -'- (1) CO - - CO .0 __ __D __ _ LL.(i LI.. 0 4-1 =3 0 2CL 0- 4C 0-0 C: 0.0C () ( M)0 C/:) 4-' 4- 0 - - (

Q) (VO 0 0 4-' 0) (0 C(V a) 0 LU 0 ' 0

C- CI C 2E-= 0 4- E 204-0

Industrial Applicability

[0116] The aqueous coating material formed from the resin

composition for an aqueous coating material of the present

invention can form a coating film, which has excellent initial

gloss and initial water resistance, on a surface of an object to be coated such as a building material, whereby the surface of the object to be coated can be coated.

[0117] (Cross-reference to related application)

The present application claims the priority under

Japanese Patent Application No. 2019-51959, filed March 19,

2019, the disclosure of which is incorporated herein in its

entirety by reference.

[0118]

It is to be understood that, if any prior art publication

is referred to herein, such reference does not constitute an

admission that the publication forms a part of the common

general knowledge in the art, in Australia or any other

country.

[0119]

In the claims which follow and in the preceding

description of the invention, except where the context

requires otherwise due to express language or necessary

implication, the word "comprise" or variations such as

"comprises" or "comprising" is used in an inclusive sense, i.e.

to specify the presence of the stated features but not to

preclude the presence or addition of further features in

various embodiments of the invention.

49 20607895_1 (GHMatters) P117157.AU

Claims (5)

1. A resin composition for an aqueous coating material

comprising a copolymer that includes a styrene-based monomer

unit, an acrylic monomer unit, and an unsaturated fatty acid

salt unit, and has a glass transition temperature (Tg) of -4°C

to 40°C,

wherein the unsaturated fatty acid salt includes a

polymerized fatty acid salt,

wherein the polymerized fatty acid salt includes at least

one of a dimer acid salt and a trimer acid salt, and

wherein the glass transition temperature (Tg) of the

copolymer is measured using a differential scanning

calorimetry (DSC) device according to JIS K7121-1987.

2. The resin composition for an aqueous coating material

according to claim 1, wherein the polymerized fatty acid salt

includes a dimer acid salt.

3. The resin composition for an aqueous coating material

according to claim 1 or claim 2,

wherein the unsaturated fatty acid salt includes a

potassium salt.

4. The resin composition for an aqueous coating material

according to any one of claims 1 to 3, wherein the copolymer

50 20996083_1 (GHMatters) P117157.AU is an emulsion polymerization product of a monomer composition including a styrene-based monomer, an acrylic monomer, and an unsaturated fatty acid salt serving as a reactive emulsifier.

5. A coating film being a solidified product of an applied

layer of the resin composition for an aqueous coating material

according to any one of claims 1 to 4 on an object to be

coated.

51 20996083_1 (GHMatters) P117157.AU