AU2021347006A1 - Coating material composition - Google Patents
Coating material composition Download PDFInfo
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- AU2021347006A1 AU2021347006A1 AU2021347006A AU2021347006A AU2021347006A1 AU 2021347006 A1 AU2021347006 A1 AU 2021347006A1 AU 2021347006 A AU2021347006 A AU 2021347006A AU 2021347006 A AU2021347006 A AU 2021347006A AU 2021347006 A1 AU2021347006 A1 AU 2021347006A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/02—Polyamines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
- C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
Abstract
Provided is a coating material composition which exhibits good storage stability and can be cured in a short time. This coating material composition contains a hydroxyl group-containing resin (A), an amino resin (B), a covalent bonding block type acid catalyst (C) and a phosphoric acid-modified epoxy resin (D). Relative to a total of 100 parts by mass of the solid resin content of the hydroxyl group-containing resin (A) and the solid resin content of the amino resin (B), the content of the hydroxyl group-containing resin (A) is 60-90 parts by mass, the content of the amino resin (B) is 10-40 parts by mass, the content of an acid catalyst part of the covalent bonding block type acid catalyst (C) is 1-10 parts by mass, and the content of the solid content of the phosphoric acid-modified epoxy resin (D) is 1-10 parts by mass.
Description
[0001]
The present invention relates to a coating composition.
[0002]
In a wide range of industrial products such as home electric appliances,
electronic devices, decorations, furniture, and building materials, a coating film is
commonly formed by applying a coating composition on the surfaces and the like of the
products and the parts for the purpose of protection, decoration, and the like.
[0003]
Coating compositions include a two-pack type comprising a main agent and a
crosslinking agent, and a one-pack type in which a main agent and a crosslinking agent
are mixed in advance in a stable state. In the two-pack type, it is comperaratively easy
to achieve both the storage stability of the coating composition and the physical
properties of a resulting coating film. However, the two-pack type has a problem in
handling and coating workability, such as that a user needs to accurately mix a main
agent and a crosslinking agent in a prescribed ratio at a coating site and sufficiently stir
them, and that there is a limitation on the usable time. A one-pack coating
composition is hence demanded.
[0004]
Meanwhile, in recent years, shortening of a coating process has been required from the viewpoint of energy saving and reduction of carbon dioxide emission.
For example, JP-A-2020-100740 (Patent Literature 1) describes an invention
relating to a precoated metal sheet (also referred to as "PCM"), which is a coated steel
sheet in which a cold-rolled steel sheet or a plated steel sheet as a substrate is coated.
Commonly, coating is applied onto a surface of a steel sheet, then a coating
film is formed through heating step (baking step) at a peak temperature of the steel
sheet, which is an article to be coated, (this temperature is also referred to as peak metal
temperature "PMT") of 200 to 270°C for 30 to 60 seconds to form a coating film, and
then the resulting precoated metal sheet is processed into a required product. In this
case, as a baking furnace to be used for baking, a hot air furnace using a gas or the like
as a means for heating is commonly used.
In this case, however, it is necessary to constantly maintain an ambient
temperature at 300°C or higher, and reduction in energy cost is demanded.
[0005]
Patent Literature 1: JP-A-2020-100740
[0006]
Instead of the hot air type furnace as described above, an induction heater (also
referred to as "IH") type furnace has been developed and is beginning to be introduced
in companies. As a result, the furnace length is shortened, so that the manufacturing space can be reduced, and the PMT can be raised to 220°C in a short time.
On the other hand, since the furnace length of the IH type furnace as described
above is shortened, the curing time of a coating composition is also required to be
shortened. In order to shorten the curing time of a one-pack coating composition, it is
necessary to increase the curing reaction rate using a large amount of an acid catalyst.
However, when the coating composition contains a large amount of an acid catalyst,
there is a problem in storage stability of the coating composition.
As described above, it has been difficult to obtain a coating composition which
has good storage stability and can be cured in a short time.
[0007]
An object of the present invention is to provide a coating composition that has
good storage stability and can be cured in a short time.
Further, another object of the present invention is to provide a method for
producing a coating film by heating for a short time using the coating composition.
Another object of the present invention is to provide a method for producing a
precoated metal sheet by heating for a short time using the coating composition.
[0008]
The present invention provides the following embodiments [1] to [13].
[1] A coating composition comprising a hydroxyl group-containing resin (A), an
amino resin (B), a covalently bonded blocked acid catalyst (C), and a phosphoric acid
modified epoxy resin (D),
wherein
based on 100 parts by mass of a total of a resin solid content of the hydroxyl group-containing resin (A) and a resin solid content of the amino resin (B),
60 to 90 parts by mass of the hydroxyl group-containing resin (A),
10 to 40 parts by mass of the amino resin (B),
1 to 10 parts by mass of an acid catalyst moiety of the covalently bonded
blocked acid catalyst (C), and
1 to 10 parts by mass of a solid component of the phosphoric acid-modified
epoxy resin (D) are contained.
[2] The coating composition according to [1], wherein a number-average
molecular weight of the phosphoric acid-modified epoxy resin (D) is in a range of 460
to 4,000.
[3] The coating composition according to [1] or [2], wherein the covalently bonded
blocked acid catalyst (C) is a catalyst in which an aromatic sulfonic acid is blocked by a
compound having a glycidyl group.
[4] The coating composition according to [3], wherein in the covalently bonded
blocked acid catalyst (C), the compound having a glycidyl group is an epoxy resin
having two or more glycidyl groups in a molecule or a glycidyl ether compound having
one glycidyl group in a molecule.
[5] The coating composition according to [4], wherein in the covalently bonded
blocked acid catalyst (C), a number-average molecular weight of the epoxy resin having
two or more glycidyl groups is in a range of 2,000 to 7,000.
[6] The coating composition according to [5], wherein in the covalently bonded
blocked acid catalyst (C), a molecular weight of the glycidyl ether compound having
one glycidyl group in a molecule is in a range of 140 to 200.
[7] The coating composition according to any one of [1] to [6], wherein the
hydroxyl group-containing resin (A) is a polyester resin and a number-average molecular weight of the hydroxyl group-containing resin (A) is in a range of 1,500 to
,000 and a hydroxyl value is in a range of 40 to 100 mg KOH/g.
[8] The coating composition according to any one of [1] to [7], wherein the amino
resin (B) comprises a melamine resin.
[9] The coating composition according to any one of [1] to [8], further comprising
an alkanolamine (E).
[10] The coating composition according to [9], wherein the alkanolamine (E)
comprises two or more alkanol groups in a molecule.
[11] The coating composition according to [9] or [10], wherein a content of the
alkanolamine (E) is 1.0 to 4.0 parts by mass based on 100 parts by mass of the total of
the resin solid content of the hydroxyl group-containing resin (A) and the resin solid
content of the amino resin (B).
[12] A method for producing a coating film, comprising:
a step of applying the coating composition according to any one of [1] to [11]
to an article to be coated to form an applied film; and
a step of drying and/or curing the applied film under a condition in which a
peak temperature of the article is 180°C to 270°C and a drying and/or curing time is 1 to
seconds.
[13] A method for producing a precoated metal sheet, comprising:
a step of applying the coating composition according to any one of [1] to [11]
to at least one surface of a metal sheet to form an applied film such that a film thickness
after curing is 5 to 25 pm; and
a step of drying and/or curing the applied film under a condition in which a
peak temperature of the metal sheet is 180°C to 270°C and a drying and/or curing time
is 1 to 10 seconds.
[0009]
The coating composition of the present invention exhibits good storage
stability, and a curing reaction thereof can sufficiently proceed even by heating for a
short time.
Furthermore, by the method for producing a coating film of the present
invention, a coating film can be produced by heating for a short time.
In addition, by the method for producing a precoated metal sheet of the present
invention, a precoated metal sheet can be produced by heating for a short time.
[0010]
[Coating composition]
The coating composition of the present disclosure will be described.
[0011]
The coating composition of the present disclosure comprises a hydroxyl group
containing resin (A), an amino resin (B), a covalently bonded blocked acid catalyst (C),
and a phosphoric acid-modified epoxy resin (D),
wherein
based on 100 parts by mass of a total of a resin solid content of the hydroxyl
group-containing resin (A) and a resin solid content of the amino resin (B),
60 to 90 parts by mass of the hydroxyl group-containing resin (A),
10 to 40 parts by mass of the amino resin (B),
1 to 10 parts by mass of an acid catalyst moiety of the covalently bonded blocked acid catalyst (C), and
1 to 10 parts by mass of a solid component of the phosphoric acid-modified
epoxy resin (D) are contained.
[0012]
<Hydroxyl group-containing resin (A)>
The hydroxyl group-containing resin (A) is a resin having a hydroxyl group in
a molecular structure thereof. The hydroxyl group-containing resin (A) reacts with the
amino resin (B) as a curing agent to form a coating film.
Examples of the hydroxyl group-containing resin (A) include a polyester resin,
an epoxy resin, and an acrylic resin, and a polyester resin is preferable.
[0013]
(Polyester resin)
The polyester resin is not particularly limited as long as it is a polyester resin
commonly used for coating materials. Unless otherwise specified in the present
disclosure, when simply described as "polyester resin", it means that the polyester resin
comprises at least one species selected from the group consisting of polyester resin and
modified products of polyester resin.
[0014]
The hydroxyl value of the hydroxyl group-containing polyester resin is
preferably 40 to 100 mg KOH/g, and more preferably 60 to 100 mg KOH/g. Whenthe
hydroxyl value of the polyester resin is in the above range, the reaction with the amino
resin (B) as a curing agent proceeds well. When the coating composition contains
such a polyester resin, there is an advantage that a resulting coating film is high in
solvent resistance, folding processability, processing adhesive property, and chemical
resistance.
In the present disclosure, the hydroxyl value represents a solid hydroxyl value
and is a value measured by the method described in JIS K 0070.
[0015]
The number-average molecular weight of the polyester resin is preferably
1,500 to 5,000, more preferably 2,000 to 4,500, and particularly preferably 2,000 to
4,000. When the number-average molecular weight of the polyester resin is in the
above range, the curing reaction with the amino resin (B) sufficiently proceeds and a
coating film having high solvent resistance and chemical resistance can be formed.
Further, it is possible to inhibit the crosslink density of the coating film from becoming
excessively high, and it is possible to form a coating film having a sufficient elongation
rate and, for example, it is possible to form a coating film having sufficient folding
processability and processing adhesive property. Furthermore, the coating
composition of the present disclosure has an appropriate viscosity and is good in
handleability.
In the present disclosure, the number-average molecular weight is a
polystyrene-equivalent value determined by gel permeation chromatography (GPC).
[0016]
The glass transition temperature (Tg) of the polyester resin is preferably -35°C
or higher and 110°C or lower, for example, -30°C or higher and 80°C or lower, and may
be -30°C or higher and 60°C or lower. When the glass transition temperature (Tg) of
the polyester resin is in the above range, the moisture permeability of a coating film is
not excessively high and the coating film has sufficient moisture resistance and
chemical resistance.
In the present disclosure, the glass transition temperature (Tg) can be measured
using, for example, a thermal analyzer (TMA7100 (manufactured by Hitachi High-Tech
Science Corporation) or the like).
[0017]
The acid value of the polyester resin is, for example, 0.1 mg KOH/g or more
and 30 mg KOH/g or less, or 0.2 mg KOH/g or more and 30 mg KOH/g or less, and
may be 0.3 mg KOH/g or more and 30 mg KOH/g or less. When the acid value of the
polyester resin is in the above range, for example, hydrolysis resistance can be
improved, and a coating film having moisture resistance and chemical resistance can be
formed.
In the present disclosure, the acid value represents a solid acid value, and is a
value measured by the method described in JIS K 0070.
[0018]
The polyester resin can be obtained by polycondensation of a polyhydric
alcohol and a polybasic acid. Examples of the polyhydric alcohol include ethylene
glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol,
polypropylene glycol, neopentyl glycol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol
or 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, hydrogenated bisphenol A,
hydroxyalkylated bisphenol A, 1,4-cyclohexanedimethanol, 2,2-dimethyl-3
hydroxypropyl-2,2-dimethyl-3-hydroxypropionate (BASHPN), N,N-bis-(2
hydroxyethyl)dimethylhydantoin, polycaprolactone polyol, glycerin, sorbitol, annitol,
trimethylolethane, trimethylolpropane, trimethylolbutane, hexanetriol, pentaerythritol,
dipentaerythritol, and tris(2-hydroxyethyl)isocyanurate. As the polyhydric alcohol,
only one species may be used, or two or more species may be used in combination.
[0019]
Examples of the polybasic acid include phthalic acid, phthalic anhydride,
tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, methyltetraphthalic acid, methyltetrahydrophthalic anhydride, hymic anhydride, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic dianhydride, isophthalic acid, terephthalic acid, maleic acid,-maleic anhydride, fumaric acid, itaconic acid, adipic acid, azelaic acid, sebacic acid, succinic acid, succinic anhydride, lactic acid, dodecenylsuccinic acid, dodecenylsuccinic anhydride, cyclohexane-1,4-dicarboxylic acid, and endic anhydride. Asthepolybasic acid, only one species may be used, or two or more species may be used in combination.
[0020]
Examples of the modified products of polyester resin include modified
polyester resins such as urethane-modified polyester resins, epoxy-modified polyester
resins, acrylic-modified polyester resins, and silicone-modified polyester resins. For
example, the urethane-modified polyester resin is a resin having polyester as its main
chain and urethane-modified by modifying the ends thereof with isocyanate. For
example, the silicone-modified polyester resin can be prepared by reacting a polyester
resin with an organic silicone (for example, an organic silicone having an -Si-OCH 3
group and/or an Si-OH group as a functional group and having a number-average
molecular weight of about 300 to about 1,000). The amount of the organic silicone
used is usually about 5 to about 50 parts by mass per 100 parts by mass of the polyester
resin. For example, the urethane-modified polyester resin can be prepared by reacting
the polyester resin with a polyisocyanate compound.
[0021]
As the polyester resin, a commercially available product may also be used, and
examples thereof include DYNAPOL LH820, DYNAPOL LH826, and DYNAPOL
LH727 (all manufactured by Evonik Industries AG), ETERKYD 5084-R-60-6E,
ETERKYD 3103-X-70, ETERKYD 50528-R-70, and ETERKYD 5055R-65-3 (all manufactured by Eternal Materials Co., Ltd.), BECKOLITE M-6902-50 (manufactured by DIC Corporation), and SYNOLAC 9605 (manufactured by ARKEMA).
[0022]
(Epoxy resin)
The epoxy resin is not particularly limited as long as it is an epoxy resin
commonly used for coating materials. Unless otherwise specified in the present
disclosure, when simply described as "epoxy resin", it means that the epoxy resin
comprises at least one species selected from the group consisting of epoxy resin and
modified products of epoxy resin.
[0023]
The hydroxyl value of the epoxy resin is preferably 40 to 200 mg KOH/g, and
more preferably 60 to 180 mg KOH/g. When the hydroxyl value of the epoxy resin is
in the above range, the reaction with the amino resin (B) as a curing agent proceeds
well. When the coating composition contains such an epoxy resin, there is an
advantage that a resulting coating film exhibits high solvent resistance, sufficient
folding processability, processing adhesive property, and chemical resistance.
[0024]
The number-average molecular weight of the epoxy resin is preferably 1,500 to
,000, and more preferably 2,000 to 4,000. When the number-average molecular
weight of the epoxy resin is in the above range, a curing reaction with the amino resin
(B) to be described later sufficiently proceeds, so that a coating film having good
coating film appearance can be formed. Further, it is possible to inhibit the crosslink
density of the coating film from becoming excessively high, and it is possible to form a
coating film having a sufficient elongation rate and, for example, it is possible to form a
coating film having sufficient folding processability and processing adhesive property.
Furthermore, the coating composition of the present disclosure has an appropriate
viscosity and is good in handleability.
[0025]
The glass transition temperature (Tg) of the epoxy resin may be 120°C or
lower, and maybe 115°C or lower. For example, the glass transition temperature (Tg)
of the epoxy resin maybe 110°C or lower. In one embodiment, the glass transition
temperature (Tg) of the epoxy resin is 500 C or higher and maybe 55°C or higher. For
example, the glass transition temperature (Tg) of the epoxy resin may be in a range of
°C or higher and 120°C or lower. When the glass transition temperature (Tg) of the
epoxy resin is in the above range, the moisture permeability of a coating film is not
excessively high and the coating film has sufficient moisture resistance and chemical
resistance.
[0026]
The epoxy resin may be a hydroxyl group-containing epoxy resin (including a
modified hydroxyl group-containing epoxy resin). Examples of the epoxy resin
include a resin prepared by condensing epichlorohydrin and bisphenol to a high
molecular weight in the presence of a catalyst such as an alkaline catalyst as necessary;
bisphenol type epoxy resins such as bisphenol A type and bisphenol F type; and novolak
type epoxy resins.
Examples of the modified products of epoxy resin include modified epoxy
resins such as acrylic-modified epoxy resins, urethane-modified epoxy resins, and
amine-modified epoxy resins. For example, the acrylic-modified epoxy resin can be
prepared by reacting the bisphenol type epoxy resin described above or the novolac type
epoxy resin described above with a polymerizable unsaturated monomer component
containing acrylic acid, methacrylic acid, or the like. For example, the urethane- modified epoxy resin can be prepared by reacting the bisphenol type epoxy resin described above or the novolak type epoxy resin described above with a polyisocyanate compound.
In one embodiment, the modified product of the epoxy resin is a resin other
than phosphoric acid-modified epoxy resins and sulfonic acid-modified epoxy resins.
[0027]
Commercially available products may also be used as the epoxy resin, and
examples thereof include jER825, jER828, jER835, jER1004, jER1007, jER1010,
jER1255HX30, jER YX8100BH30 (all are of bisphenol A type, manufactured by
Mitsubishi Chemical Corporation), and jERI009 F (Bisphenol F type, manufactured by
Mitsubishi Chemical Corporation).
[0028]
(Acrylic resin)
The acrylic resin is not particularly limited as long as it is an acrylic resin
commonly used for coating materials. Unless otherwise specified in the present
disclosure, when simply described as "acrylic resin", it means that it comprises at least
one species selected from the group consisting of acrylic resin and modified products of
acrylic resin.
[0029]
The hydroxyl value of the acrylic resin is preferably 40 to 100 mg KOH/g, and
more preferably 60 to 100 mg KOH/g. When the hydroxyl value of the acrylic resin is
in the above range, the reaction with the amino resin (B) as a curing agent proceeds
well. When the coating composition contains such an acrylic resin, there is an
advantage that a resulting coating film has high solvent resistance and chemical
resistance, and sufficient folding processability and processing adhesive property.
[0030]
The number-average molecular weight of the acrylic resin is preferably 1,500
to 5,000, and more preferably 2,000 to 4,000. When the number-average molecular
weight of the acrylic resin is in the above range, the curing reaction with the amino resin
(B) sufficiently proceeds and a coating film having good coating film appearance can be
formed. Further, it is possible to inhibit the crosslink density of the coating film from
becoming excessively high, and it is possible to form a coating film having a sufficient
elongation rate and, for example, it is possible to form a coating film having sufficient
folding processability. Furthermore, the coating composition of the present disclosure
has an appropriate viscosity and is good in handleability.
[0031]
The glass transition temperature (Tg) of the acrylic resin is preferably -35°C or
higher and 110°C or lower, for example, -30°C or higher and 80°C or lower, and may be
-30°C or higher and 60°C or lower. When the glass transition temperature (Tg) of the
acrylic resin is in the above range, the moisture permeability of a coating film is not
excessively high and the coating film has good moisture resistance and chemical
resistance.
[0032]
The acid value of the acrylic resin (including modified products thereof) is, for
example, 0.1 mg KOH/g or more and 30 mg KOH/g or less, or 0.2 mg KOH/g or more
and 30 mg KOH/g or less, and may be 0.3 mg KOH/g or more and 30 mg KOH/g or
less. When the acid value of the acrylic resin is in such a range, for example,
hydrolysis resistance can be improved, and a coating film having moisture resistance
and chemical resistance can be formed.
[0033]
Examples of the acrylic resin include acrylic resins made up of one or two or
more of monomer selected from among (meth)acrylic monomers having a hydroxy
group, such as hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate,
hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate and N-methylolacrylamide,
and lactone adducts thereof; (meth)acrylic acid; (meth)acrylic acid esters, such as alkyl
(meth)acrylate; and (meth)acrylonitrile. The acrylic resin may contain, in addition to
the constitutional units derived from the above-mentioned monomers, constitutional
units derived from other monomers (for example, carboxy group-containing ethylenic
monomers such as crotonic acid, itaconic acid, fumaric acid, and maleic acid, and vinyl
based monomers such as styrene). Examples of the modified products of acrylic resin
include modified acrylic resins such as silicone-modified acrylic resins. For example,
the silicone-modified acrylic resin can be prepared by reacting an acrylic resin with an
organic silicone such as that described above. The amount of the organic silicone used
is usually about 5 to about 50 parts by mass per 100 parts by mass of the acrylic resin.
In the present disclosure, (meth)acrylic acid represents acrylic acid or methacrylic acid.
As the acrylic resin, a commercially available product may also be used, and
examples thereof include ACRYDIC A-608, ACRYDIC A-452, and ACRYDIC A-830
(all manufactured by DIC Corporation).
[0034]
As the hydroxyl group-containing resin (A), only one species may be used, or
two or more species may be used in combination.
[0035]
<Amino resin (B)>
The amino resin (B) is a resin that reacts with the hydroxyl group-containing
resin (A) and the phosphoric acid-modified epoxy resin (D) to form a cured coating film.
The amino resin (B) is superior in curing reactivity with the hydroxyl group
containing resin (A) and the like and can afford a coating film having good appearance
and moisture resistance.
[0036]
Examples of the amino resin include melamine resin, urea resin, and
benzoguanamine, and melamine resin and urea resin are preferable. Especially from
the viewpoint of weather resistance, the amino resin preferably contains melamine resin,
and more preferably is melamine resin.
[0037]
"Melamine resin" generally means a thermally curable resin synthesized from
melamine and aldehyde, and has three reactive functional groups -NX1X2 in one triazine
nucleus molecule.
Examples of the melamine resin include the following four types: afully
alkylated type containing -N(CH 2 OR) 2 [R represents an alkyl group having 1 to 8
carbon atoms, the same applies hereinafter] as a reactive functional group; a methylol
group type containing -N(CH2 OR)(CH 2 OH) as a reactive functional group; an imino
group type containing -N(CH 20R)(H) as a reactive functional group; a methylol/imino
group type containing -N(CH 2OR)(CH 2 OH) and -N(CH 2 OR)(H) or containing
N(CH 2 OH)(H) as reactive functional groups.
In the present invention, it is preferable to use a fully alkylated melamine resin
among the melamine resins described above, and examples of such a resin include
methylated melamine resin, butylated melamine resin, and isobutylated melamine resin.
As the melamine resin, a commercially available product may also be used, and
examples thereof include CYMEL 303, CYMEL 325, CYMEL 350, CYMEL 370,
MYCOAT 715 (all are methylated melamine resins, manufactured by Allnex Japan
Inc.), CYMEL 202, CYMEL 235, CYMEL 254, CYMEL 1123, CYMEL 1128, CYMEL
1170, MYCOAT 212, (all are methylated-butylated mixed melamine resins,
manufactured by Allnex Japan Inc.), SUMIMAL M-40S (methylated melamine resin,
manufactured by Sumitomo Chemical Co., Ltd.), AMIDIR J-820-60, and AMIDIR L
127-60 (all are butylated melamine resins, manufactured by DIC Corporation).
[0038]
As the amino resin (B), only one species may be used, or two or more species
may be used in combination.
[0039]
In one embodiment, a polyester resin is used as the hydroxyl group-containing
resin (A) and a melamine resin is used as the amino resin (B).
[0040]
The coating composition of the present disclosure contains 60 to 90 parts by
mass of the hydroxyl group-containing resin (A) and 10 to 40 parts by mass of the
amino resin (B), preferably 70 to 80 parts by mass of the hydroxyl group-containing
resin (A) and 20 to 30 parts by mass of the amino resin (B), based on 100 parts by mass
of the total of the resin solid content of the hydroxyl group-containing resin (A) and the
resin solid content of the amino resin (B). When the hydroxyl group-containing resin
(A) and the amino resin (B) are contained in the above ranges, the curing reaction
between the hydroxyl group-containing resin (A) and the amino resin (B) proceeds well.
When these resins are contained in the above ranges, the appearance of a resulting
coating film can be improved. In addition, the solvent resistance, folding
processability, processing adhesive property, and chemical resistance of a coating film
obtained from the coating composition of the present disclosure are improved.
[0041]
<Covalently bonded blocked acid catalyst (C)>
The covalently bonded blocked acid catalyst (C) has a structure in which an
acid catalyst is blocked by a blocking agent, for example, a structure in which the acid
catalyst is protected by covalently bonding the blocking agent to the acid catalyst
(especially, an acid group of the acid catalyst). When the blocking agent protects the
acid catalyst, the action as a curing catalyst is suppressed during storage and the storage
stability of the coating composition is improved. When the blocking agent is
dissociated by heating or the like, the acid catalyst acts as a curing catalyst to accelerate
the reaction of the hydroxyl group-containing resin (A), the amino resin (B), and the
phosphoric acid-modified epoxy resin (D).
In the coating composition of the present disclosure, the acid catalyst moiety of
the covalently bonded blocked acid catalyst (C) is contained in an amount of 1 to 10
parts by mass, preferably 1 to 7 parts by mass, and more preferably 1 to 5 parts by mass,
based on 100 parts by mass of the total of the resin solid content of the hydroxyl group
containing resin (A) and the resin solid content of the amino resin (B). When the
covalently bonded blocked acid catalyst (C) is contained in the above range, the storage
stability of the resulting coating composition is good, and a coating film having high
solvent resistance and sufficient folding processability, processing adhesive property,
and chemical resistance will be formed by curing.
The acid catalyst moiety refers to, for example, a sulfonic acid when the
covalently bonded blocked acid catalyst (C) has a structure in which a blocking agent is
covalently bonded to a sulfonic acid.
[0042]
Usually, a coating composition often contains an acid catalyst in order to increase a curing rate. However, when the content of the acid catalyst increases, the storage stability of the coating composition tends to deteriorate. When an acid catalyst not protected by a blocking agent is used as the acid catalyst or when an acid catalyst neutralized by an amine (that is, an amine blocked acid catalyst) is used, the storage stability of a resulting coating composition and the physical properties of a coating film to be formed may be deteriorated.
In contrast, the coating composition of the present disclosure contains the
covalently bonded blocked acid catalyst (C), and hencet the curing reaction is
accelerated and the storage stability is improved.
[0043]
The covalently bonded blocked acid catalyst (C) preferably comprises a
sulfonic acid as an acid catalyst, and the acid catalyst is more preferably a sulfonic acid.
The number of sulfonic acid groups in the sulfonic acid is 1 or more per molecule, and
may be, for example, 2 or less, and is particularly 1.
[0044]
In one embodiment, the covalently bonded blocked acid catalyst (C) excludes a
phosphate compound.
[0045]
The covalently bonded blocked acid catalyst (C) is preferably one in which a
blocking agent is covalently bonded to all the sulfonic acid groups of the sulfonic acid
as an acid catalyst.
Examples of the sulfonic acid include aliphatic sulfonic acids such as
methanesulfonic acid, and aromatic sulfonic acids such as p-toluenesulfonic acid,
dinonylnaphthalenesulfonic acid, dinonylnaphthalenedisulfonic acid, and
dodecylbenzenesulfonic acid. These may be used singly, or two or more of them may be used in combination. In the present disclosure, the aromatic sulfonic acid refers to a sulfonic acid having a structure in which one or more sulfonic acid groups (e.g., one or two, specifically one sulfonic acid group) are directly bonded to an aromatic ring.
In the aromatic sulfonic acid, examples of the aromatic ring include a benzene
ring and a naphthalene ring.
In the aromatic sulfonic acid, one or more alkyl groups having 1 to 15 carbon
atoms may be bonded to a carbon atom constituting an aromatic ring; more specifically,
one or two alkyl groups, for example, one alkyl group may be bonded.
[0046]
Preferably, the covalently bonded blocked acid catalyst (C) has a blocked
structure in which a compound having a glycidyl group as a blocking agent is
covalently bonded to a sulfonic acid as an acid catalyst. In other words, it has a
structure in which a sulfonic acid (specifically, a sulfonic acid group of the sulfonic
acid) is blocked with a compound having a glycidyl group (specifically, a glycidyl
group of a compound having a glycidyl group).
[0047]
Furthermore, the covalently bonded blocked acid catalyst (C) preferably has a
structure in which an aromatic sulfonic acid is blocked with a compound having a
glycidyl group. In other words, it is preferable that the sulfonic acid group of the
aromatic sulfonic acid is blocked with the glycidyl group of the compound having a
glycidyl group. Due to the inclusion of such a covalently bonded blocked acid catalyst
(C), the stability of the coating composition during storage can be further improved, and
the glycidyl group is dissociated by heating or the like, so that the curing reaction can be
further accelerated.
[0048]
Examples of the aromatic sulfonic acid blocked with a glycidyl group include
compounds in which an aromatic sulfonic acid such as dinonylnaphthalenesulfonic acid,
dinonylnaphthalenedisulfonic acid, paratoluenesulfonic acid, or dodecylbenzenesulfonic
acid is blocked with a glycidyl group. Among them, a catalyst in which
dinonylnaphthalenesulfonic acid is blocked with a glycidyl group is particularly
preferable. As the aromatic sulfonic acid blocked with a glycidyl group, a
commercially available product may be used, and examples thereof include Nacure
1419 (trade name, manufactured by King Industries, Ltd.).
[0049]
In the covalently bonded blocked acid catalyst (C), the compound having a
glycidyl group to be used for blocking the sulfonic acid is preferably an epoxy resin
having two or more glycidyl groups in the molecule or a glycidyl ether compound
having one glycidyl group in the molecule. When such a compound is used, the
stability of the resulting coating composition during its storage can be further improved,
and the glycidyl group is dissociated by heating or the like, so that the curing reaction
can be further promoted.
Hereinafter, a covalently bonded blocked acid catalyst prepared by using an
epoxy resin having two or more glycidyl groups in the molecule as a blocking agent
may be referred to as a covalently bonded blocked acid catalyst (Cl), and a covalently
bonded blocked acid catalyst prepared by using a glycidyl ether compound having one
glycidyl group in the molecule as a blocking agent may be referred to as a covalently
bonded blocked acid catalyst (C2).
[0050]
The number of the glycidyl groups in the compound having a glycidyl group is
1 or more per molecule, and may be, for example, 5 or less, and may be 3 or less.
The number-average molecular weight of the compound having a glycidyl
group is preferably 100 to 10,000, and more preferably 140 to 7,000.
[0051]
In one embodiment, the compound having a glycidyl group to be used for
blocking the sulfonic acid is preferably an epoxy resin having two or more glycidyl
groups in the molecule.
The epoxy resin to be used for blocking the sulfonic acid is not particularly
limited as long as it is an epoxy resin having two or more glycidyl groups in the
molecule.
The epoxy resin may be a hydroxyl group-containing epoxy resin (including a
modified hydroxyl group-containing epoxy resin).
Examples of the epoxy resin include a resin prepared by condensing
epichlorohydrin and bisphenol to a high molecular weight in the presence of a catalyst
such as an alkaline catalyst as necessary; bisphenol type epoxy resins such as bisphenol
A type and bisphenol F type; and novolak type epoxy resins, and among these,
bisphenol type epoxy resins are preferable, and bisphenol A type epoxy resins are more
preferable.
[0052]
Examples of the modified products of epoxy resin include modified epoxy
resins such as acrylic-modified epoxy resins, urethane-modified epoxy resins, and
amine-modified epoxy resins. For example, taking an acrylic-modified epoxy resin as
an example, it can be prepared by reacting the bisphenol type epoxy resin or the novolac
type epoxy resin with a polymerizable unsaturated monomer component containing
acrylic acid, methacrylic acid, or the like. Taking a urethane-modified epoxy resin as
an example, it can be prepared by reacting the bisphenol type epoxy resin or the novolak type epoxy resin with a polyisocyanate compound.
[0053]
In one embodiment, the modified product of the epoxy resin excludes a
phosphoric acid-modified epoxy resin.
As the epoxy resin, a commercially available product may be used, and
examples thereof include jER825, jER828, jER834, jER1004, jER1007, jER1009,
jER1010, jER1255HX30 (all are of bisphenol A type, manufactured by Mitsubishi
Chemical Corporation), and jER1009F (bisphenol F type, manufactured by Mitsubishi
Chemical Corporation), andjER1007,jER1009, andjER1010 are preferable.
[0054]
The number-average molecular weight of the epoxy resin is preferably 2,000 to
7,000. When the number-average molecular weight of the epoxy resin is in the above
range, a curing reaction with the hydroxyl group-containing resin (A), the amino resin
(B), and the phosphoric acid-modified epoxy resin (D) sufficiently proceeds, and a
coating film having high solvent resistance and sufficient folding processability,
processing adhesive property, and chemical resistance can be formed.
[0055]
In one embodiment, the compound having a glycidyl group to be used for
blocking the sulfonic acid is preferably a glycidyl ether compound having one glycidyl
group in the molecule.
[0056]
The glycidyl ether compound to be used for blocking the sulfonic acid is not
particularly limited as long as it is a glycidyl ether compound having one glycidyl group
in the molecule.
Examples of the glycidyl ether compound include aromatic glycidyl ether compounds, aliphatic glycidyl ether compounds, and alicyclic glycidyl ether compounds. Among these, aromatic glycidyl ether compounds are preferable, and phenyl glycidyl ether is more preferable.
[0057]
As the glycidyl ether compound, a commercially available product may be
used, and examples thereof include phenyl glycidyl ether, o-cresyl glycidyl ether (both
are aromatic glycidyl ether compounds, manufactured by Yokkaichi Chemical Co.,
Ltd.), DY-BP, EPOGOSEY-2EH, EPOGOSEY-LA(D), and EPOGOSEY-AN (all are
aliphatic glycidyl ether compounds, manufactured by Yokkaichi Chemical Co., Ltd.),
and phenyl glycidyl ether are preferable.
[0058]
The molecular weight of the glycidyl ether compound is preferably 140 to 200.
When the molecular weight of the glycidyl ether compound is in the above range, a
curing reaction with the hydroxyl group-containing resin (A), the amino resin (B), and
the phosphoric acid-modified epoxy resin (D) sufficiently proceeds, and a coating film
having high solvent resistance and sufficient folding processability, processing adhesive
property, and chemical resistance can be formed. In the present disclosure, the
molecular weight of the glycidyl ether compound is a value calculated from a molecular
formula.
[0059]
The covalently bonded blocked acid catalyst (C) can be formed by, for
example, blocking a sulfonic acid group of a sulfonic acid with a glycidyl group of a
compound having a glycidyl group (specifically, an epoxy resin having two or more
glycidyl groups or a glycidyl ether compound having one glycidyl group; hereinafter,
the same applies in this paragraph). Specifically, the covalently bonded blocked acid catalyst (C) can be formed by weighing a sulfonic acid and a compound having a glycidyl group in such a mass that a molar ratio of the sulfonic acid groups of the sulfonic acid to the glycidyl groups of the compound having a glycidyl group is in a range of 1:1 to 1:2, adding them to a container, and stirring them, for example, at 90°C for 120 minutes thereby blocking the sulfonic acid group with the glycidyl group.
A coating composition can be formed by mixing the formed covalently bonded
blocked acid catalyst (C) with the hydroxyl group-containing resin (A), the amino resin
(B), the phosphoric acid-modified epoxy resin (D), and other components as necessary.
[0060]
<Phosphoric acid-modified epoxy resin (D)>
The phosphoric acid-modified epoxy resin (D) contains a phosphoric acid
group [-OPO(OH)(OR )]1 wherein R is a hydrogen atom, a phenyl group, or an alkyl
group having 1 to 20 carbon atoms and is particularly preferably a hydrogen atom. As
the phosphoric acid-modified epoxy resin (D), one compatible with the hydroxyl group
containing resin (A) and the amino resin (B) is used.
In the coating composition of the present disclosure, a solid component of the
phosphoric acid-modified epoxy resin (D) is contained in an amount of 1 to 10 parts by
mass, preferably I to 5 parts by mass, based on 100 parts by mass of the total of the
resin solid content of the hydroxyl group-containing resin (A) and the resin solid
content of the amino resin (B). When the phosphoric acid-modified epoxy resin (D) is
contained in the above range, a coating film having high solvent resistance and
sufficient folding processability, processing adhesive property, and chemical resistance
can be formed. In particular, even when the curing time is short, curing proceeds
sufficiently, so that a coating film having good physical properties can be formed.
[0061]
The number-average molecular weight of the phosphoric acid-modified epoxy
resin (D) is preferably 400 to 6,000, and more preferably 460 to 4,000. The
phosphoric acid-modified epoxy resin (D) having such a number-average molecular
weight can further contribute to a formation of a coating film having high solvent
resistance and sufficient folding processability, processing adhesive property, and
chemical resistance.
[0062]
The phosphoric acid-modified epoxy resin (D) can be obtained, for example,
by adding a phosphoric acid-based compound to an epoxy resin. Specifically, the
phosphoric acid-modified epoxy resin (D) can be obtained by mixing the epoxy resin
and the phosphoric acid-based compound in such a mass that a molar ratio of the
glycidyl groups of the epoxy resin to the phosphoric acid groups of the phosphoric acid
based compound is 1:1 to 1:2, and reacting the mixture, for example, at 80°C for 120
minutes.
In one embodiment, the epoxy resin comprises glycidyl groups only at both
ends.
In one embodiment, the phosphoric acid-modified epoxy resin (D) excludes a
phosphoric acid-modified epoxy resin reacted with a sulfonic acid.
[0063]
In the phosphoric acid-modified epoxy resin (D), examples of the epoxy resin
include bisphenol type epoxy resins, novolac type epoxy resins, and modified epoxy
resins obtained by reacting various modifiers with glycidyl groups or hydroxyl groups
in these epoxy resins. Among them, bisphenol type epoxy resins are preferably used,
and bisphenol A type epoxy resins are more preferably used.
As the epoxy resin, a commercially available product may be used, and examples thereof include jER825,jER828,jER834,jER1004,jER1007,jER1009, jER1010, jER1255HX30 (all are of bisphenol A type, manufactured by Mitsubishi
Chemical Corporation), and jER1009F (bisphenol F type, manufactured by Mitsubishi
Chemical Corporation), and jER828, jER834, jERI004, jER1007, and jER1009 are
preferable.
The number-average molecular weight of the epoxy resin is preferably 370 to
3,800, for example, when the phosphoric acid compound for modification is phosphoric
acid.
As the epoxy resin, an acrylic-modified epoxy resin, a polyester-modified
epoxy resin, or the like may be used.
[0064]
In one embodiment, in the phosphoric acid-modified epoxy resin (D), the
molecular weight of the phosphoric acid-based compound is 98 to 1,200.
[0065]
In the phosphoric acid-modified epoxy resin (D), the phosphoric acid-based
compound is not particularly limited as long as it can introduce a phosphoric acid group
into the epoxy resin, and examples thereof include orthophosphoric acid and acidic
phosphoric acid esters.
The acidic phosphoric acid ester refers to a structure in which one or two
hydrogens among three hydrogens of phosphoric acid (O=P(OH) 3) are replaced by an
organic group. Examples of the organic group include an alkyl group (for example,
having 1 to 24 carbon atoms), an alkyl ether group (for example, represented by R
OR4 0-, wherein R3 is an alkyl group having 1 to 5 carbon atoms, andR4 is methylene
group, ethylene group, propylene group, preferably ethylene group or propylene group),
and an aromatic group. Examples of the acidic phosphoric acid ester include methyl acid phosphate, butyl acid phosphate, 2-ethylhexyl acid phosphate, isodecyl acid phosphate, lauryl acid phosphate, isotridecyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, and phenyl acid phosphate.
[0066]
The coating composition of the present disclosure comprises the covalently
bonded blocked acid catalyst (C) and the phosphoric acid-modified epoxy resin (D)
together with the hydroxyl group-containing resin (A) and the amino resin (B) as
described above. When both the covalently bonded blocked acid catalyst (C) and the
phosphoric acid-modified epoxy resin (D) are contained, storage stability of the coating
composition, specifically, viscosity increase during storage can be suppressed, and the
curing reaction is sufficiently advanced even by heating for a short time (for example, 1
to 10 seconds, specifically 1 to 6 seconds), so that a coating film can be formed. For
example, in an 1H type furnace, the temperature can be raised in a short time, and
specifically, the PMT can be raised to 220°C in about 6 seconds. In the coating
composition of the present disclosure, even when such an IH type furnace is used, the
curing reaction sufficiently proceeds and a coating film having good physical properties
can be formed.
Furthermore, by heating the coating composition of the present disclosure at,
for example, 170°C to 280°C, the curing reaction sufficiently proceeds, so that a coating
film can be formed. In particular, in the coating composition of the present disclosure,
a curing reaction sufficiently proceeds even when heated at a relatively low temperature
(for example, 170 0C to 220°C, specifically, 180°C to 220°C), and a coating film having
good physical properties, such as coating film appearance, solvent resistance, folding
processability, processing adhesive property, alkali resistance, and acid resistance is
obtained. Coating films obtained by heating at a relatively low temperature exhibits the same physical properties as coating films obtained at a commonly used temperature suchas270°Cor280°C.
When the coating composition of the present disclosure is used, a coating film
having good physical properties, such as solvent resistance, folding processability,
processing adhesive property, and chemical resistance is obtained even when the coating
film is formed by heating for a short time. The physical properties of the coating film
formed by such short-time heating are equivalent to the physical properties of the
coating film formed in a normal heating time (for example, 25 seconds, 30 seconds, and
the like).
[0067]
<Other resins>
The coating composition may contain other resin to be used in the field of
coating compositions as long as the effects exhibited by the present disclosure are not
impaired. Examples of such other resin include polyester resin other than those
described above, and modified products thereof (urethane-modified polyester resins,
epoxy-modified polyester resins, silicone-modified polyester resins, and the like);
urethane resin and modified products thereof (ester-based urethane resins, ether-based
urethane resins, carbonate-based urethane resins, epoxy-based urethane resins, and the
like); phenol resin and modified products thereof (acrylic-modified phenolic resins,
epoxy-modified phenolic resins, and the like); phenoxy resin; alkyd resin and modified
products thereof (urethane-modified alkyd resins, acrylic-modified alkyd resins, and the
like); and such resins as fluororesin. These resins may be used singly, or two or more
of them may be used in combination.
[0068]
<Alkanolamine (E)>
The coating composition of the present disclosure may further comprise an
alkanolamine (E). The alkanolamine (E) is a compound having one or more alkanol
groups, and particularly is an amine having one or more alkanol groups. In the present
disclosure, an alkanol group refers to a group represented by -R2-OH wherein R2 is an
alkylene group having 1 or more carbon atoms.
The inclusion of the alkanolamine (E) has the advantage of making the storage
stability of the coating composition better.
[0069]
The alkanolamine (E) preferably has one or more amino groups and two or
more alkanol groups per molecule, more preferably has one or more amino groups and
two or three alkanol groups per molecule, and still more preferably has one amino group
and two or three alkanol groups per molecule.
[0070]
In one embodiment, the molecular weight of the alkanolamine (E) is in a range
of60to200.
The alkanol group of the alkanolamine (E) preferably has 1 to 3, and more
preferably 2 to 3 carbon atoms. 2 2 -n(-R-OH)". In one embodiment, the alkanolamine (E) is represented by NR 3
n is an integer of1 to 3, preferably 2 or 3, and eachR 22 independently represents, for
example, a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (specifically, 1
to 3 carbon atoms), and each R independently represents an alkylene group having 1 to
3 carbon atoms (preferably 2 to 3 carbon atoms).
The alkanolamine (E) is not particularly limited, and examples thereof include
amines having one alkanol group such as ethanolamine and dimethylaminoethanol;
amines having two alkanol groups such as diisopropanolamine and diethanolamine; and amines having three alkanol groups such as triisopropanolamine and triethanolamine.
Among these, diisopropanolamine, triisopropanolamine, diethanolamine, and
triethanolamine are preferable, and diisopropanolamine and triisopropanolamine are
more preferable. As the alkanolamine (E), only one species may be used, or two or
more species may be used in combination.
[0071]
The content of the alkanolamine (E) is preferably 1.0 to 10.0 parts by mass,
more preferably 1.0 to 4.0 parts by mass, still more preferably 1.0 to 3.5 parts by mass,
and may be 1.0 to 3.0 parts by mass, based on 100 parts by mass of the total of the resin
solid content of the hydroxyl group-containing resin (A) and the resin solid content of
the amino resin (B). The inclusion of the alkanolamine (E) in the above range has the
advantage of making the storage stability of the coating composition better.
[0072]
<Other additives>
The coating composition of the present disclosure may comprise additives
other than those mentioned above, as necessary.
Examples of such other additives include extender pigments; colorants such as
coloring pigments and dyes; luster pigments; aggregates (resin particles, silica particles,
and the like); waxes; solvents; ultraviolet absorbers (benzophenone-based ultraviolet
absorbers); antioxidants (phenolic, sulfide-based, or hindered amine antioxidants, and
the like); plasticizers; coupling agents (silane-based, titanium-based, zirconium-based
coupling agents, and the like); sagging inhibitors; viscosity control agents; pigment
dispersants; pigment wetting agents; surface conditioning agents (silicone-based,
organic polymer-based, and the like); leveling agents; color separation inhibitors;
suspending agents; antifoaming agents; antifreezing agents; emulsifiers; antiseptic agents; antifungal agents; antibacterial agents; and stabilizers. These additives may be used singly, or two or more of them may be used in combination.
[0073]
Examples of the extender pigment include calcium carbonate, barium sulfate,
clay, talc, mica, and glass fiber. These may be used singly, or two or more of them
may be used in combination.
In one embodiment, an amount of the extender pigment is 1 part by mass or
more and 40 parts by mass or less, for example 10 parts by mass or more and 30 parts
by mass or less, based on 100 parts by mass of the total of the resin solid content of the
hydroxyl group-containing resin (A) and the resin solid content of the amino resin (B).
When the amount of the extender pigment is in such a range, there is an advantageous
effect of improving scratch resistance of a coating film.
[0074]
Examples of the coloring pigments include coloring inorganic pigments such as
titanium dioxide, carbon black, graphite, iron oxide, and coal dust; coloring organic
pigments such as phthalocyanine blue, phthalocyanine green, quinacridone, perylene,
anthrapyrimidine, carbazole violet, anthrapyridine, azo orange, flavanthrone yellow,
isoindoline yellow, azo yellow, indanthrone blue, dibromanzathrone red, perylene red,
azo red, and anthraquinone red; aluminum powder, alumina powder, bronze powder,
copper powder, tin powder, zinc powder, iron phosphide, and atomized titanium.
These may be used singly, or two or more of them may be used in combination.
[0075]
In one embodiment, the coating composition may comprise a heat shielding
pigment. The heat shielding pigment to be used is not particularly limited, and
examples thereof include the following heat shielding pigments. In the present disclosure, the heat shielding pigment refers to a pigment that does not absorb light in the near-infrared wavelength range (wavelength: 780 nmto 2,500 nm) or has a small light absorption rate in the near-infrared wavelength range (wavelength: 780 nm to
2,500 nm).
[0076]
The heat shielding pigment includes inorganic heat shielding pigments and
organic heat shielding pigments.
Examples of the inorganic heat shielding pigments include metal oxide
pigments such as titanium oxide, magnesium oxide, barium oxide, calcium oxide, zinc
oxide, zirconium oxide, yttrium oxide, indium oxide, sodium titanate, silicon oxide,
nickel oxide, manganese oxide, chromium oxide, iron oxide, copper oxide, cerium
oxide, and aluminum oxide; complex inorganic colored pigments such as iron oxide
manganese oxide, iron oxide-chromium oxide (for example, DAIPYROXIDE COLOR
BLACK #9595 manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd. and
Black 6350 manufactured by Asahi Kasei Kogyo Co., Ltd.), iron oxide-cobalt oxide
chromium oxide (for example, DAIPYROXIDE COLOR BROWN #9290 and
DAIPYROXIDE COLOR BLACK #9590 manufactured by Dainichiseika Color &
Chemicals Mfg. Co., Ltd.), copper oxide-magnesium oxide (for example,
DAIPYROXIDE COLOR BLACK #9598 manufactured by Dainichiseika Color &
Chemicals Mfg. Co., Ltd.), manganese oxide-bismuth oxide (for example, Black 6301
manufactured by Asahi Kasei Kogyo Co., Ltd.), and manganese oxide-yttrium oxide
(for example, Black 6303 manufactured by Asahi Kasei Kogyo Co., Ltd.); metallic
pigments such as silicon, aluminum, iron, magnesium, manganese, nickel, titanium,
chromium, and calcium; and alloy pigments such as iron-chromium, bismuth
manganese, iron-manganese, and manganese-yttrium. These may be used singly, or two or more of them may be used in combination.
Examples of the organic heat shielding pigment include azo pigments,
azomethine pigments, lake pigments, thioindigo pigments, anthraquinone pigments
(anthanthrone pigment, diaminoanthraquinonyl pigment, indanthrone pigment,
flavanthrone pigment, anthrapyrimidine pigment, and the like), perylene pigments,
perinone pigments, diketopyrrolopyrrole pigments, dioxazine pigments, phthalocyanine
pigments, quinophthalone pigments, quinacridone pigments, isoindoline pigments, and
isoindolinone pigments. These can be used singly or two or more of them may be used
in combination.
[0077]
Examples of the luster pigments include foil pigments such as aluminum foil,
bronze foil, tin foil, gold foil, silver foil, titanium metal foil, stainless steel foil, alloy
foil of nickel and copper, and the like, and foil-like phthalocyanine blue. These may
be used singly, or two or more of them may be used in combination.
[0078]
As the wax, waxes known to those skilled in the art for coating materials can
be used, and examples thereof include microcrystalline wax, polyethylene wax,
polypropylene wax, paraffin wax, carnauba wax, and modified products thereof.
These may be used singly, or two or more of them may be used in combination.
[0079]
Examples of the solvent include water; glycol-based organic solvents such as
ethylene glycol monobutyl ether (butyl cellosolve), diethylene glycol monobutyl ether,
triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene
glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol
monomethyl ether, dipropylene glycol monoethyl ether, and propylene glycol monomethyl ether acetate; alcohol-based organic solvents such as methanol, ethanol, and isopropyl alcohol; ether-based organic solvents such as dioxane and tetrahydrofuran; ester-based organic solvents such as 3-methoxybutyl acetate, ethyl acetate, isopropyl acetate, and butyl acetate; ketone-based organic solvents such as methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclohexanone, and isophorone; nitrogen-containing organic solvents such as N-methyl-2-pyrrolidone; toluene, pentane, isopentane, hexane, isohexane, and cyclohexane, solvent naphtha, mineral spirits, T
SOL 100 and T-SOL 150 (both are aromatic hydrocarbon-based solvents, manufactured
by JXTG Energy Corporation). These may be used singly, or two or more of them
may be used in combination.
[0080]
The coating composition of the present invention may be either a water-borne
coating material or an organic solvent-borne coating material.
[0081]
[Method for preparing coating composition]
The method for preparing the coating composition according to the present
disclosure is not particularly limited. For example, the coating composition can be
prepared by mixing ingredients using a mixing machine such as a roller mill, a ball mill,
a beads mill, a pebble mill, a sand grind mill, a pot mill, a paint shaker, or a disper, a
dispersing machine, a kneading machine, or the like.
[0082]
[Method for manufacturing coating film]
The method for producing a coating film of the present disclosure comprises:
a step of applying the coating composition of the present disclosure to an
article to be coated such as a steel sheet to form an applied film; and a step of heating the article to dry and/or cure the applied film.
[0083]
Examples of the article to be coated include a galvanized steel sheet, a zinc
aluminum alloy plated steel sheet, an aluminum alloy plated steel sheet, and a hot-dip
zinc-aluminum-magnesium alloy plated steel sheet manufactured by a melting method
or an electrolytic method, a stainless steel sheet, and a cold rolled steel sheet. In
addition to these steel sheets or plated steel sheets, metal sheets such as aluminum sheet
(including aluminum alloy sheet) can also be used as an article to be coated.
[0084]
The article to be coated is preferably surface-treated. Specifically, the article
to be coated is preferably subjected to chemical conversion treatment after being
subjected to pretreatment such as alkali degreasing treatment, hot water washing
treatment, or water washing treatment.
The chemical conversion treatment may be carried out by a conventionally
known method, and examples thereof include chromate treatment and non-chromate
treatment such as zinc phosphate treatment. While the surface treatment may be
appropriately selected depending on the steel sheet to be used, a treatment free of heavy
metals is preferable. By applying the coating composition of the present disclosure to
an article subjected to chemical conversion treatment as described above, the adhesive
property of the coating film to a metal sheet surface is improved and corrosion
resistance is also improved. It is also possible to form an undercoat coating film
(primer coating film) on the metal sheet surface subjected to the chemical conversion
treatment and apply the coating composition onto the undercoat coating film.
[0085]
The method of applying the coating composition is not particularly limited, and conventionally publicly known means such as a roll coater, an airless spray, an electrostatic spray, and a curtain flow coater can be employed, and the coating composition is preferably applied with a roll coater or a curtain flow coater.
[0086]
The temperature at which the applied film formed by applying the coating
composition is dried and/or cured, that is, the peak temperature (the maximum
temperature to which an article to be coated such as a steel sheet reaches) is, for
example, 170°C to 280°C, specifically, 180°C to 270°C, and may be 200°C to 250°C.
The drying and/or curing time may be, for example, as short as 1 to 10 seconds,
specifically 1 to 6 seconds.
The method for drying and/or curing the applied film is not particularly limited,
and heating means such as hot air heating, infrared heating, or induction heating can be
used.
[0087]
That is, the method for producing a coating film of the present disclosure may
comprise:
a step of applying the coating composition of the present disclosure to an
article to be coated to form an applied film; and
a step of drying and/or curing the applied film under a condition in which a
peak temperature of the article is 180°C to 270°C and a drying and/or curing time is 1 to
seconds.
[0088]
The film thickness (dry film thickness) of a coating film obtained by baking the
applied film and curing the resin is usually 1 to 30 pm, and for example, in the case of a
top coating film, it is preferably 5 to 30 m. For example, the dry film thickness may be 5 to 25 m.
[0089]
In the present disclosure, drying and/or curing means performing at least one of
drying and curing, and preferably performing both drying and curing.
[0090]
[Precoated metal sheet]
The precoated metal sheet of the present disclosure comprises a coating film
formed from the coating composition according to the present disclosure on at least one
surface of the metal sheet.
For example, the film thickness of a coating film formed from the coating
composition according to the present disclosure is 5 tmor more and 30 pm or less, and
in one embodiment, the film thickness is 10 pm or more and 25 pm or less.
As the metal sheet, those described above as an article to be coated can be
used.
[0091]
When the precoated metal sheet comprises a coating film formed from the
coating composition according to the present disclosure on one surface of a metal sheet,
the other surface may be a coating film formed from a known coating composition.
For example, the other surface may have a coating film formed from a publicly known
coating composition such as a coating composition containing an epoxy resin.
[0092]
The precoated metal sheet may have an undercoat coating film between the
metal sheet and the coating film formed from the coating composition of the present
disclosure.
The undercoat coating material may be conventionally publicly known one, and examples thereof include a conventionally publicly known non-chromium rust proof coating material. By having an undercoat coating film, the adhesive property and the corrosion resistance of a coating film formed from the coating composition of the present disclosure can be enhanced.
In one embodiment, the film thickness of the undercoat coating film is 3 m or
more and 15 pm or less, for example, 5 m or more and 10 pm or less.
[0093]
In one embodiment, the precoated metal sheet of the present disclosure can be
produced by a method comprising:
a step of applying the coating composition according to the present disclosure
to at least one surface of a metal sheet such that a film thickness after curing is 5 to 25
gm to form an applied film; and
a step of drying and/or curing the applied film under a condition in which a
peak temperature of the metal sheet is 180°C to 270°C and a drying and/or curing time
is 1 to 10 seconds.
In the method for producing a precoated metal sheet, formation of an applied
film and drying and/or curing of the applied film may be performed in the same manner
as in the method for producing a coating film described above.
[0094]
The present invention will be described more specifically with reference to the
following examples, but the present invention is not limited to the examples. In the
examples, "parts" and "%" are on a mass basis unless otherwise indicated.
[0095]
Details of the hydroxyl group-containing resins (A1) to (A13) used in
Examples, Comparative Examples, and Reference Examples are as shown in Tables lA
to 1C.
[0096]
[Table 1A] Hydroxyl group-containing resin (Al) (A2) (A3) (A4) (A) Polyester Polyester Polyester Polyester resin 1 resin 2 resin 3 resin 4 ETERKYD DYNAPL ETERKYD SYNOLAC Commercial raw material 5055R-65-3 LH 538 50528-R-70 9605 Eternal Evonik Eternal Manufacturer Materials Co., Industries AG Materials Co., ARKEMA Ltd. Ltd. Solid concentration (mass%) 65 65 70 65 Number-average molecular weight 4,000 3,000 2,500 2,000 Hydroxyl value (mg KOH/g) 60 45 65 50
[0097]
[Table 1B] Hydroxyl group-containing resin (A5) (A6) (A7) (A8) (A) Polyester Polyester Polyester Polyester resin 5 resin 6 resin 7 resin 8
Commercial raw material DYNAPL DYNAPL ETERKYD DYNAPOL LH 724 LH 727 3103-X-70 LH820 Evonik Evonik Eternal Evonik Manufacturer Industries AG Industries AG Matenals Co.' Industries AG Ltd. Solid concentration (mass%) 70 65 70 50 Number-average molecular weight 2,000 2,000 1,500 5,000 Hydroxyl value (mg KOH/g) 70 100 125 20
[0098]
[Table 1C] Hydroxylgroup-containingresin (A9) (A1O) (All) (A12) (A13) (A) Polyester Polyester Polyester Epoxy resin 1 Acrylic resin resin 9 resin 10 resin 11 DYNAPOL ETERKYD BECKOLITE . ACRYDIC Commercialrawmaterial LH826 5084-R-60-6E M-6902-50 jER1007 A830 Evonik Eternal DIC Mitsubishi DIC Manufacturer Industries AG Materials Co., CorDoration Chemical CoDIration Ltd. Corporation Solid concentration (mass%) 55 60 50 100 60 Number-average molecular weight 6,000 7,200 11,700 2,900 3,000 Hydroxyl value (mg KOH/g) 20 64 8 170 80
[0099]
The hydroxyl group-containing resin (A 12) (epoxy resin 1) used was prepared
by dissolving 90 parts by mass of jER1007 (manufactured by Mitsubishi Chemical
Corporation; solid concentration: 100 mass%) in 210 parts by mass of cyclohexanone to
adjust the solid concentration to 30 mass%.
[0100]
<Amino resin (B)>
Details of the amino resins (B1) to (B6) are as shown in Tables 2A and 2B.
The details of the isocyanate compound used in Comparative Examples are also shown
in Table 2B.
[0101]
[Table 2A] Amino resin (B) Amino resin (B1) Amino resin (B2) Amino resin (B3) 1Amino resin (B4) Melamine resin 1 Melamine resin 2 Melamine resin 3 Melamine resin 4 Commercial raw material CYMEL 303 CYMEL 350 CYMEL 235 CYMEL 325 Manufacturer Allnex Japan Inc. Allnex Japan Inc. Allnex Japan Inc. Allnex Japan Inc. Solid concentration(%) 100 100 100 80 Functional group Fully Alkylated Fully Alkylated Fully Alkylated Imino Alkyl group type Methyl Methyl Methyl/butyl mix Methyl
[0102]
[Table 2B]
Amino resin (B) Amino resin (B5) Amino resin (B6) coone
Melamine resin 5 Melamine resin 6 Polyisocyanate compound 1
Commercial raw material MYCOAT 212 CYMEL 370 DESMODUR
Manufacturer Allnex Japan Inc. Allnex Japan Inc. Urehane Co.,Ltd.
Solid concentration (%) 90 88 75 Functional group Imino Methylol Blocked isocyanate Alkyl group type Methyl/butyl mix Methyl
[0103]
<Production example of covalently bonded blocked acid catalyst (C11)>
A reaction vessel equipped with a thermometer, a condenser, a dropping funnel,
and a stirrer was charged with 37 parts by mass of Nacure 1051 (manufactured by King
Industries, Ltd.), and the temperature was raised to 90°C under a nitrogen atmosphere.
To this, a mixed solution prepared by dissolving 220 parts by mass of jER 1010
(bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation) as
an epoxy resin in 220 parts by mass of methyl propylene glycol (manufactured by
Nippon Nyukazai Co., Ltd.) in advance was dropped at a constant rate over 60 minutes
through the dropping funnel. Thereafter, the reactant temperature was held at 90°C for
minutes, and thus covalently bonded blocked acid catalyst (C11) was prepared.
After the synthesis, it was confirmed that the solid acid value of the covalently bonded
blocked acid catalyst (C11) was 0, and thereby it was confirmed that the blocking agent
was covalently bonded to all sulfonic acid groups.
[0104]
<Production examples of covalently bonded blocked acid catalysts (C12) to
(C28)>
Covalently bonded blocked acid catalysts (C12) to (C28) were prepared in the
same manner as in Production Example of (C11) except that the type and amount of each component were changed as described in the table. In addition, as in the case of
(C11), it was confirmed that the solid acid value of each covalently bonded blocked acid
catalyst was 0 after synthesis.
[0105]
Various characteristic values of each component and the prepared covalently
bonded blocked acid catalysts (C11) to (C28) are shown in Tables 3A to 3D.
[0106]
<Acid catalysts (c31), (c32)>
<Production example of acid catalyst (c31)>
A reaction vessel equipped with a thermometer, a condenser, a dropping funnel,
and a stirrer was charged with 185 parts by mass of Nacure 1051 (manufactured by
King Industries, Ltd.), and the temperature was raised to 400 C under a nitrogen
atmosphere. To this, a mixed solution prepared by dissolving 20 parts by mass of
triethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) in 20 parts by mass
of methyl propylene glycol (manufactured by Nippon Nyukazai Co., Ltd.) in advance
was dropped at a constant rateover 60 minutes through the dropping funnel.
Thereafter, the reactant temperature was held at 40°C for 60 minutes, and thus acid
catalyst (C31) was prepared. After the synthesis, it was confirmed that the solid acid
value of the acid catalyst (C31) was 0, and thereby it was confirmed that the blocking
agent was covalently bonded to all sulfonic acid groups.
[0107]
Characteristic values of the prepared acid catalysts (c31) and (c32) are shown
in Table 3B.
[0108]
[Table 3A] Covalently bonded blocked acid catalyst (C) (Cl1) (C12) (C13) (C14) (C15) Nacure 1051 37 37 37 37 37 Sulfonic TAYCACURE AC400S acid_________________________ TAYCACURE AC700 Subtotal 371 37 371 37 . 37 jER 1004 66 jER 1007 116 Epoxy jER1009 152 resin jER 1010 220 jER1255HX30 400 jER 1009F
comund Triethylamine Solvent Methyl propylene glycol 220 152 116 66 933 Grand total [ 4771 3411 2691 1691 1,370 Solid concentration (mass%) 50 50 50 50 31 Blocking agent Epoxy resin Epoxy resin Epoxy resin Epoxy resin Epoxy resin Number-average molecular weight of acid 6,000 4,300 3,400 2,100 10,500 catalyst
[0109]
[Table 3B] Covalently bonded blocked acid catalyst Acid Acid (C) catalyst 1 catalyst 2 (C16) (C17) (C18) (c31) (c32) Nacure 1051 371 1 185 200 Sulfonic TAYCACURE AC400S ... . 33_1 _ 1 TAYCACURE AC700 1 28 Subtotal 1 371 331 281 1851 200 jER 1004 jER 1007 Epoxy jER 1009 resin jER 1010 220 220 jER1255HX30 jER 1009F 116
compound Triethylamine 20 Solvent Methyl propylene glycol 116 220 220 20 Grand total 1 2691 473 4681 2251 200 Solid concentration (mass%) 50 47 47 50 50 Blocking agent Epoxy resin Epoxy resin Epoxy resin Triethylamine None Number-average molecular weight of acid 3,400 5,800 5,700 - catalyst
[0110]
[Table 3C] Covalently bonded blocked acid catalyst (C) (C21) (C22) (C23) (C24) (C25) Nacure 1051 37 37 37 37 37 Sulfonic TAYCACURE AC400S TAYCACURE AC700 Subtotal 37[ 37 37 37 37 Phenyl glycidyl ether 6 o-Cresyl glycidyl ether 7 Glycidyl DY-BP 5 S ether compound EPOGOSEY 2EH 7 EPOGOSEYLA(D) 10 EPOGOSEY AN
comund Triethylamine Solvent Methyl propylene glycol 6 7 5 7 10 Grand total 491 51 47 51 57 Solid concentration (mass%) 50 50 50 50 50 Glycidyl Glycidyl Glycidyl Glycidyl Glycidyl Blocking agent ether ether ether ether ether compound compound compound compound compound Molecular weight of acid catalyst 610 590 624 646 702
[0111]
[Table 3D] Covalently bonded blocked acid catalyst (C) (C26) (C27) (C28) Nacure 1051 37 Sulfonic TAYCACURE AC400S 33 acid_____________ TAYCACURE AC700 28 Subtotal 1 371 33[ 28 Phenyl glycidyl ether 6 6 o-Cresyl glycidyl ether Glycidyl DY-BP E ether compound EPOGOSEY 2EH EPOGOSEY LA (D) EPOGOSEY AN 10
comund Triethylamine Solvent Methyl propylene glycol 10 6 6 Grand total 57 45 40 Solid concentration (mass%) 50 43 33 Glycidyl Glycidyl Glycidyl Blocking agent ether ether ether compound compound compound Molecular weight of acid catalyst 711 476 322
[0112]
The compounds shown in Tables 3A to 3D are as follows.
rSulfonic acid]
- Nacure 1051: Dinonylnaphthalenesulfonic acid (manufactured by King
Industries, Ltd.) Active ingredient concentration: 50 mass%
- TAYCACURE AC400S: Dodecylbenzenesulfonic acid (manufactured by
Tayca Corporation) Active ingredient concentration:40 mass%
- TAYCACURE AC700: Paratoluenesulfonic acid (manufactured by Tayca
Corporation) Active ingredient concentration: 25 mass%
[Epoxy resin]
- jER 1004: Bisphenol A type epoxy resin (manufactured by Mitsubishi
Chemical Corporation) Number-average molecular weight: 1,700, solid concentration:
100 mass%
- jER 1007: Bisphenol A type epoxy resin (manufactured by Mitsubishi
Chemical Corporation) Number-average molecular weight: 2,900, solid concentration:
100 mass%
-jER 1009: Bisphenol A type epoxy resin (manufactured by Mitsubishi
Chemical Corporation) Number-average molecular weight: 3,800, solid concentration:
100 mass%
-jER 1010: Bisphenol A type epoxy resin (manufactured by Mitsubishi
Chemical Corporation) Number-average molecular weight: 5,500, solid concentration:
100 mass%
- jER 1255HX30: Bisphenol A type epoxy resin (manufactured by Mitsubishi
Chemical Corporation) Number-average molecular weight: 10,000, solid concentration:
100 mass%
- jER 1009F: Bisphenol F type epoxy resin (manufactured by Mitsubishi
Chemical Corporation) Number-average molecular weight: 2,900, solid concentration:
100 mass%
[Glycidyl ether compound]
- Phenyl glycidyl ether: Aromatic glycidyl ether compound (manufactured by
Yokkaichi Chemical Co., Ltd.) Molecular weight: 150, active ingredient concentration:
100 mass%
- o-Cresyl glycidyl ether: Aromatic glycidyl ether compound (manufactured by
Yokkaichi Chemical Co., Ltd.) Molecular weight: 164, active ingredient concentration:
100 mass%
- DY-BP: Aliphatic glycidyl ether compound (butyl glycidyl ether
manufactured by Yokkaichi Chemical Co., Ltd.) Molecular weight: 130, active
ingredient concentration: 100 mass%
- EPOGOSEY 2EH: Aliphatic glycidyl ether compound (2-ethylhexyl glycidyl
ether manufactured by Yokkaichi Chemical Co., Ltd.) Molecular weight: 186, active
ingredient concentration: 100 mass%
- EPOGOSEY LA (D): Aliphatic glycidyl ether compound (lauryl glycidyl
ether manufactured by Yokkaichi Chemical Co., Ltd.) Molecular weight: 242, active
ingredient concentration: 100 mass%
- EPOGOSEY AN: Aliphatic glycidyl ether compound (C12-13 mixed alcohol
glycidyl ether manufactured by Yokkaichi Chemical Co., Ltd.) Molecular weight: 251,
active ingredient concentration: 100 mass%
[Others]
- Amine compound: Triethylamine (manufactured by Tokyo Chemical Industry
Co., Ltd.) Active ingredient concentration: 100 mass%
- Solvent: Methyl propylene glycol: propylene glycol monomethyl ether
(manufactured by Nippon Nyukazai Co., Ltd.)
[0113]
<Production example of phosphoric acid-modified epoxy resin (Dl)>
A reaction vessel equipped with a thermometer, a condenser, a dropping funnel,
and a stirrer was charged with 43 parts by mass of an 85% aqueous phosphoric acid
solution and 22 parts by mass of propylene glycol monomethyl ether, and the
temperature was raised to 80°C under a nitrogen atmosphere. To this, a mixed solution
prepared by dissolving 179 parts by mass ofjER 834 (bisphenol A type epoxy resin,
manufactured by Mitsubishi Chemical Corporation) as an epoxy resin in 32 parts by
mass of propylene glycol monomethyl ether in advance was dropped at a constant rate
over 60 minutes through the dropping funnel. Thereafter, the reactant temperature was
held at 80°C for 60 minutes, and thus phosphoric acid-modified epoxy resin (D1) was
prepared.
[0114]
<Production examples of phosphoric acid-modified epoxy resins (D2) to (D7)>
Phosphoric acid-modified epoxy resins (D2) to (D7) were prepared in the same
manner as in Production Example of (D1) except that the type and amount of each
component were changed as described in the table. Characteristic values of the
components and the prepared phosphoric acid-modified epoxy resins (D1) to (D7) are
shown in Tables 4A and 4B.
[0115]
[Table 4A] Phosphoric acid-modified epoxy resin (D) (D1) (D2) (D3) (D4) 85% Phosphoric acid 43 43 43 43 Methyl propylene glycol 22 22 22 22 Subtotal 65 65 65 65 jER 825 130 jER 828 141 jER 834 179 jER 1009 1,451 jER 1010 jER 1009F Methyl propylene glycol 32 25 23 1,451 Grand total] 2761 2311 2181 2,967 Solid concentration (%) 78 77 76 50 Number-average molecular weight 570 470 440 3,900 Numberof phosphoric acid groups in one molecule 1 1 1 1
[0116]
[Table 4B] Phosphoric acid-modified epoxy resin (D) (D5) (D6) (D7) 85% Phosphoric acid 43 43 86 Methyl propylene glycol 22 22 44 Subtotal 65 65 130 jER825 jER 828 jER 834 179 jER1009 jER 1010 2,100 jER 1009F 1,107 Methyl propylene glycol 2,100 1,107 32 Grand total[ 4,265] 2,279[ 341 Solid concentration (%) 50 50 74 Number-average molecular weight 5,600 3,000 660 Number of phosphoric acid groups in one molecule 1 1 2
[0117]
The compounds shown in Table 4A and Table 4B are as follows.
[Phosphoric acid]
- 85% phosphoric acid: manufactured by Kishida Chemical Co., Ltd.
[Epoxy resin]
-jER 825: Bisphenol A type epoxy resin (manufactured by Mitsubishi
Chemical Corporation) Number-average molecular weight: 340, solid concentration:
100 mass%
- jER 828: Bisphenol A type epoxy resin (manufactured by Mitsubishi
Chemical Corporation) Number-average molecular weight: 370, solid concentration:
100 mass%
- jER 834: Bisphenol A type epoxy resin (manufactured by Mitsubishi
Chemical Corporation) Number-average molecular weight: 470, solid concentration:
100 mass%
- jER 1009: Bisphenol A type epoxy resin (manufactured by Mitsubishi
Chemical Corporation) Number-average molecular weight: 3,800, solid concentration:
100 mass%
- jER 1010: Bisphenol A type epoxy resin (manufactured by Mitsubishi
Chemical Corporation; Number-average molecular weight) 5,500, solid concentration:
100 mass%
-jER 1009F: Bisphenol F type epoxy resin (manufactured by Mitsubishi
Chemical Corporation) Number-average molecular weight: 2,900, solid concentration:
100 mass%
[Others]
- Solvent: Methyl propylene glycol: propylene glycol monomethyl ether
(manufactured by Nippon Nyukazai Co., Ltd.)
[0118]
<Alkanolamine (E)>
Details of the alkanolamine (E) are as shown in Table 5A and Table 5B.
[0119]
[Table 5A] Alkanolamine (E) (El) (E2) (E3) Commercial raw material Diisopropanolamine Triisopropanolamine Monoisopropanolamine Manufacturer Tokyo Chemical Tokyo Chemical Tokyo Chemical Industry Co., Ltd. Industry Co., Ltd. Industry Co., Ltd. Active ingredient concentration (mass%) 100 100 100 Number of alkanol groups 2 3 Alkanol type Isopropanol Isopropanol Isopropanol
[0120]
[Table 5B] Alkanolamine (E) (E4) (E5) (E6) Commercial raw material Diethanolamine Triethanolamine Dimethylaminoethanol Manufacturer Tokyo Chemical Tokyo Chemical Tokyo Chemical Industry Co., Ltd. Industry Co., Ltd. Industry Co., Ltd. Active ingredient concentration (mass%) 100 100 100 Number of alkanol groups 2 3 Alkanol type Ethanol Ethanol Ethanol
[0121]
<Production example of coating composition 1>
107.7 parts by mass of the hydroxyl group-containing resin (Al), 2.4 parts by
mass of T-SOL 100 (manufactured by JXTG Energy Corporation) and 2.4 parts by mass
of ethylene glycol monobutyl ether (manufactured by The Dow Chemical Company) as
solvents, and 67.0 parts by mass of TIPAQUE CR-97 (titanium oxide, manufactured by
Ishihara Sangyo Kaisha, Ltd.) as a pigment were mixed by stirring with a disper,
affording a mixture.
Next, the whole amount of the mixture obtained and glass beads (in the same
amount as the total parts by mass of the mixture) were put in a tabletop SG Mill 1500 W
type disperser (manufactured by Ohira System Co., Ltd.), and pigment dispersion was
performed until the particle size of TIPAQUE CR-97 became 10 pm or less, thereby
preparing a pigment dispersion coating material.
Furthermore, 30.0 parts by mass of the amino resin (B1), 38.5 parts by mass of
the covalently bonded blocked acid catalyst (C11), and 3.9 parts by mass of the phosphoric acid-modified epoxy resin (D1) were mixed with 179.5 parts by mass of the pigment dispersion coating material by stirring with a disper, affording a coating composition.
The resulting coating composition was diluted with a mixed solution of T-SOL
100/ethylene glycol monobutyl ether = 1/1 (mass ratio) in a Ford cup No. 4 such that
100 seconds (at 25°C) was achieved, affording coating composition 1.
[0122]
<Production examples of coating compositions 2 to 69>
Coating compositions 2 to 69 were prepared in the same manner as in the
production example of the coating composition 1 except that the type and amount of
each component were changed as shown in Tables 6A to 6P.
[0123]
[Table 6A] Example I Example 2 Example 3 Example 4 Example 5 Coating Coating Coating Coating Coating composition composition composition composition composition 1 2 3 4 5 (Al) Polyester resin 1 107.7 138.5 92.3 107.7 107.7 (A2) Polyester resin 2 (A3) Polyester resin 3 (A4) Polyester resin 4 (A5) Polyester resin 5 Hydroxyl (A6) Polyester resin 6 cotai (A7) Polyester resin 7 containing (A8) Polyester resin 8 resin(A) (A9) Polyester resin 9 (Al0) Polyester resin 10 (Al1) Polyester resin I (A12) Epoxy resin I (A13) Acrylic resin 1 (B1) Melamine resin 1 30.0 10.0 40.0 30.0 30.0 (B2) Melamine resin 2 Amino resin (B3) Melamine resin 3 (B) (B4) Melamine resin 4 (B5) Melamine resin 5 (B6) Melamine resin 6 Isocyanate Polyisocyanate compound I compound (Cl1) 38.5 38.5 38.5 128.2 256.4 (C12) (C13). (C14) (C15) (C16) Covalently (C17) bonded (C18) blocked acid (C21) catalyst (C) (C22) (C23) (C24) (C25) (C26) (C27) (C28) Acid catalyst 1 (c31) Blocking agent: triethylamine Acid catalyst 2 (c32) No blocking agent (DI) 3.9 3.9 3.9 3.9 3.9 Phosphoric (D2) acid-modified (D3) epoxy resin (D5) (D) (D5) (D6) (D7) (El) (E2) Alkanolamine (E3) (E) (E4) (E5) (E6) Total 180.1 190.8 174.7 269.8 398.0
[0124]
[Table 6B] Example 6 Example 7 Example 8 Example 9 Example 10 Coating Coating Coating Coating Coating composition composition composition composition composition 6 7 8 9 10 (Al) Polyester resin 1 107.7 107.7 107.7 107.7 107.7 (A2) Polyester resin 2 (A3) Polyester resin 3 (A4) Polyester resin 4 (A5) Polyester resin 5 Hydroxyl (A6) Polyester resin 6 group (A7) Polyester resin 7 containing (A8) Polyester resin 8 resin(A) (A9) Polyester resin 9 (A1O) Polyester resin 10 (Al 1) Polyester resin 11 (A12) Epoxy resin 1 (A13) Acrylic resin I (B) Melamine resin 1 30.0 30.0 30.0 30.0 30.0 (B2) Melamine resin 2 Amino resin (B3) Melamine resin 3 (B) (B4) Melamine resin 4 (B5) Melamine resin 5 (B6) Melamine resin 6 Isocyanate Polyisocyanate compound 1 compound (CI1) 38.5 38.5 38.5 38.5 38.5 (C12) (C13) (C14) (C15) (C16) Covalently (C17) bonded (C18) blocked acid (C21) catalyst (C) (C22) (C23) (C24) (C25) (C26) (C27) (C28) Acid catalyst 1 (c31) Blocking agent: triethylamine Acid catalyst 2 (c32) No blocking agent (Dl) 1.3 12.8 3.9 3.9 3.9 Phosphoric (D2) acid-modified (D3) epoxy resin (135) (D) (D6) (D7) (El) 1.0 0.5 3.0 (E2) Alkanolamine (E3) (E) (E4) (E5) (E6) Total 177.4 189.0 181.1 180.6 183.1
[0125]
[Table 6C] Example 11 Example 12 Example 13 Example 14 Example 15 Coating Coating Coating Coating Coating composition composition composition composition composition 11 12 13 14 15 (Al) Polyester resin 1 107.7 107.7 107.7 107.7 107.7 (A2) Polyester resin 2 (A3) Polyester resin 3 (A4) Polyester resin 4 (A5) Polyester resin 5 Hydroxyl (A6) Polyester resin 6 group- (A7) Polyester resin 7 containing (A8) Polyester resin 8 resin (A) (A9) Polyester resin 9 (AlO) Polyester resin 10 (Al l) Polyester resin 11 (A12) Epoxy resin 1 (A13) Acrylic resin 1 (B1) Melamine resin 1 30.0 30.0 30.0 30.0 30.0 (B2) Melamine resin 2 Amino resin (B3) Melamine resin 3 (B) (B4) Melamine resin 4 (B5) Melamine resin 5 (B6) Melamine resin 6 Isocyanate Polyisocyanate compound 1 compound (CI1) 38.5 38.5 38.5 38.5 38.5 (C12) (C13) (C14) (C15) (C16) Covalently (C17) bonded (C18) blocked acid (C21) catalyst (C) (C22) (C23) (C24) (C25) (C26) (C27) (C28) Acid catalyst 1 (c31) Blocking agent: triethylamine Acid catalyst 2 (c32) No blocking agent (D1) 3.9 3.9 Phosphoric (D2) (D2) 3.9 3.9 acid-modified (D3) 6.9 epoxy resin (65) (D) (D6)
(D7) (El) 4.0 6.0 (E2) Alkanolamine (E3) (E) (E4) (E5) (E6) Total 184.1 186.1 180.1 180.1 182.2
[0126]
[Table 6D] Example 16 Example 17 Example 18 |Example 19 Example 20 Coating Coating Coating Coating Coating composition composition composition composition composition 16 17 18 19 20 (A1) Polyester resin 1 107.7 107.7 107.7 107.7 107.7 (A2) Polyester resin 2 (A3) Polyester resin 3 (A4) Polyester resin 4 (A5) Polyester resin 5 Hydroxyl (A6) Polyester resin 6 group- (A7) Polyester resin 7 containing (A8) Polyester resin 8 resin (A) (A9) Polyester resin 9 (Al0) Polyester resin 10 (Al 1) Polyester resin 11 (A12) Epoxy resin 1 (Al 3) Acrylic resin 1 (BI) Melamine resin 1 30.0 30.0 30.0 30.0 30.0 (B2) Melamine resin 2 Amino resin (B3) Melamine resin 3 (B) (B4) Melamine resin 4 (B5) Melamine resin 5 (B6) Melamine resin 6 Isocyanate Polyisocyanate compound I compound (CI1) 38.5 38.5 38.5 (C12) 27.8 (C13) 21.7 (C14) (C15) (C16) Covalently (C17) bonded (C18) blocked acid (C21) catalyst (C) (C22) (C23) (C24) (C25) (C26) (C27) (C28) Acid catalyst I (c31) Blocking agent: triethylamine Acid catalyst 2 (c32) No blocking agent (D1) 3.9 3.9 (132) Phosphoric (D2) acid-modified (D4) epoxy resin (D5) 6.0 (D) (D6) 6.0 (D7) 4.1 (El) (E2) Alkanolamine (E3) (E) (E4) (E5) (E6) _ _ _ I Total 182.2 182.2| 180.2 169.4 163.3
[0127]
[Table 6E] Example 21 Example 22 Example 23| Example 24 Example 25 Coating Coating Coating Coating Coating composition composition composition composition composition 21 22 23 24 25 (Al) Polyester resin 1 107.7 107.7 107.7 107.7 107.7 (A2) Polyester resin 2 (A3) Polyester resin 3 (A4) Polyester resin 4 (A5) Polyester resin 5 Hydroxyl (A6) Polyester resin 6 group- (A7) Polyester resin 7 containing (A8) Polyester resin 8 resin (A) (A9) Polyester resin 9 (Al0) Polyester resin 10 (Al l) Polyester resin II (A12) Epoxy resin 1 (A13) Acrylic resin 1 (B1) Melamine resin 1 30.0 30.0 30.0 30.0 30.0 (B2) Melamine resin 2 Amino resin (B3) Melamine resin 3 (B) (B4) Melamine resin 4 (B5) Melamine resin 5 (B6) Melamine resin 6 Isocyanate Polyisocyanate compound 1 compound (C11) (C12) (C13) (C14) 13.8 (C15) 107.1 (C16) 21.7 Covalently (C17) 53.6 bonded (C18) 100.0 blocked acid (C21) catalyst (C) (C22) (C23) (C24) (C25) (C26) (C27) (C28) Acid catalyst I (c31) Blocking agent: triethylamine Acid catalyst 2 (c32) No blocking agent (D1) 3.9 3.9 3.9 3.9 3.9 (D2)_ __ Phosphoric (D3) acid-modified (D4) epoxy resin (D5) (D) (15 (D6) (D7) (E1) (E2) Alkanolamine (E3) (E) (E4) (E5) (E6) Total 155.4 248.7 163.3 195.2 241.6
[0128]
[Table 6F] Example 26 Example 27 Example 28 Example 29 Example 30 Coating Coating Coating Coating Coating composition composition composition composition composition 26 27 28 29 30 (Al) Polyester resin 1 107.7 107.7 107.7 107.7 107.7 (A2) Polyester resin 2 (A3) Polyester resin 3 (A4) Polyester resin 4 (A5) Polyester resin 5 Hydroxyl (A6) Polyester resin 6 cotai (A7) Polyester resin 7 containing (A8) Polyester resin 8 resin (A) (A9) Polyester resin 9 (AlO) Polyester resin 10 (Al l) Polyester resin 11 (A12) Epoxy resin I (A13) Acrylic resin 1 (B1) Melamine resin 1 30.0 30.0 30.0 30.0 30.0 (B2) Melamine resin 2 Amino resin (B3) Melamine resin 3 (B) (B4) Melamine resin 4 (B5) Melamine resin 5 (B6) Melamine resin 6 Isocyanate Polyisocyanate compound 1 compound (C11) (C12) (C13) (C14) (C15) (C16) Covalently (C17) bonded (C18) blocked acid (C21) 4.0 catalyst (C) (C22) 4.1 (C23) 3.8 (C24) 4.1 (C25) 4.6 (C26) (C27) (C28) Acid catalyst I (c31) Blocking agent: triethylamine Acid catalyst 2 (c32) No blocking agent (D1) 3.9 3.9 3.9 3.9 3.9 (132) Phosphoric (D2) acid-modified (D3) epoxy resin (D5) (D) (D6) (D7) (E 1) (E2) Alkanolamine (E3) (E) (E4) (E5) (E6) Total , 145.6 145.7, 145.4 145.7 146.2
[0129]
[Table 6G] Example 31 Example 32 Example 33 Example 34 Example 35 Coating Coating Coating Coating Coating composition composition composition composition composition 31 32 33 34 35 (Al) Polyester resin 1 107.7 107.7 107.7 107.7 107.7 (A2) Polyester resin 2 (A3) Polyester resin 3 (A4) Polyester resin 4 (A5) Polyester resin 5 Hydroxyl (A6) Polyester resin 6 group- (A7) Polyester resin 7 containing (A8) Polyester resin 8 resin (A) (A8) Polyesterresm 9 (A9) Polyester resin 9 (All) Polyester resin 10 (Al l) Polyester resin 11I (A12) Epoxy resin I (Al 3) Acrylic resin 1 (B1) Melamine resin 1 30.0 30.0 30.0 30.0 30.0 (B2) Melamine resin 2 Amino resin (B3) Melamine resin 3 (B) (B4) Melamine resin 4 (B5) Melamine resin 5 (B6) Melamine resin 6 Isocyanate Polyisocyanate compound 1 compound (Cl1) (C12) (C13) (C14) (C15) (C16) Covalently (C17) bonded (C18) blocked acid (C21) 13.2 26.5 catalyst (C) (C22) (C23) (C24) (C25) (C26) 4.6 (C27) 5.1 (C28) 8.6 Acid catalyst I (c31) Blocking agent: triethylamine Acid catalyst 2 (c32) No blocking agent (D1) 3.9 3.9 3.9 3.9 3.9 Phosphoric (D2) acid-modified (D3) epoxy resin (D4)
(D6) (El) (E1) (E2) Alkanolamine (E3) (E) (E4) (E5) (E6) Total 146.2 146.7 150.2 154.8 168.1
[0130]
[Table 6H] Example 36 Example 37 Example 38 Example 39- Example40 Coating Coating Coating Coating Coating composition composition composition composition composition 36 37 38 39 40 (Al) Polyester resin 1 (A2) Polyester resin 2 107.7 (A3) Polyester resin 3 100.0 (A4) Polyester resin 4 107.7 (A5) Polyester resin 5 100.0 Hydroxyl (A6) Polyester resin 6 107.7 group- (A7) Polyester resin 7 containing (A8) Polyester resin 8 resin (A) (A9) Polyester resin 9 (AlO) Polyester resin 10 (Al 1) Polyester resin II (A12) Epoxy resin 1 (Al3) Acrylic resin 1 (B1) Melamine resin 1 30.0 30.0 30.0 30.0 30.0 (B2) Melamine resin 2 Amino resin (B3) Melamine resin 3 (B) (B4) Melamine resin 4 (B5) Melamine resin 5 (B6) Melamine resin 6 Isocyanate Polyisocyanate compound I compound (Cl1) 38.5 38.5 38.5 38.5 38.5 (C12) (C13) (C14) (C15) (C16) Covalently (C17) bonded (C18) blocked acid (C21) catalyst (C) (C22) (C23) (C24) (C25) (C26) (C27) (C28) Acid catalyst 1 (c31) Blocking agent: triethylamine Acid catalyst 2 (c32) No blocking agent (Dl) 3.9 3.9 3.9 3.9 3.9 Phosphoric (D2) acid-modified (D3) (134) epoxy resin (D) (D6)
(D7) (El) (E2) Alkanolamine (E3) (E) (E4) (E5) (E6) Total 180.1 172.4 180.1 172.4 180.1
[0131]
[Table 61] Example 41 Example 42 Example 43 Example 44 Example 45 Coating Coating Coating Coating Coating composition composition composition composition composition 41 42 43 44 45 (Al) Polyester resin 1 (A2) Polyester resin 2 (A3) Polyester resin 3 (A4) Polyester resin 4 (A5) Polyester resin 5 Hydroxyl (A6) Polyester resin 6 group (A7) Polyester resin 7 100.0 containing (8 oysersn 4. resin (A) (A8) Polyester resin 8 140.0 (A9) Polyester resin 9 127.3 (AlO) Polyester resin 10 116.7 (Al l) Polyester resin 11 140.0 (A12) Epoxy resin 1 (A13) Acrylic resin I (B1) Melamine resin 1 30.0 30.0 30.0 30.0 30.0 (B2) Melamine resin 2 Amino resin (B3) Melamine resin 3 (B) (B4) Melamine resin 4 (B5) Melamine resin 5 (B6) Melamine resin 6 Isocyanate Polyisocyanate compound 1 compound (C11) 38.5 38.5 38.5 38.5 38.5 (C12) (C13) (C14) (C15) (C16) Covalently (C17) bonded (C18) blocked acid (C21) catalyst (C) (C22) (C23) (C24) (C25) (C26) (C27) (C28) Acid catalyst 1 (c31) Blocking agent: triethylamine Acid catalyst 2 (c32) No blocking agent (DI) 3.9 3.9 3.9 3.9 3.9 Phosphoric (D2) acid-modified (D3) epoxy resin (13) (D) (D6) (D6) (D7) (El) (E2) Alkanolamine (E3) (E) (E4) (E5) (E6) Total 172.4 212.4 199.6 189.0 212.4
[0132]
[Table 6J] IExample Coating 46
composition Example 47 Coating composition Example 48 Example 49 Example 50 Coating Coating Coating composition composition composition 46 47 48 49 50 (Al) Polyester resin 1 107.7 107.7 107.7 (A2) Polyester resin 2 (A3) Polyester resin 3 (A4) Polyester resin 4 (A5) Polyester resin 5 Hydroxyl (A6) Polyester resin 6 group (A7) Polyester resin 7 containing (A8) Polyester resin 8 resin (A) (A9) Polyester resin 9 (Al0) Polyester resin 10 (Al l) Polyester resin II (A12) Epoxy resin 1 233.3 (Al 3) Acrylic resin 1 116.7 (B1) Melamine resin 1 30.0 30.0 (B2) Melamine resin 2 30.0 Amino resin (B3) Melamine resin 3 30.0 (B) (B4) Melamine resin 4 37.5 (B5) Melamine resin 5 (B6) Melamine resin 6 Isocyanate Polyisocyanate compound I compound (CI1) 38.5 38.5 38.5 38.5 38.5 (C12) (C13) (C14) (C15) (C16) Covalently (C17) bonded (C18) blocked acid (C21) catalyst (C) (C22) (C23) (C24) (C25) (C26) (C27) (C28) Acid catalyst I (c31) Blocking agent: triethylamine Acid catalyst 2 (c32) No blocking agent (DI) 3.9 3.9 3.9 3.9 3.9 Phosphoric (D2) acid-modified (D4) epoxy resin (D5) (D) (D6) (D7) (El) (E2) Alkanolamine (E3) (E) (E4) (E5) (E6) Total 305.7 189.1 180.1 180.1 187.6
[0133]
[Table 6K] Example 51 | Example 52 Example 53 Example 54 Example 55 Coating Coating Coating Coating Coating composition composition composition composition composition 51 52 53 54 55 (Al) Polyester resin 1 107.7 107.7 107.7 107.7 107.7 (A2) Polyester resin 2 (A3) Polyester resin 3 (A4) Polyester resin 4 (A5) Polyester resin 5 Hydroxyl (A6) Polyester resin 6 cotai (A7) Polyester resin 7 containing (A8) Polyester resin 8 resin (A) (A9) Polyester resin 9 (A10) Polyester resin 10 (Al 1) Polyester resin 11 (A12) Epoxy resin I (A13) Acrylic resin 1 (BI) Melamine resin 1 30.0 30.0 30.0 (B2) Melamine resin 2 Amino resin (B3) Melamine resin 3 (B) (B4) Melamine resin 4 (B5) Melamine resin 5 33.3 (B6) Melamine resin 6 34.1 Isocyanate Polyisocyanate compound I compound (CI1) 38.5 38.5 38.5 38.5 38.5 (C12) (C13) (C14) (C15) (C16) Covalently (C17) bonded (C18) blocked acid (C21) catalyst (C) (C22) (C23) (C24) (C25) (C26) (C27) (C28) Acid catalyst I (c31) Blocking agent: triethylamine Acid catalyst 2 (c32) No blocking agent (DI) 3.9 3.9 3.9 3.9 3.9 Phosphoric (D2) acid-modified (D4) epoxy resin (D5) (D6) (D7) (El) (E2) 3.0 Alkanolamine (E3) 3.0 (E) (E4) 3.0 (E5) (E6) Total 183.4 184.1 183.1 183.1 183.1
[0134]
[Table 6L] Example 56 Example 57 Example 58 Example 59 Example 60 Coating Coating Coating Coating Coating composition composition composition composition composition 56 57 1 1 1 (Al) Polyester resin 1 107.7 107.7 107.7 107.7 107.7 (A2) Polyester resin 2 (A3) Polyester resin 3 (A4) Polyester resin 4 (A5) Polyester resin 5 Hydroxyl (A6) Polyester resin 6 group- (A7) Polyester resin 7 containing (A8) Polyester resin 8 resin (A) (A9) Polyester resin 9 (Al0) Polyester resin 10 (Al 1) Polyester resin 11 (A12) Epoxy resin I (Al3) Acrylic resin 1 (B1) Melamine resin 1 30.0 30.0 30.0 30.0 30.0 (B2) Melamine resin 2 Amino resin (B3) Melamine resin 3 (B) (B4) Melamine resin 4 (B5) Melamine resin 5 (B6) Melamine resin 6 Isocyanate Polyisocyanate compound 1 compound (C11) 38.5 38.5 38.5 38.5 38.5 (C12) (C13) (C14) (C15) (C16) Covalently (C17) bonded (C18) blocked acid (C21) catalyst (C) (C22) (C23) (C24) (C25) (C26) (C27) (C28) Acid catalyst 1 (c31) Blocking agent: triethylamine Acid catalyst 2 (c32) No blocking agent (D1) 3.9 3.9 3.9 3.9 3.9 Phosphoric (12) acid-modified (D4) epoxy resin (D5) (D) -D (D6) (D7) (El) (E2) Alkanolamine (E3) (E) (E4) (E5) 3.01 (E6) 3.0 Total 183.1, 183.1 180.1 180.1 180.1
[0135]
[Table 6M] Example 61 Example 62 Example 63 Example 64 Coating Coating Coating Coating composition composition composition composition
(Al) Polyester resin 1 107.7 107.7 107.7 107.7 (A2) Polyester resin 2 (A3) Polyester resin 3 (A4) Polyester resin 4 (A5) Polyester resin 5 Hydroxyl (A6) Polyester resin 6 cotai (A7) Polyester resin 7 containing (A8) Polyester resin 8 resin (A) (A9) Polyester resin 9 (Al0) Polyester resin 10 (Al1) Polyester resin 11 (A12) Epoxy resin I (A13) Acrylic resin I (BI) Melamine resin 1 30.0 30.0 30.0 30.0 (B2) Melamine resin 2 Amino resin (B3) Melamine resin 3 (B) (B4) Melamine resin 4 (B5) Melamine resin 5 (B6) Melamine resin 6 Isocyanate Polyisocyanate compound 1 compound (CI1) 38.5 38.5 38.5 38.5 (C12) (C13) (C14) (C15) (C16) Covalently (C17) bonded (C18) blocked acid (C21) catalyst (C) (C22) (C23) (C24) (C25) (C26) (C27) (C28) Acid catalyst I (c31) Blocking agent: triethylamine Acid catalyst 2 (c32) No blocking agent (DI) 3.9 3.9 3.9 3.9 Phosphoric (D2) acid-modified (D3) epoxy resin (D5) (D) (D5) (D6) (D7) (El) (E2) Alkanolamine (E3) (E) (E4) (E5) (E6) Total 180.1 180.1 180.1 180.1
[0136]
[Table 6N] Comparative Comparative Comparative Comparative Comparative Example I Example 2 Example 3 Example 4 Example 5 Coating Coating Coating Coating Coating composition composition composition composition composition 58 59 60 61 62 (A) Polyester resin 1 146.2 76.9 107.7 107.7 107.7 (A2) Polyester resin 2 (A3) Polyester resin 3 (A4) Polyester resin 4 (A5) Polyester resin 5 Hydroxyl (A6) Polyester resin 6 group (A7) Polyester resin 7 containing (A8) Polyester resin 8 .
(A9) Polyester resin 9 (Al0) Polyester resin 10 (Al1) Polyester resin 11 (A12) Epoxy resin 1 (A13) Acrylic resin 1 (B1) Melamine resin 1 5.0 50.0 30.0 30.0 30.0 (B2) Melamine resin 2 Amino resin (B3) Melamine resin 3 (B) (B4) Melamine resin 4 (B5) Melamine resin 5 (B6) Melamine resin 6 Isocyanate Polyisocyanate compound 1 compound (C11) 38.5 38.5 12.8 0.0 384.6 (C12) (Cl3) (C14) (C15) (C16) Covalently (C17) bonded (C18) blocked acid (C21) catalyst (C) (C22) (C23) (C24) (C25) (C26) (C27) (C28) Acid catalyst 1 (c31) Blocking agent: triethylamine Acid catalyst 2 (c32) No blocking agent (D1) 3.9 3.9 3.9 3.9 3.9 Phosphoric acid-modified (D4) epoxy resin (D5) (D) (D6) (D7) (El) (E2) Alkanolamine (E3) (E) (E4) (E5) (E6) Total 193.5 169.3 154.4, 141.6 526.2
[0137]
[Table 60] Comparative Comparative Comparative Comparative Comparative Example 6 Example 7 Example 8 Example 9 Example 10 Coating Coating Coating Coating Coating composition composition composition composition composition 63 64 65 66 67 (Al) Polyester resin 1 107.7 107.7 107.7 107.7 107.7 (A2) Polyester resin 2 (A3) Polyester resin 3 (A4) Polyester resin 4 (A5) Polyester resin 5 Hydroxyl (A6) Polyester resin 6 group (A7) Polyester resin 7 containing (A8) Polyester resin 8 resin(A) (A9) Polyester resin 9 (AlO) Polyester resin 10 (Al 1) Polyester resin II (A12) Epoxy resin 1 (Al 3) Acrylic resin 1 (B1) Melamine resin 1 30.0 30.0 30.0 30.0 30.0 (B2) Melamine resin 2 Amino resin (B3) Melamine resin 3 (B) (B4) Melamine resin 4 (B5) Melamine resin 5 (B6) Melamine resin 6 Isocyanate Polyisocyanate compound I compound (Cl 1) 38.5 38.5 38.5 (C12) (C13) (C14) (C15) (C16) Covalently (C17) bonded (C18) blocked acid (C21) catalyst (C) (C22) (C23) (C24) (C25) (C26) (C27) (C28) Acid catalyst 1 (c31) Blocking agent: triethylamine 3.7 Acid catalyst 2 (c32) No blocking agent 3.0 (D1) 0.6 0.0 19.2 3.9 3.9 Phosphoric (D3) acid-modified D4) epoxy resin (D5) (D) (D5) (D6) (D7) (El) (E2) Alkanolamine (E3) (E) (E4) (E5) (E6) Total 176.8 176.2 195.4 145.3 144.6
[0138]
[Table 6P] Comparative Comparative Reference Example example 12 Example I Coating Coating Coating composition composition composition 68 69 69 (Al) Polyester resin 1 107.7 107.7 107.7 (A2) Polyester resin 2 (A3) Polyester resin 3 (A4) Polyester resin 4 (A5) Polyester resin 5 Hydroxyl (A6) Polyester resin 6 group (A7) Polyester resin 7 containing (A8) Polyester resin 8 resin (A) (A9) Polyester resin 9 (Al0) Polyester resin 10 (Al1) Polyester resin I1 (A12) Epoxy resin I (Al3) Acrylic resin 1 (BI) Melamine resin I (B2) Melamine resin 2 Amino resin (B3) Melamine resin 3 (B) (B4) Melamine resin 4 (B5) Melamine resin 5 33.3 33.3 (B6) Melamine resin 6 Isocyanate Polyisocyanate compound 1 40.0 compound (C11) 38.5 (C12) (C13) (C14) (C15) (C16) Covalently (C17) bonded (C18) blocked acid (C21) catalyst (C) (C22) (C23) (C24) (C25) (C26) (C27) (C28) Acid catalyst 1 (c31) Blocking agent: triethylamine Acid catalyst 2 (c32) No blocking agent (DI) 3.9 Phosphoric D acid-modified (D4) epoxy resin (D5) (D) (D6) (D7) (El) (E2) Alkanolamine (E3) (E) (E4) (E5) (E6) Total 190.6 141.0 141.0
[0139]
(Examples 1 to 64, Comparative Examples 1 to 12, and Reference Example 1)
As to Examples 1 to 64, Comparative Examples 1 to 12, and Reference
Example 1, evaluations were carried out using the coating compositions shown in
Tables 6A to 6P, respectively. The evaluation results are shown in Tables 7A to 7P.
In Comparative Example 11, a coating composition in which 0.5 parts by mass
of TVS#Tin Lau (dibutyltin dilaurate, manufactured by Nitto Kasei Co., Ltd.; active
ingredient concentration: 100 mass%) was further added as a catalyst was used. The
value of "parts by mass (solid content) of (B) based on 100 parts by mass of the solid
content of (A) and (B)" in Comparative Example 11 in Table 7N means "parts by mass
(solid content) of the polyisocyanate compound 1 based on 100 parts by mass of the
solid content of (A) and the polyisocyanate compound 1".
[0140]
In addition, the coated steel sheet in Example 1 was manufactured as shown in
the following production example.
[0141]
<Production example of coated steel sheet of Example 1>
A 0.4 mm thick molten zinc plated steel sheet was alkali-degreased, and then
subjected to non-chromium chemical conversion treatment by applying a phosphoric
acid treatment agent, SURFCOAT EC2310 (manufactured by Nippon Paint Surf
Chemicals Co., Ltd.) on the front and back surfaces of the steel sheet, followed by
drying.
Next, the coating composition 1 was applied on a surface of the steel sheet
using a bar coater such that the dry coating film was 10 pm in thickness, and baked
(heated) for 6 seconds using an induction heater type furnace under the condition that
the peak temperature (PMT) of the steel sheet was 220°C to form a surface coating film, thereby affording a coated.steel sheet.
[0142]
<Production examples of coated steel sheets in Examples 2 to 64, Comparative
Examples 1 to 12 and Reference Example 1>
The coated steel sheets in Examples 2 to 64, Comparative Examples 1 to 12,
and Reference Example 1 were produced by changing the coating film composition, the
baking temperature, and the baking time to the conditions shown in Tables 7A to 7P in
the production example of the coated steel sheet in Example 1. In Tables 7A to 7P,
"based on 100 parts by mass of the solid content of (A) and (B) " means "based on 100
parts by mass of the total of the resin solid content of the hydroxyl group-containing
resin (A) and the resin solid content of the amino resin (B)".
[0143]
[Table 7A] Example 1 Example 2 Example 3 Example 4 Example 5 Coating Coating Coating Coating Coating composition composition composition composition composition 1 2 3 4 5 (Al) (Al) (Al) (Al) (Al) Hydroxyl group-containing resin (A) Polyester Polyester Polyester Polyester Polyester resin 1 resin 1 resin I resin 1 resin 1 Amino resin (B) or other material (B1) (B1) (B1) (B1) (B1) Covalently bonded blocked acid catalyst (C) or other (C1I) (Cl1) (Cl1) (Cl1) (Ci1) material Phosphoric acid-modified epoxy resin (D) (DI) (D1) (Dl) (DI) (DI) Alkanolamine (E) Part(s) by mass (solid content) of (A) per 100 parts by 70.0 90.0 60.0 70.0 70.0 mass of solid content of (A) and (B) Part(s) by mass (solid content) of (B) per 100 parts by 30.0 10.0 40.0 30.0 30.0 mass of solid content of (A) and (B) Part(s) by mass (active ingredient) of acid catalyst part of 1 1.5 1.5 5.0 10.0 (C) per 100 parts by mass of solid content of (A) and (B) Part(s) by mass (solid content) of (D) per 100 parts by 3.0 3.0 3.0 3.0 3.0 mass of solid content of (A) and (B) Part(s) by mass (active ingredient) of(E) per 100 parts 0.0 0.0 0.0 0.0 0.0 by mass of solid content of(A) and (B) Baking temperature (PMT) (°C) 220 220 220 220 220 Baking time (s) 6 6 6 6 6 Coating film appearance 0 0 0 0 0 Storage stability Viscosity ratio (%) 140 140 140 140 140 Solvent resistance 5 3 5 5 5 Folding test 5 5 4 5 4 Processability Adhesive property 5 4 4 5 5 Alkali resistance 8FM 8FM 8FM 8FM 8FM Acid resistance 8FM 8FM 8FM 8FM 8FM
[0144]
[Table 7B] Example 6 Example 7 Example 8 Example 9 Example 10 Coating Coating Coating Coating Coating composition composition composition composition composition 6 7 8 9 10 (Al) (Al) (Al) (Al) (Al) Hydroxyl group-containing resin (A) Polyester Polyester Polyester Polyester Polyester resin 1 resin 1 resin 1 resin I resin 1 Amino resin (B) or other material (B1) (B1) (B1) (B1) (B1) Covalently bonded blocked acid catalyst (C) or other (Cl1) (Cl1) (C11) (C1) (CI1) material Phosphoric acid-modified epoxy resin (D) (D1) (D1) (D1) (D1) (DI) Alkanolamine (E) (El) (El) (El) Part(s) by mass (solid content) of (A) per 100 parts by 70.0 70.0 70.0 70.0 70.0 mass of solid content of (A) and (B) Part(s) by mass (solid content) of (B) per 100 parts by 30.0 30.0 30.0 30.0 30.0 mass of solid content of(A) and (B) Part(s) by mass (active ingredient) of acid catalyst part of 1.5 1.5 1.5 1.5 1.5 (C) per 100 parts by mass of solid content of(A) and (B) Part(s) by mass (solid content) of (D) per 100 parts by 1.0 10.0 3.0 3.0 3.0 mass of solid content of(A) and (B) Part(s) by mass (active ingredient) of (E) per 100 parts 0.0 0.0 1.0 0.5 3.0 by mass of solid content of (A) and (B) Baking temperature (PMT) (°C) 220 220 220 220 220 Baking time (s) 6 6 6 6 6 Coating film appearance 0 0 0 0 0 Storage stability Viscosity ratio (%) 140 140 120 130 110 Solvent resistance 4 5 5 5 5 Folding test 5 4 5 5 5 Processability Adhesive property 4 4 5 5 5 Alkali resistance 8FM 8FM 8FM 8FM 8FM Acid resistance 8FM 8FM 8FM 8FM 8FM
[0145]
[Table 7C] Example 11 Example 12 Example 13 Example 14 Example 15 Coating Coating Coating Coating Coating composition composition composition composition composition 11 12 13 14 15 (Al) (Al) (Al) (Al) (Al) Hydroxyl group-containing resin (A) Polyester Polyester Polyester Polyester Polyester resin I resin 1 resin I resin 1 resin I Amino resin (B) or other material (B1) (B1) (B1) (Bl) (B1) Covalently bonded blocked acid catalyst (C) or other (C1) (CI1) (CI1) (Cl1) (CI1) material Phosphoric acid-modified epoxy resin (D) (DI) (Dl) (D2) (D3) (D4) Alkanolamine (E) (El) (El) Part(s) by mass (solid content) of (A) per 100 parts by 70.0 70.0 70.0 70.0 70.0 mass of solid content of (A) and (B) Part(s) by mass (solid content) of (B) per 100 parts by 30.0 30.0 30.0 30.0 30.0 mass of solid content of (A) and (B) Part(s) by mass (active ingredient) of acid catalyst part of 1.5 1.5 1.5 1.5 1.5 (C) per 100 parts by mass of solid content of (A) and (B) Part(s) by mass (solid content) of (D) per 100 parts by 3.0 3.0 3.0 3.0 3.0 mass of solid content of(A) and (B) Part(s) by mass (active ingredient) of (E) per 100 parts 4.0 6.0 0.0 0.0 0.0 by mass of solid content of(A) and (B) Baking temperature (PMT) (°C) 220 220 220 220 220 Baking time (s) 6 6 6 6 6 Coating film appearance 0 0 0 0 0 Storage stability Viscosity ratio (%) 110 110 140 140 140 Solvent resistance 4 3 5 5 4 Folding test 5 5 5 4 5 Processability Adhesive property 5 5 5 4 4 Alkali resistance 8FM 8FM 8FM 8F 8FM Acid resistance 8FM 8FM 8FM 8F 8FM
[0146]
[Table 7D] Example 16 Example 17 Example 18 Example 19 Example 20 Coating Coating Coating Coating Coating composition composition composition composition composition 16 17 18 19 20 (Al) (Al) (Al) (Al) (Al) Hydroxyl group-containing resin (A) Polyester Polyester Polyester Polyester Polyester resin I resin 1 resin 1 resin 1 resin 1 Amino resin (B) or other material (B1) (B1) (B1) (BI) (B1) Covalently bonded blocked acid catalyst (C) or other (Cl1) (Cl1) (Cl1) (C12) (C13) material Phosphoric acid-modified epoxy resin (D) (D5) (D6) (D7) (DI) (DI) Alkanolamine (E) Part(s) by mass (solid content) of (A) per 100 parts by 70.0 70.0 70.0 70.0 70.0 mass of solid content of (A) and (B) Part(s) by mass (solid content) of (B) per 100 parts by 30.0 30.0 30.0 30.0 30.0 mass of solid content of (A) and (B) Part(s) by mass (active ingredient) of acid catalyst part of 1.5 1.5 1.5 1.5 1.5 (C) per 100 parts by mass of solid content of(A) and (B) Part(s) by mass (solid content) of (D) per 100 parts by 3.0 3.0 3.0 3.0 3.0 mass of solid content of (A) and (B) Part(s) by mass (active ingredient) of (E) per 100 parts 0.0 0.0 0.0 0.0 0.0 by mass of solid content of (A) and (B) Baking temperature (PMT) (°C) 220 220 220 220 220 Baking time (s) 6 6 6 6 6 Coating film appearance 0 0 0 0 0 Storage stability Viscosity ratio (%) 140 140 140 140 140 Solvent resistance 3 4 4 5 5 Folding test 5 4 5 5 5 Processability Adhesive property 4 4 4 5 4 Alkali resistance 8FM 8FM 8FM 8FM 8FM Acid resistance 8FM 8FM 8FM 8FM 8FM
[0147]
[Table 7E] Example 21 Example 22 Example 23 Example 24 Example 25 Coating Coating Coating Coating Coating composition composition composition composition composition 21 22 23 24 25 (Al) (Al) (Al) (A) (Al) Hydroxyl group-containing resin (A) Polyester Polyester Polyester Polyester Polyester resin 1 resin 1 resin 1 resin 1 resin 1 Amino resin (B) or other material (B1) (B1) (B1) (B1) (B1) Covalently bonded blocked acid catalyst (C) or other (C14) (C15) (C16) (C17) (C18) material Phosphoric acid-modified epoxy resin (D) (D1) (D1) (D) (D1) (D1) Alkanolamine (E) Part(s) by mass (solid content) of (A) per 100 parts by 70.0 70.0 70.0 70.0 70.0 mass of solid content of (A) and (B) Part(s) by mass (solid content) of (B) per 100 parts by 30.0 30.0 30.0 30.0 30.0 mass of solid content of (A) and (B) Part(s) by mass (active ingredient) of acid catalyst part of 1.5 1.5 1.5 1.5 1.5 (C) per 100 parts by mass of solid content of(A) and (B) Part(s) by mass (solid content) of (D) per 100 parts by 3.0 3.0 3.0 3.0 3.0 mass of solid content of (A) and (B) Part(s) by mass (active ingredient) of(E) per 100 parts 0.0 0.0 0.0 0.0 0.0 by mass of solid content of (A) and (B) Baking temperature (PMT) (°C) 220 220 220 1 220 220 Baking time (s) 6 6 6 6 6 Coating film appearance 0 0 0 0 0 Storage stability Viscosity ratio (%) 140 140 140 150 150 Solvent resistance 5 3 4 5 5 Folding test 4 5 4 4 4 Processability Adhesive property 4 4 4 4 4 Alkali resistance 8FM 8FM 8FM 8FM 8F Acid resistance 8FM 8FM 8FM 8FM 8F
[0148]
[Table 7F] Example 26 Example 27 Example 28 Example 29 Example 30 Coating Coating Coating Coating Coating composition composition composition composition composition 26 27 28 29 30 (Al) (Al) (Al) (Al) (Al) Hydroxyl group-containing resin (A) Polyester Polyester Polyester Polyester Polyester resin 1 resin 1 resin 1 resin 1 resin I Amino resin (B) or other material (B1) (B1) (B1) (B1) (B1) Covalently bonded blocked acid catalyst (C) or other (C21) (C22) (C23) (C24) (C25) material Phosphoric acid-modified epoxy resin (D) (D1) (D1) (D1) (D1) (D1) Alkanolamine (E) Part(s) by mass (solid content) of (A) per 100 parts by 70.0 70.0 70.0 70.0 70.0 mass of solid content of (A) and (B) Part(s) by mass (solid content) of (B) per 100 parts by 30.0 30.0 30.0 30.0 30.0 mass of solid content of (A) and (B) Part(s) by mass (active ingredient) of acid catalyst part of 1.5 1.5 1.5 1.5 1.5 (C) per 100 parts by mass of solid content of (A) and (B) Part(s) by mass (solid content) of (D) per 100 parts by 3.0 3.0 3.0 3.0 3.0 mass of solid content of(A) and (B) Part(s) by mass (active ingredient) of (E) per 100 parts 0.0 0.0 0.0 0.0 0.0 by mass of solid content of (A) and (B) III Baking temperature (PMT) (°C) 220 220 220 220 220 Baking time (s) 6 6 6 6 6 Coating film appearance 0 0 0 0 0 Storage stability Viscosity ratio (%) 140 140 140 150 150 Solvent resistance 5 5 5 4 3 Folding test 5 5 4 5 5 Processability Adhesive property 5 5 4 4 4 Alkali resistance 8FM 8FM 8FM 8FM 8FM Acid resistance 8FM 8FM 8FM 8FM 8FM
[0149]
[Table 7G] Example 31 Example 32 Example 33 Example 34 Example 35 Coating Coating Coating Coating Coating composition composition composition composition composition 31 32 33 34 35 (Al) (Al) (Al) (Al) (Al) Hydroxyl group-containing resin (A) Polyester Polyester Polyester Polyester Polyester resin 1 resin I resin 1 resin 1 resin I Amino resin (B) or other material (B1) (B1) (B1) (B1) (B1) Covalently bonded blocked acid catalyst (C) or other (C26) (C27) (C28) (C21) (C21) material Phosphoric acid-modified epoxy resin (D) (Dl) (D1) (D1) (Dl) (D1) Alkanolamine (E) Part(s) by mass (solid content) of (A) per 100 parts by 70.0 70.0 70.0 70.0 70.0 mass of solid content of (A) and (B) Part(s) by mass (solid content) of (B) per 100 parts by 30.0 30.0 30.0 30.0 30.0 mass of solid content of (A) and (B) Part(s) by mass (active ingredient) of acid catalyst part of 1.5 1.5 1.5 5.0 10.0 (C) per 100 parts by mass of solid content of (A) and (B) Part(s) by mass (solid content) of (D) per 100 parts by 3.0 3.0 3.0 3.0 3.0 mass of solid content of (A) and (B) Part(s) by mass (active ingredient) of (E) per 100 parts by 0.0 0.0 0.0 0.0 0.0 mass of solid content of (A) and (B) Baking temperature (PMT) (°C) 220 220 220 220 220 Baking time (s) 6 6 6 6 6 Coating film appearance 0 0 0 0 0 Storage stability Viscosity ratio (%) 140 150 150 140 140 Solvent resistance 3 5 5 5 5 Processability Folding test 5 4 4 5 4 Adhesive property 4 4 4 5 5 Alkali resistance 8FM 8FM 8F 8FM 8FM Acid resistance 8FM 8FM 8F 8FM 8FM
[0150]
[Table 7H] Example 36 Example 37 Example 38 Example 39 Example 40 Coating Coating Coating Coating Coating composition composition composition composition composition 36 37 38 39 40 (A2) (A3) (A4) (A5) (A6) Hydroxyl group-containing resin (A) Polyester Polyester Polyester Polyester Polyester resin 2 resin 3 resin 4 resin 5 resin 6 Amino resin (B) or other material (B1) (B1) (B1) (B1) (B1) Covalently bonded blocked acid catalyst (C) or other (C1i) (C1) (C1) (C1) (Ci1) material Phosphoric acid-modified epoxy resin (D) (D1) (D1) (D) (D1) (Dl) Alkanolamine (E) Part(s) by mass (solid content) of (A) per 100 parts by 70.0 70.0 70.0 70.0 70.0 mass of solid content of(A) and (B) Part(s) by mass (solid content) of (B) per 100 parts by 30.0 30.0 30.0 30.0 30.0 mass of solid content of (A) and (B) Part(s) by mass (active ingredient) of acid catalyst part of 1.5 1.5 1.5 1.5 1.5 (C) per 100 parts by mass of solid content of (A) and (B) Part(s) by mass (solid content) of (D) per 100 parts by 3.0 3.0 3.0 3.0 3.0 mass of solid content of (A) and (B) Part(s) by mass (active ingredient) of (E) per 100 parts 0.0 0.0 0.0 0.0 0.0 by mass of solid content of (A) and (B) Baking temperature (PMT) (°C) 220 220 220 220 220 Baking time (s) 6 6 6 6 6 Coating film appearance 0 0 0 0 0 Storage stability Viscosity ratio (%) 140 140 140 140 140 Solvent resistance 5 5 5 5 5 Folding test 5 4 4 4 4 Processability Adhesive property 5 5 5 5 5 Alkali resistance 8FM 8FM 8FM 8FM 8FM Acid resistance 8FM 8FM 8FM 8FM 8FM
[0151]
[Table 71] Example 41 Example 42 Example 43 Example 44 Example 45 Coating Coating Coating Coating Coating composition composition composition composition composition 41 42 43 44 45 (A7) (A8) (A9) (AlO) (Al l) Hydroxyl group-containing resin (A) Polyester' Polyester Polyester Polyester Polyester resin 7 resin 8 resin 9 resin 10 resin 11 Amino resin (B) or other material (B1) (B1) (B1) (B1) (B1) Covalently bonded blocked acid catalyst (C) or other (Cl1) (C11) (Cl1) (Cl1) (C11) material Phosphoric acid-modified epoxy resin (D) (DI) (D1) (Dl) (D1) (D1) Alkanolamine (E) Part(s) by mass (solid content) of (A) per 100 parts by 70.0 70.0 70.0 70.0 70.0 mass of solid content of (A) and (B) Part(s) by mass (solid content) of (B) per 100 parts by 30.0 30.0 30.0 30.0 30.0 mass of solid content of (A) and (B) Part(s) by mass (active ingredient) of acid catalyst part of 1.5 1.5 1.5 1.5 1.5 (C) per 100 parts by mass of solid content of (A) and (B) Part(s) by mass (solid content) of (D) per 100 parts by 3.0 3.0 3.0 3.0 3.0 mass of solid content of (A) and (B) Part(s) by mass (active ingredient) of (E) per 100 parts 0.0 0.0 0.0 0.0 0.0 by mass of solid content of (A) and (B) Baking temperature (PMT) (°C) 220 220 220 220 220 Baking time (s) 6 6 6 6 6 Coating film appearance 0 0 0 0 0 Storage stability Viscosity ratio (%) 140 140 140 140 140 Solvent resistance 5 4 3 4 3 Folding test 4 5 5 5 5 Processability Adhesive property 4 4 4 4 4 Alkali resistance 8FM 8FM 8FM 8FM 8FM Acid resistance 8FM 8FM 8FM 8FM 8FM
[0152]
[Table 7J] Example 46 Example 47 Example 48 Example 49 Example 50 Coating Coating Coating Coating Coating composition composition composition composition composition 46 47 48 49 50 (A12) (A13) (Al) (Al) (Al) Hydroxyl group-containing resin (A) Epoxy resin Acrylic Polyester Polyester Polyester I resin 1 resin I resin 1 resin 1 Amino resin (B) or other material (B1) (B1) (B2) (B3) (B4) Covalently bonded blocked acid catalyst (C) or other (Cl1) (Cl1) (Cl1) (Cl1) (C11) material Phosphoric acid-modified epoxy resin (D) (D1) (D1) (D) (D1) (D1) Alkanolamine (E) Part(s) by mass (solid content) of (A) per 100 parts by 70.0 70.0 70.0 70.0 70.0 mass of solid content of(A) and (B) Part(s) by mass (solid content) of (B) per 100 parts by 30.0 30.0 30.0 30.0 30.0 mass of solid content of (A) and (B) Part(s) by mass (active ingredient) of acid catalyst part of 1.5 1.5 1.5 1.5 1.5 (C) per 100 parts by mass of solid content of (A) and (B) Part(s) by mass (solid content) of (D) per 100 parts by 3.0 3.0 3.0 3.0 3.0 mass of solid content of (A) and (B) Part(s) by mass (active ingredient) of (E) per 100 parts 0.0 0.0 0.0 0.0 0.0 by mass of solid content of(A) and (B) Baking temperature (PMT) (°C) 220 220 220 220 220 Baking time (s) 6 6 6 6 6 Coating film appearance 0 0 0 0 0 Storage stability Viscosity ratio (%) 140 140 140 140 140 Solvent resistance 3 3 5 4 4 Folding test 4 4 5 5 5 Processability Adhesive property 4 4 5 5 4 Alkali resistance 8FM 8FM 8FM 8FM 8FM Acid resistance 8FM 8FM 8FM 8FM 8FM
[0153]
[Table 7K] Example 51 Example 52 Example 53 Example 54 Example 55 Coating Coating Coating Coating Coating composition composition composition composition composition 51 52 53 54 55 (Al) (Al) (Al) (Al) (Al) Hydroxyl group-containing resin (A) Polyester Polyester Polyester Polyester Polyester resin I resin 1 resin 1 resin 1 resin 1 Amino resin (B) or other material (B5) (B6) (B1) (B1) (B1) Covalently bonded blocked acid catalyst (C) or other (Cl1) (Cl1) (Cl1) (C11) (Ci1) material Phosphoric acid-modified epoxy resin (D) (DI) (D1) (DI) (D) (D1) Alkanolamine (E) (E2) (E3) (E4) Part(s) by mass (solid content) of (A) per 100 parts by 70.0 70.0 70.0 70.0 70.0 mass of solid content of(A) and (B) Part(s) by mass (solid content) of (B) per 100 parts by 30.0 30.0 30.0 30.0 30.0 mass of solid content of(A) and (B) Part(s) by mass (active ingredient) of acid catalyst part of 1.5 1.5 1.5 1.5 1.5 (C) per 100 parts by mass of solid content of (A) and (B) Part(s) by mass (solid content) of (D) per 100 parts by 3.0 3.0 3.0 3.0 3.0 mass of solid content of (A) and (B) Part(s) by mass (active ingredient) of (E) per 100 parts 0.0 0.0 3.0 3.0 3.0 by mass of solid content of (A) and (B) Baking temperature (PMT) (°C) 220 220 220 220 220 Baking time (s) 6 6 6 6 6 Coating film appearance 0 0 0 0 0 Storage stability Viscosityratio(%) 140 140 110 130 120 Solvent resistance 3 3 5 4 5 Folding test 4 4 5 5 5 Processability Adhesive property 4 4 5 5 5 Alkali resistance 8FM 8FM 8FM 8FM 8FM Acid resistance 8FM 8FM 8FM 8FM 8FM
[0154]
[Table 7L] Example 56 Example 57 Example 58 Example 59 Example 60 Coating Coating Coating Coating Coating composition composition composition composition composition 56 57 1 1 1 (Al) (Al) (Al) (Al) (Al) Hydroxyl group-containing resin (A) Polyester Polyester Polyester Polyester Polyester resin 1 resin I resin 1 resin 1 resin I Amino resin (B) or other material (B1) (B1) (B1) (B1) (B1) Covalently bonded blocked acid catalyst (C) or other (C11) (C11) (C11) (CI) (Cl1) material Phosphoric acid-modified epoxy resin (D) (D1) (DI) (Dl) (D1) (D1) Alkanolamine (E) (E5) (E6) Part(s) by mass (solid content) of (A) per 100 parts by 70.0 70.0 70.0 70.0 70.0 mass of solid content of (A) and (B) Part(s) by mass (solid content) of (B) per 100 parts by 30.0 30.0 30.0 30.0 30.0 mass of solid content of (A) and (B) Part(s) by mass (active ingredient) of acid catalyst part of 1.5 1.5 1.5 1.5 1.5 (C) per 100 parts by mass of solid content of (A) and (B) Part(s) by mass (solid content) of (D) per 100 parts by 3.0 3.0 3.0 3.0 3.0 mass of solid content of (A) and (B) Part(s) by mass (active ingredient) of(E) per 100 parts 3.0 3.0 0.0 0.0 0.0 by mass of solid content of (A) and (B) Baking temperature (PMT) (°C) 220 220 180 170 270 Baking time (s) 6 6 6 6 6 Coating film appearance 0 0 0 0 0 Storage stability Viscosity ratio (%) 120 130 140 140 140 Solvent resistance 5 4 4 3 5 Folding test 5 5 5 5 5 Processability Adhesive property 5 5 4 4 4 Alkali resistance 8FM 8FM 8FM 8FM 8FM Acid resistance 8FM 8FM 8FM 8FM 8FM
[0155]
[Table 7M] Example 61 Example 62 Example 63 Example 64 Coating Coating Coating Coating composition composition composition composition 1 1 1 j 1 (Al) (Al) (Al) (Al) Hydroxyl group-containing resin (A) Polyester Polyester Polyester Polyester resin I resin 1 resin 1 resin 1 Amino resin (B) or other material (B1) (B1) (B1) (B1) Covalently bonded blocked acid catalyst (C) or other (Cl1) (Cl1) (Cl1) (C11) material Phosphoric acid-modified epoxy resin (D) (D1) (DI) (D1) (D1) Alkanolamine (E) Part(s) by mass (solid content) of (A) per 100 parts by 70.0 70.0 70.0 70.0 mass of solid content of(A) and (B) Part(s) by mass (solid content) of (B) per 100 parts by 30.0 30.0 30.0 30.0 mass of solid content of (A) and (B) Part(s) by mass (active ingredient) of acid catalyst part of 1.5 1.5 1.5 1.5 (C) per 100 parts by mass of solid content of (A) and (B) Part(s) by mass (solid content) of (D) per 100 parts by 3.0 3.0 3.0 3.0 mass of solid content of(A) and (B) Part(s) by mass (active ingredient) of (E) per 100 parts 0.0 0.0 0.0 0.0 by mass of solid content of (A) and (B) Baking temperature (PMT) (°C) 1 280 220 220 [ 220 Baking time (s) 6 1 10 25 Coating film appearance 0 0 0 0 Storage stability Viscosity ratio (%) 140 140 140 140 Solvent resistance 5 5 5 5 Folding test 4 5 5 5 Processability Adhesive property 4 5 5 5 Alkali resistance 8FM 8FM 8FM 8FM Acid resistance 8FM 8FM 8FM 8FM
[0156]
[Table 7N] Comparative Comparative Comparative Comparative Comparative Example l Example 2 Example 3 Example 4 Example 5 Coating Coating Coating Coating Coating composition composition composition composition composition 58 59 60 61 62 (Al) (Al) (Al) (Al) (Al) Hydroxyl group-containing resin (A) Polyester Polyester Polyester Polyester Polyester resin 1 resin 1 resin I resin 1 resin 1 Amino resin (B) or other material (B1) (B1) (B1) (B1) (B1) Covalently bonded blocked acid catalyst (C) or other (Cl1) (Cl1) (Cl1) (Cl1) material Phosphoric acid-modified epoxy resin (D) (D1) (D1) (D1) (D1) (D1) Alkanolamine (E) Part(s) by mass (solid content) of (A) per 100 parts by 95.0 50.0 70.0 70.0 70.0 mass of solid content of (A) and (B) Part(s) by mass (solid content) of (B) per 100 parts by 5.0 50.0 30.0 30.0 30.0 mass of solid content of (A) and (B) Part(s) by mass (active ingredient) of acid catalyst part of 1.5 1.5 0.5 0.0 15.0 (C) per 100 parts by mass of solid content of (A) and (B) Part(s) by mass (solid content) of (D) per 100 parts by 3.0 3.0 3.0 3.0 3.0 mass of solid content of (A) and (B) Part(s) by mass (active ingredient) of (E) per 100 parts 0.0 0.0 0.0 0.0 0.0 by mass of solid content of(A) and (B) Baking temperature (PMT) (C) 220 220 220 220 220 Baking time (s) 6 6 6 6 6 Coating film appearance 0 X 0 0 X Storage stability Viscosity ratio (%) 140 140 140 140 140 Solvent resistance 1 5 1 1 5 Folding test 5 2 5 4 2 Processability Adhesive property 4 2 4 1 2 Alkali resistance 8M 8F 8M 8D 8F Acid resistance 8M 8F 8M 8D 8F
[0157]
[Table 70] Comparative Comparative Comparative Comparative Comparative Example 6 Example 7 Example 8 Example 9 Example 10 Coating Coating Coating Coating Coating composition composition composition composition composition 63 64 65 66 67 (Al) (Al) (Al) (Al) (Al) Hydroxyl group-containing resin (A) Polyester Polyester Polyester Polyester Polyester resin 1 resin 1 resin 1 resin 1 resin I Amino resin (B) or other material (B1) (B1) (B1) (B1) (B1) Covalently bonded blocked acid catalyst (C) or other (C11) (C1) (C11) (c31) (c32) material Phosphoric acid-modified epoxy resin (D) (D1) (D1) (D1) (D1) Alkanolamine (E) Part(s) by mass (solid content) of (A) per 100 parts by 70.0 70.0 70.0 70.0 70.0 mass of solid content of(A) and (B) Part(s) by mass (solid content) of.(B) per 100 parts by 30.0 30.0 30.0 30.0 30.0 mass of solid content of (A) and (B) Part(s) by mass (active ingredient) of acid catalyst part of 1.5 1.5 1.5 0.0 0.0 (C) per 100 parts by mass of solid content of (A) and (B) Part(s) by mass (solid content) of (D) per 100 parts by 0.5 0.0 15.0 3.0 3.0 mass of solid content of (A) and (B) Part(s) by mass (active ingredient) of (E) per 100 parts 0.0 0.0 0.0 0.0 0.0 by mass of solid content of (A) and (B) Baking temperature (PMT) (°C) 220 220 220 220 220 Baking time (s) 6 6 6 6 6 Coating film appearance 0 0 x x x Storage stability Viscosity ratio (%) 140 140 140 200 250 Solvent resistance 1 1 5 2 1 Folding test 5 4 2 5 5 Processability Adhesive property 4 1 2 2 2 Alkali resistance 8M 8D 8F 8D 8D Acid resistance 8M 8D 8F 8D 8D
[0158]
[Table 7P] Comparative Comparative Reference Example 11 Example 12 Example 1 Coating Coating Coating composition composition composition 68 69 69 (Al) (Al) (Al) Hydroxyl group-containing resin (A) Polyester Polyester Polyester resin I resin 1 resin 1 Amino resin (B) or other material Polyisocyanate (B5) (B5) compound1I Covalently bonded blocked acid catalyst (C) or other (C11) - material Phosphoric acid-modified epoxy resin (D) (D1) - Alkanolamine (E) Part(s) by mass (solid content) of (A) per 100 parts by 70.0 70.0 70.0 mass of solid content of (A) and (B) Part(s) by mass (solid content) of (B) per 100 parts by 30.0 30.0 30.0 mass of solid content of (A) and (B) Part(s) by mass (active ingredient) of acid catalyst part of 1.5 0.0 0.0 (C) per 100 parts by mass of solid content of (A) and (B) Part(s) by mass (solid content) of (D) per 100 parts by 3.0 0.0 0.0 mass of solid content of (A) and (B) Part(s) by mass (active ingredient) of (E) per 100 parts 0.0 0.0 0.0 by mass of solid content of(A) and (B) Baking temperature (PMT) (°C) 220 220 220 Baking time (s) 6 6 25 Coating film appearance 0 x 0 Storage stability Viscosity ratio (%) 150 150 150 Solvent resistance 1 1 5 Folding test 3 2 5 Processability Adhesive property 1 2 5 Alkali resistance 8D 8D 8FM Acid resistance 8D 8D 8FM
[0159]
<Evaluation items>
1) Storage stability
Evaluation was carried out using a Ford cup No. 4 (manufactured by Ueshima
Seisakusho Co., Ltd.) in accordance with the method specified in JIS K 5600-2-2 (the
flow cup method).
The coating compositions obtained in Examples, Comparative Examples, and
Reference Example were each stirred at 1,000 rpm for 3 minutes using a disper.
Immediately after stirring, a cup was filled up with the coating material such that air
bubbles did not enter in the coating material. At this time, the lower flow outlet
(orifice) was pressed so that the coating material did not leak from the outlet.
Thereafter, the presser was removed and measurement of time was started with a
stopwatch at the same time as the coating material flowed down. When the flow down
from the lower flow outlet (orifice) turned to a discontinuous flow, the stopwatch was
stopped and the number of seconds at that time was read, and the time was recorded
(initial viscosity). The temperature of the coating composition was adjusted to 250 C.
Each of the coating compositions of Examples, Comparative Examples, and
Reference Examples whose initial viscosity had been measured was charged into a 1/5 L
can to 80 to 90%, sealed, and then allowed to stand in a thermostatic chamber at 500 C.
Thereafter, the sample was taken out after 28 days, and the viscosity was measured in
the same manner as described above (viscosity over time).
The ratio of the viscosity over time to the initial viscosity (viscosity ratio) was
calculated from the following formula and the storage stability was evaluated. When
the viscosity ratio was 150% or less, it was determined that the storage stability was
good.
Viscosity ratio (%)= viscosity over time/initial viscosity x 100
[0160]
2) Coating film appearance
The appearance of the coating films obtained in Examples, Comparative
Examples, and Reference Example was visually observed, and the degree of bubbles
was evaluated according to the following criteria.
0: No bubbles were generated in the coating film.
x: Bubbles were generated in the coating film.
[0161]
3) Solvent resistance
The coated steel sheets obtained in Examples, Comparative Examples, and
Reference Example were attached to an evaluation table of an abrasion resistance tester
IMC-155F (manufactured by Imoto Machinery Co., Ltd.) with an adhesive tape, and a
rubbing test was carried out. Under the measurement conditions, absorbent cotton
containing methyl ethyl ketone and wrapped with four gauzes was used as an abrasion
material, a load was set to 2 kgf, a reciprocating speed was set to 30 times/min, a
reciprocating distance was set to 70 mm, and the number of reciprocations was set to
200 times. The number of rubbing reciprocations until the substrate of the base steel
sheet was exposed was counted and evaluated according to the following criteria.
Score 3 or higher was regarded as acceptable, and score 5 was regarded as good. The
test condition was adjusted to a temperature of 23°C and a humidity of 60 RH%.
Score 5: 200 times or more
Score 4: 100 times or more and less than 200 times
Score 3: 50 times or more and less than 100 times
Score 2: 10 times or more and less than 50 times
Score 1: less than 10 times
[0162]
4) Processability (folding test)
Each of the coated steel sheets obtained in Examples, Comparative Examples,
and Reference Example was cut into a size of 5 cm x 3 cm, and subjected to preliminary
folding using a seam folding machine (manufactured by Ueshima Seisakusho Co., Ltd.)
such that the coated film surface was on the front side. Five steel sheets having the
same thickness (0.4 mm) were sandwiched between the test pieces, and folded by a
pressing machine (manufactured by Kyoritsu Kogyo Co., Ltd.). The state (crack) of
the coating film of the processed part was observed with a loupe of 15 magnification, and the processability was evaluated according to the following criteria. Score 4 or higher was regarded as acceptable. The test condition was adjusted to a temperature of
23°C and a humidity of 60 RH%.
5: No crack is observed in the processed part.
4: Cracks are observed in less than 20% (and more than 0%) of the area of the
processed part.
3: Cracks are observed in 20% or more and less than 50% of the area of the
processed part.
2: Cracks are observed in 50% or more and less than 80% of the area of the
processed part.
1: Cracks are observed in 80% or more of the area of the processed part.
[0163]
5) Processability (adhesive property)
Each of the coated steel sheets obtained in Examples, Comparative Examples,
and Reference Example was cut into a size of 5 cm x 3 cm, and subjected to preliminary
folding using a seam folding machine (manufactured by Ueshima Seisakusho Co., Ltd.)
such that the coated film surface was on the front side. Two steel sheets having the
same thickness (0.4 mm) were sandwiched between the test pieces, and folded by a
pressing machine (manufactured by Kyoritsu Kogyo Co., Ltd.). Cellophane tape
(trademark) (LP-24, manufactured by NICHIBAN Co., Ltd.) was brought into close
contact with the processed part of the coated steel sheet, and peeled off at once. The
appearance of the part peeled off with the tape was observed with a loupe of 15
magnification, and the processing adhesive property was evaluated according to the
following criteria. Score 4 or higher was regarded as acceptable. The test condition
was adjusted to a temperature of 23°C and a humidity of 60 RH%.
5: The metal substrate is not observed in the tape peeled part.
4: The metal substrate is observed in less than 20% (more than 0%) of the area
of the tape peeled part.
3: The metal substrate is recognized in 20% or more and less than 50% of the
area of the tape peeled part.
2: The metal substrate is recognized in 50% or more and less than 80% of the
area of the tape peeled part.
1: Metal basis material is recognized in 80% or more of the area of the tape
peeled portion.
[0164]
6) Alkali resistance test
Each of the coated steel sheets obtained in Examples, Comparative Examples,
and Reference Example was cut into a size of 5 cm x 10 cm, and each specimen was
immersed in a 5% aqueous sodium hydroxide solution at 23°C for 48 hours, taken out,
washed with water, and dried at 20°C for 2 hours. The resulting coated steel sheet
specimen was evaluated for blister on a flat portion in accordance with ASTM D714-56.
Here, ASTM D714-56 evaluates the size (mean diameter) and density of each blister in
comparison with a standard judgment photograph and indicates a grade symbol. The
size was classified in four grades in the order of 8 (diameter: about 1 mm), 6 (diameter:
about 2 mm), 4 (diameter: about 3 mm) and 2 (diameter: about 5 mm), and the density
was classified in five grades in the ascending order of F, FM, M, MD and D, and when
there was no blister, this was evaluated as 10. Ascore of 8FM ormore was defined to
be acceptable.
[0165]
7) Acid resistance test
Each of the coated steel sheets obtained in Examples, Comparative Examples,
and Reference Example was cut into a size of 5 cm x 10 cm, and each specimen was
immersed in a 5% aqueous sulfuric acid solution at 23°C for 48 hours, taken out,
washed with water, and dried at 20°C for 2 hours. The resulting coated steel sheet
specimen was visually observed for blister on a flat portion in accordance with ASTM
D714-56 and the acid resistance was evaluated. A score of 8FM or more was defined
to be acceptable.
[0166]
As shown in the above tables, in Examples 1 to 64, the storage stability of the
coating composition was good.
In Examples 1 to 57 among Examples, a coating film was formed at a baking
temperature of 220°C for a baking time of 6 seconds. In these Examples, a coating
film having good physical properties in all of coating appearance, solvent resistance,
folding processability, processing adhesive property, alkali resistance, and acid
resistance was obtained.
Examples 62, 1, 63, and 64 are examples in which the baking temperature was
220°C and the baking time was 1 second, 6 seconds, 10 seconds, and 25 seconds,
respectively. In Example 62, although the baking time was set to 1 second, a coating
film having good physical properties was obtained, and it was confirmed that the
coating composition was sufficiently cured even in a short time of1 second. In
Example 63, the baking time was 10 seconds, and in Example 64, the baking time was
seconds. Also in these Examples, a coating film having good physical properties
was obtained. That is, it was found that when the coating composition of the present
invention is used, the coating composition is sufficiently cured even in a short time, and
a coating film obtained by short-time baking (Examples 62, 1, 63) has the same good physical properties as a coating film obtained by relatively long-time baking (Example
64).
Examples 58, 59, 1, 60, and 61 are examples in which the baking time was set
to 6 seconds and the baking temperatures were set to 180°C, 170°C, 220°C, 270°C, and
280°C, respectively. For example, in Examples 58 and 59, although a coating film was
formed at a low baking temperature, a coating film having good physical properties was
obtained, and it has been confirmed that the coating composition of the present
invention was sufficiently cured even when baked at a low temperature. In Examples
and 61, a coating film was formed at a relatively high baking temperature, and it has
been confirmed that the coating composition of the present invention can afford a
coating film having good physical properties.
[0167]
In Comparative Examples 1 to 12, it is shown that the storage stability of the
coating composition and the curing in a short time are not compatible. Hereinafter,
each comparative example will be described in detail.
The coating composition of Comparative Example 1 contains 95 parts by mass
of the hydroxyl group-containing resin (A1) and 5 parts by mass of the amino resin (B1)
based on 100 parts by mass of the total of the hydroxyl group-containing resin (Al) and
the amino resin (B1). The results of solvent resistance, alkali resistance, and acid
resistance of the coating film formed in Comparative Example 1 were not good. That
is, in Comparative Example 1, it is found that the curing reaction does not sufficiently
proceed by heating at 220°C for 6 seconds and a coating film having good physical
properties is not obtained.
The coating composition in Comparative Example 2 contains 50 parts by mass
of the hydroxyl group-containing resin (Al) and 50 parts by mass of the amino resin
(B1) based on 100 parts by mass of the total of the hydroxyl group-containing resin
(Al) and the amino resin (B1). The coating film formed in Comparative Example 2
was unsatisfactory in coating film appearance, folding processability, and processing
adhesive property. That is, in Comparative Example 2, it is found that the curing
reaction does not appropriately proceed by heating at 220°C for 6 seconds and a coating
film having good physical properties is not obtained.
The coating composition in Comparative Example 3 has a small content of the
covalently bonded blocked acid catalyst (C11), and the coating composition in
Comparative Example 5 has a large content of the covalently bonded blocked acid
catalyst(C1I). The coating film formedin Comparative Example 3 was unsatisfactory
in solvent resistance, alkali resistance, and acid resistance, and the coating film formed
in Comparative Example 5 was unsatisfactory in coating appearance, folding
processability, and processing adhesive property. That is, in Comparative Examples 3
and 5, it is found that an appropriate curing reaction does not proceed by heating at
220°C for 6 seconds and a coating film having good physical properties is not obtained.
The coating composition in Comparative Example 4 does not contain a
covalently bonded blocked acid catalyst (C). The coating film formed in Comparative
Example 4 exhibited poor results in solvent resistance, processing adhesive property,
alkali resistance, and acid resistance. That is, in Comparative Example 4, it is found
that the curing reaction does not sufficiently proceed by heating at 220°C for 6 seconds
and a coating film having good physical properties is not obtained.
The coating composition in Comparative Example 6 has a low content of the
phosphoric acid-modified epoxy resin (D1), and the coating composition in
Comparative Example 8 has a high content of the phosphoric acid-modified epoxy resin
(Dl). The coating film formed in Comparative Example 6 was unsatisfactory in solvent resistance, alkali resistance, and acid resistance, and the coating film formed in
Comparative Example 8 was unsatisfactory in coating film appearance, folding
processability, and processing adhesive property. That is, in Comparative Examples 6
and 8, it is found that an appropriate curing reaction does not proceed by heating at
220°C for 6 seconds and a coating film having good physical properties is not obtained.
The coating composition in Comparative Example 7 does not contain any
phosphoric acid-modified epoxy resin (D). The coating film formed in Comparative
Example 7 exhibited poor results in solvent resistance, processing adhesive property,
alkali resistance, and acid resistance. That is, in Comparative Example 7, it is found
that the curing reaction does not sufficiently proceed by heating at 220°C for 6 seconds
and a coating film having good physical properties is not obtained.
The coating composition in Comparative Example 9 contains an amine blocked
acid catalyst (acid catalyst 1 (c31)) as an acid catalyst, and the coating composition in
Comparative Example 10 contains an unblocked sulfonic acid (acid catalyst 2 (c32)) as
an acid catalyst. In these Comparative Examples, the viscosity of the coating
composition increased, and the formed coating film had poor appearance, solvent
resistance, processability adhesive property, alkali resistance, and acid resistance. That
is, in Comparative Examples 9 and 10, the storage stability of the coating composition
significantly deteriorated, and in the formation of a coating film, the curing reaction did
not appropriately proceed by heating at 220°C for 6 seconds, and a coating film having
good physical properties was not obtained. In Comparative Example 10, it is
considered that the sulfonic acid acted as a curing catalyst during storage, so that the
viscosity of the coating composition increased. In Comparative Example 9, it is
considered that the amine compound blocking the sulfonic acid dissociated from the
sulfonic acid during storage, and the sulfonic acid acted as a curing catalyst. In general, in the curing process of a coating film, the solvent evaporates from the applied film and then the coating film starts to be cured. In Comparative Examples 9 and 10, it is considered that in the curing process of the coating film, the catalyst worked to accelerate the curing before the evaporation of the solvent completed, so that pinhole shaped holes called bubbles were generated in the coating film appearance after the curing. It is considered that these bubbles caused exposure of the substrate in the solvent resistance test and peeling of the coating film in the processing adhesive property test.
The coating composition in Comparative Example 11 contains not an amino
resin but a polyisocyanate compound as a curing agent. The coating film formed in
Comparative Example 11 exhibited poor results in solvent resistance, processing
adhesive property, alkali resistance, and acid resistance. That is, in Comparative
Example 11, it is found that the curing reaction does not sufficiently proceed by heating
at 220°C for 6 seconds and a coating film having good physical properties is not
obtained. When an amino resin is used as in Examples, it is considered that in addition
to a curing reaction with a hydroxyl group-containing resin or a phosphoric acid
modified epoxy resin in the presence of an acid catalyst, self-condensation also occurs,
and the overall curing reaction proceeds sufficiently. However, when an isocyanate
compound was used as in Comparative Example 11, it is considered that a curing
reaction with a hydroxyl group-containing resin and a phosphoric acid-modified epoxy
resin occurred, but a self-condensation reaction did not occur, and the overall curing
reaction did not sufficiently proceed. In addition, since the polyisocyanate compound
is blocked with the blocking agent, the blocking agent needs to dissociate before the
reaction of isocyanate in order for the curing reaction to proceed, but it is considered
that the blocking agent could not sufficiently dissociate in a short time of 6 seconds, and the curing reaction did not proceed.
[0168]
In Reference Example 1, a common coating composition for a precoated steel
sheet was used. This coating composition contains neither the covalently bonded
blocked acid catalyst (C) nor the phosphoric acid-modified epoxy resin (D). The
coating composition in Reference Example 1 exhibited good evaluation of storage
stability, and a coating film having good physical properties has been obtained by
heating the coating composition at a baking temperature of 200°C for 25 seconds. In
Comparative Example 12, the coating composition in Reference Example 1 was heated
at a baking temperature of 220°C for 6 seconds. The coating film formed in
Comparative Example 12 was unsatisfactory in coating film appearance, solvent
resistance, folding processability, processing adhesive property, alkali resistance, and
acid resistance. That is, in Comparative Example 12, it is found that the curing
reaction does not sufficiently proceed by heating at a baking temperature of 220°C for 6
seconds and a coating film having good physical properties is not obtained.
[0169]
The coating composition of the present disclosure has good storage stability, a
curing reaction thereof proceeds by baking in a short time, so that a coating film having
good physical properties can be formed even by baking in a short time. In the coating
composition of the present disclosure, the curing reaction proceeds well even in a
furnace having a shortened furnace length like an IH type furnace, and a coating film
having good physical properties can be formed.
Claims (11)
1. A coating composition comprising
a hydroxyl group-containing resin (A),
an amino resin (B),
a covalently bonded blocked acid catalyst (C), and
a phosphoric acid-modified epoxy resin (D),
wherein
based on 100 parts by mass of a total of a resin solid content of the hydroxyl
group-containing resin (A) and a resin solid content of the amino resin (B),
60 to 90 parts by mass of the hydroxyl group-containing resin (A),
10 to 40 parts by mass of the amino resin (B),
1 to 10 parts by mass of an acid catalyst moiety of the covalently bonded
blocked acid catalyst (C), and
1 to 10 parts by mass of a solid component of the phosphoric acid-modified
epoxy resin (D) are contained.
2. The coating composition according to claim 1, wherein a number-average
molecular weight of the phosphoric acid-modified epoxy resin (D) is in a range of 460
to 4,000.
3. The coating composition according to claim 1 or 2, wherein the covalently
bonded blocked acid catalyst (C) is a catalyst in which an aromatic sulfonic acid is
blocked by a compound having a glycidyl group.
4. The coating composition according to claim 3, wherein in the covalently
bonded blocked acid catalyst (C), the compound having a glycidyl group is an epoxy
resin having two or more glycidyl groups in a molecule or a glycidyl ether compound
having one glycidyl group in a molecule.
5. The coating composition according to claim 4, wherein in the covalently
bonded blocked acid catalyst (C), a number-average molecular weight of the epoxy
resin having two or more glycidyl groups in a molecule is in a range of 2,000 to 7,000.
6. The coating composition according to claim 4, wherein in the covalently
bonded blocked acid catalyst (C), a molecular weight of the glycidyl ether compound
having one glycidyl group in a molecule is in a range of 140 to 200.
7. The coating composition according to any one of claims 1 to 6, wherein the
hydroxyl group-containing resin (A) is a polyester resin and
a number-average molecular weight of the hydroxyl group-containing resin (A)
is in a range of 1,500 to 5,000 and a hydroxyl value is in a range of 40 to 100 mg
KOH/g.
8. The coating composition according to any one of claims 1 to 7, wherein the
amino resin (B) comprises a melamine resin.
9. The coating composition according to any one of claims 1 to 8, further
comprising an alkanolamine (E).
10. The coating composition according to claim 9, wherein the alkanolamine (E)
comprises two or more alkanol groups in a molecule.
11. The coating composition according to claim 9 or 10, wherein a content of the
alkanolamine (E) is 1.0 to 4.0 parts by mass based on 100 parts by mass of the total of
the resin solid content of the hydroxyl group-containing resin (A) and the resin solid
content of the amino resin (B).
12. A method for producing a coating film, comprising:
a step of applying the coating composition according to any one of claims 1 to
11 to an article to be coated to form an applied film; and
a step of drying and/or curing the applied film under a condition in which a peak temperature of the article to be coated is 180°C to 270°C and a drying and/or curing time is 1 to 10 seconds.
13. A method for producing a precoated metal sheet, comprising:
a step of applying the coating composition according to any one of claims 1 to
11 on at least one surface of a metal sheet to form an applied film such that a film
thickness after curing is 5 to 25 tm; and
a step of drying and/or curing the applied film under a condition in which a
peak temperature of the metal sheet is 180°C to 270°C and a drying and/or curing time
is 1 to 10 seconds.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020-162362 | 2020-09-28 | ||
| JP2020162362 | 2020-09-28 | ||
| PCT/JP2021/027157 WO2022064829A1 (en) | 2020-09-28 | 2021-07-20 | Coating material composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| AU2021347006A1 true AU2021347006A1 (en) | 2022-09-15 |
Family
ID=80845268
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU2021347006A Pending AU2021347006A1 (en) | 2020-09-28 | 2021-07-20 | Coating material composition |
Country Status (6)
| Country | Link |
|---|---|
| JP (1) | JPWO2022064829A1 (en) |
| KR (1) | KR20230075379A (en) |
| CN (1) | CN114829520A (en) |
| AU (1) | AU2021347006A1 (en) |
| TW (1) | TW202212505A (en) |
| WO (1) | WO2022064829A1 (en) |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5536276A (en) * | 1978-09-08 | 1980-03-13 | Kansai Paint Co Ltd | One-pack type high-solid coating composition |
| JPH0692559B2 (en) * | 1989-02-10 | 1994-11-16 | 東洋インキ製造株式会社 | Paint composition |
| US5178915A (en) * | 1992-01-10 | 1993-01-12 | Morton International, Inc. | Coating composition and metal coil coating process employing same |
| JP3200462B2 (en) * | 1992-03-19 | 2001-08-20 | 関西ペイント株式会社 | Paint composition |
| JPH07331164A (en) * | 1994-06-14 | 1995-12-19 | Dainippon Ink & Chem Inc | Coating resin composition and coated steel sheet |
| JPH10130583A (en) * | 1996-10-31 | 1998-05-19 | Kanegafuchi Chem Ind Co Ltd | Curable composition for coating material and coated material coated with the same |
| JP2005139343A (en) * | 2003-11-07 | 2005-06-02 | Nippon Yushi Basf Coatings Kk | Thermosetting coating material composition, method for coating finishing and coated article |
| TWI458793B (en) * | 2009-08-05 | 2014-11-01 | Kansai Paint Co Ltd | Excellent corrosion-resistant coating composition |
| JP6939142B2 (en) * | 2017-06-27 | 2021-09-22 | 日本製鉄株式会社 | Paint for metal plate and manufacturing method of painted metal plate using it |
| JP6681459B1 (en) | 2018-12-21 | 2020-04-15 | 日本ペイント・インダストリアルコ−ティングス株式会社 | Pre-coated metal plate coating composition, pre-coated metal plate and method for producing the same |
| JP7143786B2 (en) * | 2019-03-04 | 2022-09-29 | 日本製鉄株式会社 | Painted metal plate and its manufacturing method |
-
2021
- 2021-07-20 AU AU2021347006A patent/AU2021347006A1/en active Pending
- 2021-07-20 JP JP2022551162A patent/JPWO2022064829A1/ja active Pending
- 2021-07-20 CN CN202180007841.3A patent/CN114829520A/en active Pending
- 2021-07-20 WO PCT/JP2021/027157 patent/WO2022064829A1/en active Application Filing
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| WO2022064829A1 (en) | 2022-03-31 |
| JPWO2022064829A1 (en) | 2022-03-31 |
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