US 20150.

064378A1
(19) United States
(12) Patent Application Publication (10) Pub. No.: US 2015/0064378 A1
KaWakusu (43) Pub. Date: Mar. 5, 2015
(54) POLYESTER RESIN, RESIN COMPOSITION (52) U.S. Cl.
FOR CAN PAINT, PAINTED METAL PLATE CPC ............ C09D 167/02 (2013.01); C08G 63/183
FOR CAN, AND CAN (2013.01); C08G 63/00 (2013.01); C09D
167/00 (2013.01); B65D 25/14 (2013.01);
(71) Applicant: TOYOBO CO.,LTD., Osaka (JP) B65D 25/34 (2013.01)
USPC ....... 428/35.8: 528/298; 524/605; 427/388.2:
(72) Inventor: Tetsuo Kawakusu, Shiga (JP) 428/458
(57) ABSTRACT
(21) Appl. No.: 14/384,228 This invention provides a polyester resin that is capable of
(22) PCT Filed: Feb. 25, 2013 forming a coating film having extremely excellent curability,
processability, retort resistance, content resistance, and dent
(86). PCT No.: PCT/UP2O13AOS4685 resistance, and also provides a resin composition for a coating
composition containing the polyester resin. The polyester
S371 (c)(1), resin obtained from a polycarboxylic acid component and a
(2) Date: Sep. 10, 2014 polyol component, wherein the polyester resin meets the
conditions (i) to iii) described below:
(30) Foreign Application Priority Data (i) among the polycarboxylic acid components constitut
ing the polyester resin, the total copolymerization ratio
Mar. 28, 2012 (JP) ................................. 2012-073858 of terephthalic acid component and 2,6-naphthalenedi
carboxylic acid component is 80 mol % or more;
(ii) among the polycarboxylic acid components constitut
ing the polyester resin, the copolymerization ratio of
Publication Classification 2,6-naphthalenedicarboxylic acid component is 2 to 80
mol%; and
(51) Int. Cl. (iii) among the polyol components constituting the poly
C09D 67/02 (2006.01) ester resin, the total copolymerization ratio of ethylene
B65D 25/34 (2006.01) glycol component and 1,2-propylene-glycol component
C09D 67/00 (2006.01) is 50 mol% or more, wherein the copolymerization ratio
B65D 25/14 (2006.01) of 1,2-propylene-glycol component is excessive relative
C08G 63/83 (2006.01) to the copolymerization ratio of the ethylene glycol
C08G 63/00 (2006.01) component.
US 2015/OO64378 A1 Mar. 5, 2015

POLYESTER RESIN, RESIN COMPOSITION external can Surfaces are also required to have countermea
FOR CAN PAINT, PAINTED METAL PLATE Sures against environmental hormones.
FOR CAN, AND CAN 0007. In order to solve the above problems, the application
of a polyester-based resin to a coating composition for the
TECHNICAL FIELD inner Surfaces of cans has been attempted, therein the poly
ester-based resin does not generate a toxic gas and/or corro
0001. The present invention relates to a polyester resin that sive gas during incineration, and does not contain an environ
is capable of forming a coating film having excellent process mental hormone, Such as bisphenol A, in the coating film.
ability, curability, retort resistance, content resistance, and However, a coating composition resin and a coating compo
dent resistance when the resin is used as a base resin to be sition resin composition that simultaneously exhibit satisfac
added to a coating composition (paint) that is to be applied to tory processability, curability, retort resistance, content resis
foods and beverages cans. The invention, in particular, relates tance, and dent resistance that are Suitable for use in cans have
to a polyester resin that is suitably usable as a base resin for not been obtained.
the inner Surface can coating composition. Furthermore, the 0008 Patent Literature 1 discloses a polyester resin that
present invention relates to a resin composition for can coat has excellent flavor preservability, that is environmentally
ing (paint), a coated (painted) metal plate for can, and to cans. friendly and highly safe from a health standpoint, wherein the
polyester resin is used for a coating composition for a metal
BACKGROUND ART package. The polyester resin is obtainable by copolymerizing
a dicarboxylic acid component composed of 80 to 100 mol%
0002 Generally, coating is applied to the inner surfaces of ofterephthalic acid and 0 to 20 mol% ofisophthalic acid with
food and beverage cans in order to prevent the corrosion of the a glycol component composed of 60 to 90 mol% of propylene
can material due to the wide variety of contents therein. The glycol, and 10 to 30 mol% of ethylene glycol or 1,3-butylene
coating composition applied to the inner Surfaces of food and glycol. However, Such a technique has drawbacks in regards
beverage cans is required to have the following properties. to achieving Sufficient processability and/or curability.
First, the coating composition should be free from toxicity, 0009 Patent Literature 2 discloses a polyester resin for use
and have sufficient curability (curability); second, the coating in a can coating composition, the polyester resin being obtain
composition is required to have excellent processability dur able by reacting an acid component composed of 80 to 100
ing molding (processability), tolerance during heat steriliza mol % aromatic dicarboxylic acid containing 70 to 95 mol%
tion (retort resistance), no blister or blushing when contents terephthalic acid and 0 to 20 mol% polybasic acid other than
containing salt or that exhibit acidity are subjected to heat aromatic dicarboxylic acid with a glycol component compris
sterilization (content resistance), impact resistance after heat ing 2-methyl-1.3 propanediol and 1.4-cyclohexane dimetha
sterilization (dent resistance), and the like. In recent years, the nol as essential components, wherein among the glycol com
use of bisphenol-type epoxy resins and the like has been ponents constituting the polyester resin, the content of
avoided since there is a concern that such resins function as
2-methyl-1,3 propanediol is 25 to 50 mol % relative to the
extrinsic factor endocrine disrupters (hereinafter, these may total glycol components, and wherein the total weight of
be referred to as environmental hormones). terephthalic acid and 1,4-cyclohexane dimethanol falls
0003 Currently, polyvinyl chloride-based resins and within the range of 45 to 65 wt % relative to the polyester
epoxy-phenol-based resins are often used as a base resin for resin. Patent Literature 2 also discloses that the resulting
coating compositions for the inner Surfaces of cans. However, polyester resin is excellent in processability and stain resis
because these resins have the serious problems indicated tance. However, the above technique has drawbacks in
below, there is a demand for the development of a coating regards to obtaining satisfactory processability and/or cur
agent for inner Surfaces that will replace the above-mentioned ability.
CS1S. 0010 Patent Literature 3 discloses a coating composition
0004 Although polyvinyl chloride-based resins exhibit comprising hydroxy-containing polyester resin and phenol
excellent retort resistance, content resistance, and process formaldehyde resin as essential components, and further
ability, the vinyl chloride monomer remaining in the resins comprising benzoguanamine-formaldehyde resin and/or
are indicated to have serious health dangers such as carcino blocked polyisocyanate, etc. Patent Literature 3 also discloses
genicity. Furthermore, when the cans are incinerated, there is that the resulting coating composition is excellent in process
a risk that highly toxic and corrosive chlorine gas, hydrogen ability, curability, and retort resistance. However, the above
chloride gas, and extremely toxic dioxin may be generated technique has drawbacks in regards to obtaining satisfactory
from the polyvinyl chloride-based resins, which may cause processability and/or curability.
the corrosion of the incinerator and environmental pollution.
In addition, polyvinyl chloride-based resins have insufficient CITATION LIST
adhesion with metals, which are materials for cans; therefore, Patent Literature
it is necessary to perform a Surface treatment using an epoxy
resin before coating, complicating the coating process. O011 PTL 1:JP2004-359759A
0005 Epoxy-phenol-based resins require a high baking O012 PTL 2: JP2008-81617A
temperature; accordingly, poor appearance, such as foaming, 0013 PTL3: JP2005-42110A
may easily occur during baking. Furthermore, as described
above, bisphenol A contained in epoxy resins may function as SUMMARY OF INVENTION
an environmental hormone.
Technical Problem
0006. In addition to the above-described processability
and retort resistance that are required for coating composi 0014. The present invention was made in consideration of
tions for inner can Surfaces, coating compositions for the the drawbacks of the prior art techniques. Specifically, an
US 2015/OO64378 A1 Mar. 5, 2015

object of the present invention is to provide a polyester resin 0028 (i) Among the polycarboxylic acid components con
that is capable of forming a coating film having extremely stituting the polyester resin, the octal copolymerization ratio
high curability, as well as excellent processability, retort of terephthalic acid component and 2,6-naphthalenedicar
resistance, content resistance, and dent resistance. boxylic acid component is 80 mol % or more;
0029 (ii) among the polycarboxylic acid components
Solution to Problem constituting the polyester resin, the copolymerization ratio of
0015 The present inventors conducted research in order to 2,6-naphthalenedicarboxylic acid component is 2 to 80 mol
achieve the above object, and thus accomplished the present %; and
invention. The present invention has the following features 0030 (iii) among the polyol components constituting the
(1) to (7). polyester resin, the total copolymerization ratio of ethylene
0016 (1) A polyester resin obtained from a polycarboxylic glycol component and 1,2-propylene-glycol component is 50
acid component and a polyol component, wherein the poly mol % or more, wherein the copolymerization ratio of 1,2-
ester resin insets the conditions (i) to (iii) described below. propylene-glycol component is excessive relative to the copo
0017 (i) among the polycarboxylic acid components con lymerization ratio of the ethylene glycol component.
stituting the polyester resin, the total copolymerization ratio 0031 Examples of polycarboxylic acid components con
of terephthalic acid component and 2,6-naphthalenedicar stituting the polyester resin of the present invention include
boxylic acid component is 80 mol % or more; aromatic dicarboxylic acids such as terephthalic acid, isoph
0018 (ii) among the polycarboxylic acid components thalic acid, orthophthalic acid, phenylenedicarboxylic acid,
constituting the polyester resin, the copolymerization ratio of and 2.6-naphthalenedicarboxylic acid; aliphatic dicarboxylic
2,6-naphthalenedicarboxylic acid component is 2 to 80 mol acids such as Succinic acid, glutaric acid, adipic acid, azelaic
%; and acid, sebacic acid, dodecanedioic acid, and dimer acid; alicy
0019 (iii) among the polyol components constituting the clic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic
polyester resin, the total copolymerization ratio of ethylene acid, tetrahydrophthalic acid, hexahydroisophthalic acid, and
glycol component and 1,2-propylene-glycol component is 50 1.2-cyclohexene dicarboxylic acid; and unsaturated dicar
mol % or more, wherein the copolymerization ratio of 1,2- boxylic acids such as fumaric acid, maleic acid, and terpene
propylene-glycol component is excessive relative to the copo maleic acid adduct. One, two, or more of the acids above may
lymerization ratio of the ethylene glycol component. be selected for use. Among these, in terms of processability,
0020 (2) The polyester resin of (1), which has a reduced retort resistance, and content resistance, the use of tereph
viscosity of 0.3 to 0.7 dl/g, a glass transition temperature of thalic acid and/or 2,6-naphthalenedicarboxylic acid is pref
70° C. or more, a specific gravity (30°C.) of 1.245 or more, erable.
and an acid value of 200 eq/t or less. 0032. The total copolymerization ratio ofterephthalic acid
0021 (3) A resin composition for can coating comprising and 2,6-naphthalenedicarboxylic acid constituting the poly
the polyester resin of (1) or (2) and a curing agent, which ester resin of the present invention, relative to the total acid
contains the polyester resin and the curing agent in a weight components (total polycarboxylic acid components), is pref
ratio of polyester resin/curing agent=98/2 to 50/50 (parts by erably 80 to 100 mol %, more preferably 85 to 100 mol %,
weight). even more preferably 90 to 100 mol %, and particularly
0022 (4) The resin composition for can coating of (3), preferably 95 to 100 mol%. A total copolymerization ratio
wherein the curing agent is a blocked isocyanate compound. lower than the above-mentioned ranges may result in unduly
0023 (5) A method for producing a coated metal plate for low processability and/or dent resistance.
can, comprising a step of applying the resin composition for 0033. The lower limit of the copolymerization ratio of
can coating of (3) or (4) to a metal plate, and curing the resin 2,6-naphthalenedicarboxylic acid constituting the polyester
composition. resin of the present invention, relative to the total acid com
0024 (6) A coated metal plate for can on which a layer ponents (total polycarboxylic acid components), is 2 mol%.
comprising a reactant of the polyester resin of (1) or (2) and a more preferably 3 mol %, and particularly preferably 4 mol
curing agent is placed on the Surface of the metal plate. %. A copolymerization ratio of 2,6-naphthalenedicarboxylic
0025 (7) A can comprising the coated metal plate for can acid lower than the aforementioned ranges may result in
of (6) as a constituting material. unduly low solvent solubility and/or coating composition
stability, or may undesirably lower the processability, curabil
Advantageous Effects of Invention ity, and/or dent resistance. The upper limit of the copolymer
0026. The resin composition used for the coating compo ization ratio of 2,6-naphthalenedicarboxylic acid, relative to
sition of the present invention comprises a polyester resin and the total acid component, is preferably 80 mol %, more pref
a curing agent, has extremely high curability, and allows the erably 70 mol%, even more preferably 60 mol%, particularly
resulting coating film to possess excellent processability as preferably 50 mol %, and most preferably 40 mol %. A
copolymerization ratio of 2.6-naphthalenedicarboxylic acid
well as remarkable retort resistance, content resistance, and lower than the aforementioned ranges may result in unduly
dent resistance. Therefore, the resin composition of the low solvent solubility and/or coating composition stability,
present invention is suitable for use as a can coating compo and/or undesirably lower the processability and/or dent resis
sition. tance.
DESCRIPTION OF EMBODIMENTS 0034 Examples of the polyol components constituting the
polyester resin of the present invention include aliphatic gly
0027. The polyester resin of the present invention can be cols such as ethylene glycol, 1,2-propylene glycol. 1,3-pro
obtained by reacting a polycarboxylic acid component with a panediol, 2-methyl-1,3-propanediol, neopentylglycol, 3-me
polyol component, wherein the polyester resin Satisfies the thyl-1,5-pentanediol, 1.2-butanediol, 1,3-butanediol, 1,4-
following conditions (i) to (iii). butanediol. 1,4-pentanediol. 1,3-pentanediol. 2,4-diethyl-1,
US 2015/OO64378 A1 Mar. 5, 2015

5-pentanediol, 1.6-hexanediol, 1-methyl-1,8-octanediol, 0039. In forming the polyester resin of the present inven
3-methyl-1,6-hexanediol, 4-methyl-1,7-heptanediol, 4-me tion, a polycarboxylic acid component and/or polyol compo
thyl-1,8-octanediol, 4-propyl-1,8-octanediol, and 1.9- nent may be copolymerized with a tri- or higher functional
nonanediol; polyether glycols such as diethylene glycol, tri component. Examples of tri- or higher functional polycar
ethylene glycol, polyethylene glycol, polypropylene glycol, boxylic acid components include trimellitic acid, pyromel
and polytetramethylene glycol; and alicyclic polyols such as litic acid, and benzophenone tetracarboxylic acid. Examples
1.2-cyclohexane dimethanol, 1.3-cyclohexane dimethanol, of tri- or higher functional polyols include glycerol (glyc
1,4-cyclohexane dimethanol, tricyclodecane glycols, and erin), trimethylolethane, trimethylolpropane, mannitol, Sor
hydrogenated bisphenols. One, two, or more polyol compo bitol, pentaerythritol, and C.-methyl glucoside. Use of these
nents may be selected from the above for use. Among these, components increases the crosslinking density when the coat
the use of ethylene glycol and/or 1.2-propylene glycol is ing composition is cured, improving the processability.
preferable interms of retort resistance and content resistance. 0040. The copolymerization ratio of a tri- or higher func
0035. The total copolymerization ratio of ethylene glycol tional acid component (functional polycarboxylic acid com
and 1,2-propylene glycol constituting the polyester resin of ponent) and a glycol component (polyol component), in acids
the present invention, relative to total polyol components, is or in glycol components, is preferably 0 to 5 mol %, more
preferably 50 to 100 mol%, more preferably 60 to 100 mol%. preferably 0 to 4 mol %, even more preferably 0 to 3 mol %,
even more preferably 70 to 100 mol%, particularly preferably and particularly preferably 0 to 2 mol%. When the copoly
80 to 100 mol%, and most preferably 90 to 100 mol%. A total merization ratio exceeds the aforementioned ranges, the flex
copolymerization ratio lower than the above ranges may ibility of the polyester resin is lost, lowering the processabil
unfavorably lower Tg, and may adversely affect the retort ity and/or dent resistance, or causing gelation during
resistance and/or content resistance, lowering its dent resis polymerization of polyester.
tance accordingly. 0041 An acid value may be added to the polyester resin of
0036. The lower limitation of the copolymerization ratio the present invention by any method. Providing an acid value
of ethylene glycol constituting the polyester resin of the achieves the following effects. That is, improving the curabil
present invention, relative to total polyol components, is pref ity of the polyester resin with crosslinking agent, and enhanc
erably 5 mol %, more preferably 10 mol %, even more pref ing the adhesion to the metal material for cans or the like.
erably 13 mol %, and particularly preferably 15 mol%. If the Examples of methods for providing an acid value include a
ethylene glycol copolymerization ratio is lower than the depolymerization method in which polyvalent carboxylic
aforementioned ranges, the curability may be lowered and Tg acid anhydride is added in the second half of the polyconden
may also be lowered, causing unfavorable retort resistance sation process, and a method in which a prepolymer (oligo
and/or content resistance. The upper limit of the copolymer mer) is made to have a high acid value, followed by polycon
ization ratio of ethylene glycol, relative to total polyol com densation to obtain polyester resin having an acid value. The
ponents, is preferably 45 mol %, more preferably 40 mol %, former depolymerization method is more preferable due to its
and even more preferably 35 mol%. If the copolymerization simple operation and ability to obtain a target acid value.
ratio exceeds the aforesaid ranges, the crystallinity of poly 0042 Examples of the polyvalent carboxylic acid anhy
ester resin will become unduly high, and the solvent solubility drides usable for acid addition in Such a depolymerization
and/or coating composition stability may be lowered. method include phthalic anhydride, tetrahydrophthalic anhy
0037. The lower limit of the copolymerization ratio of dride, Succinic anhydride, trimelitic anhydride, pyromellitic
1.2-propylene glycol constituting the polyester resin of the anhydride, and hexahydrophthalic anhydride. Among these,
present invention, relative to the total polyol components, is trimellitic anhydride is preferable.
preferably 45 mol %, more preferably 50 mol %, even more 0043 Among the properties of the polyester resin of the
preferably 55 mol %, particularly preferably 60 mol %, and present invention, the acid value is preferably 0 to 200 eq/t,
most preferably 65 mol%. When the copolymerization ratio more preferably 0 to 180 eq/t, even more preferably 0 to 160
is lower than the aforementioned ranges, the solvent solubil eq/t, and further more preferably 0 to 150 eq/t. If the acid
ity and/or coating composition stability may be lowered. The value exceeds the aforesaid ranges, the retort resistance and/
upper limit of the copolymerization ratio of 1,2-propylene or content resistance may become unfavorable.
glycol, relative to the total polyol components, is preferably 0044 Among the properties of the polyester resin of the
95 mol %, more preferably 90 mol %, even more preferably present invention, the lower limit of the reduced viscosity
85 mol %, and particularly preferably 80 mol%. When the (dl/g) is preferably 0.3. If the reduced viscosity is lower than
copolymerization ratio exceeds the aforementioned ranges, the aforesaid value, the processability and curability may be
the processability and/or curability may be lowered. undesirably lowered. The upper limit of the reduced viscosity
0038. In forming the polyester resin of the present inven (dl/g) is preferably 0.7. If the reduced viscosity exceeds the
tion, it is necessary that the copolymerization ratio of 1.2- aforesaid value, the solvent solubility may be lowered. This
propyleneglycol component be excessive relative to the copo may adversely affect the coating composition stability and
lymerization ratio of the ethylene glycol component. The coating operability. The term “reduced viscosity' in the
lower limit of the value subtracted from the copolymerization present invention is defined as the value measured in accor
ratio (molar ratio) of 1,2-propylene glycol to the copolymer dance with the method described in the Examples.
ization ratio of ethylene glycol is preferably 10 mol %, more 0045 Among the properties of the polyester resin of the
preferably 20 mol %, even more preferably 30 mol %, and present invention, the lower limit of the glass transition tem
particularly preferably 35 mol%. When the value is lower perature (Tg) is preferably 70° C., more preferably 75° C.,
than the aforementioned ranges, the crystallinity of polyester even more preferably 78° C., and particularly preferably 80°
resin becomes unduly high, Solvent solubility and/or coating C. If the glass transition temperature (Tg) is lower than the
composition stability may be lowered, and processability above ranges, the retort resistance and/or content resistance
and/or dent resistance may be lowered. may become undesirably low. The upper limit of the glass
US 2015/OO64378 A1 Mar. 5, 2015

transition temperature (Tg) is preferably 120°C., more pref alky; ester obtained from polycarboxylic acid is subjected to
erably 10020 C., and even more preferably 105° C. Exceed transesterification with a polyol component to obtain an oli
ing the above range is undesirable from economical and pro gomer, and the resulting oligomer is further subjected to
ductivity points of view. Tg in the present invention is almost melt-polycondensation under a reduced pressure and high
the same as that of T defined by JISK7121-1987; strictly, temperature. The polyester resin of the present invention may
however, the value is defined as the value measured by the be produced by either method, since there is no observable
method described in the Examples. difference between the properties thereof and the properties
0046 Among the properties of the polyester resin of the of the resulting resin composition for can coating.
present invention, the lower limit of the specific gravity is 0050. In terms of the solvent solubility and coating com
preferably 1.245, more preferably 1.248, even more prefer position stability, the properties of the polyester resin of the
ably 1.250, particularly preferably 1.255, and most preferably present invention are preferably such that no clear peaks of
1.260. If the specific gravity is lower than the aforesaid melting point (Tm) measured by differential scanning calo
ranges, the processability and curability may be undesirably rimetry (DSC) are observed. When the polyester resin indi
lowered. The specific gravity is preferably 1.400. Production cates a melting point and has crystallinity, the solvent solu
of resin having a specific gravity exceeding the aforemen bility and/or coating composition stability are lowered, and
tioned range is difficult from a technical standpoint. The this may cause lowered processability and/or dent resistance.
specific gravity in the present invention is defined as the value 0051. The curing agent constituting the resin composition
measured by the method described in the Examples. for can coating of the present invention is not particularly
0047 Among the properties of the polyester resin of the limited as long as it can react with the polyester resin of the
present invention, the glass transition temperature (Tg) can be present invention and form a cross linkage structure. Prefer
controlled by changing the copolymerization components able examples thereof include an isocyanate compound, phe
and the proportions thereof. For example, Tg tends to become nol resin, amino resin, and epoxy resin. In terms of the pro
higher by increasing, as the polycarboxylic acid component cessability, the curing agent constituting the resin
constituting the polyester resin, the copolymerization ratio of composition for can coating of the present invention is pref
aromatic polycarboxylic acid or alicyclic polycarboxylic erably an isocyanate compound, and more preferably a
acid. Tg also tends to become higher by increasing, as the blocked isocyanate compound.
polyol component constituting the polyester resin, the copo 0.052 Examples of the isocyanate compounds include iso
lymerization ratio of an alicyclic polyol or aliphatic polyol cyanates, for example, aromatic diisocyanates such as 2.4-
whose principal chain has 3 or fewer carbon atoms. In con tolylenediisocyanate, 2,6-tolylenediisocyanate, Xylene-1,4-
trast, Tg tends to be lowered by increasing the copolymeriza diisocyanate, Xylene-1,3-diisocyanate, tetramethylxylene
tion ratio, as the polycarboxylic acid component constituting diisocyanate, 4,4'-diphenylmethanediisocyanate, 2,4'-diphe
the polyester resin, of aliphatic polycarboxylic acid. Tg also nylmethanediisocyanate, 4,4'-diphenyletherdiisocyanate,
tends to be lowered by increasing the copolymerization ratio, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,
as the polyol component constituting the polyester resin, of an 4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocy
aliphatic polyol polyester resin whose principal chain has 4 or anate, 4,4'-diphenylpropanediisocyanate, m-phenylenediiso
more carbon atoms. cyanate, p-phenylenediisocyanate, naphthylene-1,4-
0048. Among the properties of the polyester resin of the diisocyanate, naphthylene-1,5-diisocyanate, and 3,3'-
present invention, the specific gravity can be controlled by dimethoxydiphenyl-4,4'-diisocyanate; aromatic
changing the copolymerization components and the propor polyisocyanates such as polymethylenepolyisocyanate and
tions thereof. For example, the specific gravity tends to crude tolylene diisocyanate; aliphatic diisocyanates such as
become higher by increasing the copolymerization ratio of, as tetramethylene diisocyanate, hexamethylene diisocyanate
the polyol components constituting the polyester resin, an (HDI), decamethylenediisocyanate, and lysinediisocyanate;
aliphatic polyol whose principal chain has 3 or less carbon alicyclic diisocyanates Such as isophorone diisocyanate
atoms and whose side chain has 2 or less carbon atoms. In (IPDI), hydrogenated tolylene diisocyanate, hydrogenated
contrast, the specific gravity tends to be lowered by increasing Xylenediisocyanate, and hydrogenated diphenylmethane
the copolymerization ratio of, as the polycarboxylic acid diisocyanate; biuret-modified products of the aforemen
components constituting the polyester resin, an aliphatic tioned isocyanates; urethodione-modified products of the
polycarboxylic acid whose principal chain has 4 or more aforementioned isocyanates; carbodiimide-modified prod
carbon atoms with or without a side chain. The specific grav ucts of the aforementioned isocyanates; isocyanurate-modi
ity also tends to be lowered by increasing the copolymeriza fied products of the aforementioned isocyanates; urethodi
tion ratio of as the polyol components constituting the poly one-modified products of the aforementioned isocyanates;
ester resin, an aliphatic polyol whose principal chain has 4 or adducts of the aforementioned isocyanates with polyol; and
more carbonatoms with or without a side chain, or by increas mixtures of the modified products.
ing the copolymerization ratio of an aliphatic polyol whose 0053 Among these, one, two, or more can be selected for
principal chain has 3 or more carbon atoms and whose side use. Furthermore, they may be used in the form of urethane
chain has 3 or more carbon atoms. precursors such as prepolymers, modifications, derivatives,
0049. The polyester resin of the present invention can be and mixtures of an isocyanate compound with a hydrogen
produced by a known polycondensation method of polyes group-containing compound Such as a polyol or polyamine.
ters. For example, a direct polymerization method, wherein a 0054 Preferable examples of the curing agents contained
polycarboxylic acid component and a polyol component are in the resin compositions for can coating of the present inven
esterified to obtain an oligomer, can be used. The oligomer tion include a blocked isocyanate compound whose terminal
thus obtained is further subjected to melt-polycondensation NCO groups of isocyanate compound are blocked. Examples
under a reduced pressure and high temperature. Another of the blocking agents include phenol-based compounds such
example is a transesterification method in which C-2 lower as phenol, cresol, ethylphenol, and butyl phenol; alcohol
US 2015/OO64378 A1 Mar. 5, 2015

based compounds Such as 2-hydroxypyridine, butyl cello glycol monoacetate, methanol, ethanol, butanol, ethylene
Solve, propylene glycol mono-methyl ether, benzyl alcohol, glycol monoethyl ether, ethylene glycol monobutyl ether,
methanol, ethanol, n-butanol, isobutanol, and 2-ethylhex diethylene glycol monobutyl ether, and the like. Among them,
anol; active methylene-based compounds such as dimethyl one, two, or mere compounds are selected from the viewpoint
malonate, diethyl malonate, methyl acetoacetate, ethyl of solubility, vapor rate, etc., and then used.
acetoacetate, and acetylacetone; mercaptan-based com 0059) Other resins may be added to the resin composition
pounds such as butyl mercaptan and dodecyl mercaptan; acid for can coating of the present invention in order to improve
amide-based compounds such as acetanilide and acetic acid properties such as increasing flexibility of the coating film,
amide; lactam-based compounds, such as e-caprolactam, applying adhesion, or the like. Examples of the other resins
8-valerolactam, and Y-butyrolactam, imidazole-based com include a copolymer of copolymerized ethylene and polymer
pounds Such as imidazole and 2-methylimidazole; urea-based izable unsaturated carboxylic acid, and an ionomer of a
compounds such as urea, thiourea, and ethyleneurea; oXime copolymer of copolymerized ethylene and polymerizable
based compounds such as formamideoXime, acetalde carboxylic acid. By adding at least one resin selected from the
hydeoxime, acetoneoxime, methyl ethyl ketone oXime, above, the flexibility and/or adhesion of the coating film may
methyl isobutyl ketone oxime, and cyclohexanoneoxime; and be applied.
amine-based compounds such as diphenylaniline, aniline, 0060. The resin composition for can coating of the present
carbazole, ethyleneimine, and polyethyleneimine. These may invention can be applied to one Surface, both surfaces, or the
be used singly, or in combination. edges thereof, if necessary, of any metal plate made of any
0055 A reaction of such a blocking agent with an isocy metal that can be used for items such as beverage cans, canned
anate curing agent component may be performed, for food cans, lids therefor, caps, or the like. Examples of the
example, at 20 to 200° C., using a known inactive solvent metal materials include tin plate, tin-free steel, and alumi
and/or catalyst, if necessary. The blocking agent is preferably num. The metal plate made of the aforementioned materials
used in an amount 0.7 to 1.5 times by mole that of the terminal may be subjected beforehand to phosphate treatment, chro
isocyanate groups. mic acid chromate treatment, phosphoric acid chromate treat
0056. The compounding ratio (weight ratio) of the ment, corrosion prevention treatment using a rust prevention
blocked isocyanate compound used in the present invention is agent, and a Surface treatment aiming to enhance the adhesion
polyester resin/blocked isocyanate compound=98/2 to 50/50 of the coating film.
(parts by weight), and more preferably polyester resin/curing 0061 The coated metal plate of the present invention can
agent=95/5 to 60/40 (parts by weight). When the compound be obtained by applying the coating composition of the
ing ratio of the blocked isocyanate compound is less than 2 present invention to a metal plate by roll coater painting,
parts by weight relative to 98 parts by weight of polyester spray painting, or other known coating methods. The coating
resin, satisfactory curability cannot be achieved, and the pro thickness is not particularly limited; however, the thickness is
cessability, retort resistance, content, resistance, and/or dent preferably 3 to 18 um based on a dry film thickness, and more
resistance may be undesirably lowered. When the compound preferably in the range of 3 to 10 um. The baking conditions
ing ratio of the blocked isocyanate compound exceeds 50 of the coating film is generally about 100 to 300° C. for about
parts by weight relative to 50 parts by weight of polyester 5 seconds to 30 minutes, and more preferably about 150 to
resin, unreached curing agent components remain therein, 250° C. for about 1 to 15 minutes.
which way undesirably lower the retort resistance and/or
content resistance. EXAMPLES
0057 Depending on the properties required, the resin 0062. The present invention is explained based on the
composition for can coating of the present invention can be Examples. However, the scope of the present invention is not
combined with known inorganic pigments such as titanium limited to these Examples. The evaluation of the characteris
oxide and silica; known additives Such as phosphoric acid and tic value in each Example was respectively measured based
esterified products thereof curing catalysts such as organic on the methods described below.
tin compounds; and known additives such as Surface
Smoothers, defoaming agents, dispersants, and lubricants. In (1) Measurement of Resin Composition
particular, lubricants are important to apply lubricity to coat
ing films required in forming DI cans, DR (or DRD) cans, or 0063 A sample of polyester resin was dissolved in deu
other cans. Preferable examples thereof include fatty acid terated chloroform, and H-NMR analysis was performed
ester wax, which is an esterified product of a polyol com using a 400-MR Nuclear Magnetic Resonance (NMR) sys
pound and a fatty acid, silicone-based wax, fluorine-based tem (manufactured by Varian Inc.). The molar ratio was cal
wax, polyolefin waxes such as polyethylene, lanolin-based culated from the thus-obtained integrated value ratio.
wax, montan wax, microcrystalline wax, and carnauba wax.
The lubricant may be used singly, or in a combination of two (2) Measurement of Number Average Molecular
O. O.
Weight
0058. The resin composition for can coating of the present 0064. A test sample of polyester resin was dissolved and/
invention can be formed into a coating composition under the or diluted with tetrahydrofuran in such a manner that the resin
condition of being dissolved in a known organic solvent. concentration thereof became about 0.5 wt %, and the sample
Examples of the organic solvent usable in forming a coating was filtered with a membrane filter made of polyethylene
composition include toluene, Xylene, aromatic hydrocarbon, tetrafluoride having a pore size of 0.5 um to obtain the test
compounds, ethyl acetate, butyl acetate, methyl ethyl ketone, sample for measurement. The molecular weight was mea
methyl isobutyl ketone, cyclohexanone, isophorone, methyl Sured using gel permeation chromatography (GPC) having
cellosolve, butyl cellosolve, ethylene glycol monoethyl ether tetrahydrofuran as the mobile phase and a differential refrac
acetate, diethylene glycol monoethyl ether acetate, ethylene tometer as the detector. The flow rate was 1 mL/min., and the
US 2015/OO64378 A1 Mar. 5, 2015

column temperature was set at 30° C. KF-802, 804L, and (8) Evaluation of Curability
806L manufactured by Showa Denko K.K., were used as the 0074 Gauze felt soaked in methyl ethyl ketone was
columns. Monodisperse polystyrene was used for the pressed against the coating film Surface of the test piece in
molecular weight standard. Such a manner that the contact area became 1 cm, and then a
(3) Measurement of Reduced Viscosity (Unit: d1/g) rubbing test was carried out with a load of 500 g. The number
of rubs until the coating film peeled off (one back-and-forth
0065 0.1 g of polyester resin sample was dissolved in a rub was counted as one) was counted. The results were evalu
mixture solvent (25 cc) of phenol/tetrachloroethane (weight ated based on the following criteria.
ratio 6/4), and measurement was performed at 30° C.
Criteria
(4) Measurement of Glass Transition Temperature
(Tg) (0075 A: The coating film would not peel off even after
rubbing 50 times or more, and no change in the coating film
0066. The glass transition temperature (Tg) was measured was observed.
using a differential scanning calorimeter (manufactured by (0076 B: The coating film peeled off after rubbing 25 to 49
Seiko Instruments Inc.; DSC-200). A polyester resin sample times, and the tin plate became exposed.
(5 mg) was placed in a Snap-in-lid-type aluminium container, (0077 C: The coating film peeled off after rubbing 16 to 24
and sealed. Using liquid nitrogen, the sample was cooled to times, and the tin plate became exposed.
-50° C., followed by heating to 150° C. at 20°C/min. In the (0078 D: The coating film peeled off after rubbing 15 times
endothermic curve obtained in this process, the temperature or fewer, and the tin plate became exposed.
at the intersection of the baseline before an endothermic peak
appeared, and the tangent extending toward an endothermic (9) Evaluation of Retort Resistance
peak was determined to be a glass transition temperature (Tg,
Unit: C.). 007.9 The test pieces were each individually stood in a
stainless steel cup. Ion exchange water was poured into the
(5) Measurement of Acid Value cup until the top of the water reached half the height of the
0067 0.2 g of polyester resin sample was dissolved in 40 cup. The result was placed in an autoclave of a retort testing
ml of chloroform, and the obtained solution was subjected to machine (Tommy Industry Co., Ltd.; ES-315), and then sub
titration using a 0.01 N potassium hydroxide ethanol solution, jected to a retort treatment at 125° C. for 90 minutes. Evalu
obtaining an equivalent per 10 g of carboxy group-contain ation after the treatment was performed at the portion in
ing resin (equivalent/10 g). Phenolphthalein was used as the which vapor was in contact, which is the portion of a coating
indicator. film that is generally supposed to be exposed to more severe
conditions. Blushing of the coating film and blister conditions
(6) Production of Test Piece were visually observed and evaluated based on the following
criteria.
0068 A coating composition was applied to one surface of
a tinplate (JISG3303SPTE, 70mmx150 mmx0.3 mm) with a Criteria
bar coaterin Such a manner that the film thickness after drying 0080 A: Excellent
became 5 to 8 um, followed by curing by baking at 205°C. for
10 minutes, thereby giving a test piece (hereunder, this is I0081 B: Slight blushing but no blisters were observed
referred to as a test piece). I0082 C: Some blushing and/or some blister were
observed
(7) Evaluation of Processability I0083 D: Remarkable blushing and/or remarkable blister
were observed
0069. The thus-obtained test pieces were each bent 180° in
the direction that the coating film faces outside. The process (10) Evaluation of Content Resistance
ability was evaluated by measuring the electrical current
value at the cracks of the coating film generated at the bent I0084. The test pieces were each individually stood in a
portion. A sponge (width: 20 mm, depth: 50 mm, thickness: stainless steel cup. An aqueous Solution containing 3 wt %
10 mm) soaked in a 1% NaCl aqueous solution was placed on table salt and 3 wt % citric acid was poured into the cup until
an aluminum plate electrode (width: 20 mm, depth: 50 mm, the entire test piece was immersed in the solution. The result
thickness: 0.5 mm). The central part of the bent portion of the was placed in an autoclave of a retort testing machine
test piece was made to contact the sponge in Such a manner (Tommy Industry Co., Ltd.; ES-315), and then subjected to a
that it was parallel to the 20 mm-side of the sponge. Direct treatment at 125° C. for 90 minutes. Thereafter, blushing of
current voltage of 5.0 V was applied across the aluminum the coating film and blister conditions were visually observed
plate electrode and the back surface of the test piece, and then and evaluated based on the following criteria.
the flowing current value was measured. The smaller the
flowing current value, the better the bending property. Criteria

Criteria 0085 A: Excellent

I0086 B: Slight blushing but no blisters were observed
0070 A: Less than 0.5 mA I0087 C: Some blushing and/or some blister were
(0071 B: 0.5 mA or more but less than 1.0 mA observed
0072 C: 1.0 mA or more but less than 2.0 mA I0088 D: Remarkable blushing and/or remarkable blister
0073 D: 2.0 mA or more were observed
US 2015/OO64378 A1 Mar. 5, 2015

(11) Evaluation of Dent Resistance depressurization to 10 mmHg over one hour. At the same
0089. Using a DuPont impact tester, the following test was time, the temperature was increased to 250° C. The post
performed. The test piece that was subjected to the retort polymerization was further performed under vacuum of 1
treatment described in (9) was placed with the coating surface mmHg or less for 70 minutes, giving the polyester resin of the
facing down. In the test piece, a drop punch with a head present invention (Synthetic Example (1)). The thus-obtained
portion having a diameter of /2 inch was pressed against the polyester resin had a number average molecular weight of
non-painted portion within the area that was in contact with 21,000, a reduced viscosity of 0.63 dl/g, a glass transition
steam. A weight of 1 kg was dropped onto the test piece from temperature (Tg) of 85°C., an acid value of 15 eq/t, and a
a height of 50 cm to apply impact. Subsequently, a sponge specific gravity (30° C.) of 1.280.
(width:20 mm, depth: 50 mm, thickness: 10 mm) soaked in a Synthetic Examples (2) to (8) and Comparative
1 wt % NaCl acqueous solution was placed on an aluminum Synthetic Examples (1) to (6) by a Direct
plate electrode (width: 20 mm, depth: 50 mm, thickness: 0.5 Polymerization Method
mm). The convex portion of the test piece, to which impact 0.095 The polyester resins of the present invention (Syn
was applied, was made to contact the Sponge. Direct-current thetic Examples (2) to (8) and Comparative Synthetic
voltage of 5.0 V was applied across the aluminum plate elec Examples (1) to (6)) were produced by the same direct poly
trode and the unpainted portion on the back surface of the test merization method as in Synthetic Example (1), except that
piece to measure the electrical current value. The smaller the the composition of the starting materials was changed so that
electrical current value, the better the bending property. the resulting resins would have the compositions shown in
Tables 1 and 2.
Criteria
Synthetic Example (9) of Polyester Resin by
0090 A: Less than 0.5 mA Transesterification
0091 B: 0.5 mA or more but less than 1.0 mA 0096 Dimethyl terephthalate (878 parts by weight), dim
0092 C: 1.0 mA or more but less than 2.0 mA ethyl 2,6-naphthalenedicarboxylate (71 parts by weight), tri
0093. D: 2.0 mA or more mellitic anhydride (9 parts by weight), ethylene glycol (115
Synthetic Example (1) of Polyester Resin by Direct parts by weight), 1,2-propylene glycol (599 parts by weight),
Polymerization Method and, as a catalyst, 0.3 part by weight of tetra-n-butyltitanate
(hereunder may be referred to as TBT) (0.02 mol% relative to
0094) Terephthalic acid (2251 parts by weight), 2,6-naph the total acid components) were placed in a 3 L-flash
thalenedicarboxylic acid (189 parts by weight), trimellitic equipped with a stirrer, capacitor, and thermometer. The
anhydride (28 parts by weight), ethylene glycol (344 parts by transesterification reaction was performed while heating
weight), 1,2-propylene glycol (1795 parts by weight), and, as from 160° C. to 220° C. over 4 hours. Subsequently, the
a catalyst, 1.0 part by weight of tetra-n-butyltitanate (hereun pressure of the inside system was gradually reduced to per
der may be referred to as TBT) (0.02 mol % relative to the form initial polymerization by depressurization to 5 mmHg
total acid components) were placed in a 10 L-autoclave. An over 20 minutes. At the same time, the temperature was
esterification reaction was performed while applying nitro increased to 250° C. Post-polymerization was further per
gen pressurization at 3.5 Kg/cm-G and gradually heating to formed under vacuum of 1 mmHg or less for 70 minutes,
235°C. over 3 hours. Subsequently, the pressure of the inside giving the polyester resin of the present invention (Synthetic
system was gradually reduced to perform polymerization by Example (9)).
TABLE 1.
Synthetic Synthetic Synthetic Synthetic Synthetic
Example 1 Example 2 Example 3 Example 4 Example 5
Resin Polycarboxylic acid Terephthalic acid 93 88 79 60 98
Composition Components 2,6- 6 12 18 2O 2
Naphthalenedicarboxylic
Acid
Isophthalic acid 3 9.2
Trimelitic acid 1 O.8
Sebacic acid 10
Trimelitic acid (post
synthesis addition)
Polyalcohol (Polyol) Ethylene glycol 25 30 10 2O 18
Components 1,2-propyleneglycol 75 69.5 79.3 70 66.4
Neopentylglycol 5
1,4-Cyclohexanedimethanol 10 10
2-Methyl-1,3-propanediol 10
Trimethylolpropane O.S 0.7 O.6
Resin Number average molecular 21,000 12,500 13,000 14,500 11,000
Characteristic weight
Reduced viscocity (dg) O.63 O.48 OSO O.S3 O.45
Tg (C.) 85 86 87 72 82
Acid value (eqt) 15 14 5 4 6
Specific gravity (30° C.) 1.28O 1.278 1.268 1.260 1.261
US 2015/OO64378 A1 Mar. 5, 2015
8

TABLE 1-continued
Synthetic Synthetic Synthetic Synthetic
Example 6 Example 7 Example 8 Example 9
Resin Polycarboxylic acid Terephthalic acid 90 65 93
Composition Components 2,6- 8O 9.5 35 6
Naphthalenedicarboxylic
Acid
Isophthalic acid 10
Trimelitic acid O.S 1
Sebacic acid 10
Trimellitic acid (post- 1
synthesis addition)
Polyalcohol (Polyol) Ethylene glycol 35 12 25
Components 2-propyleneglycol 99 45 64.4 75
Neopentylglycol
4-Cyclohexanedimethanol 2O 23
2-Methyl-1,3-propanediol
Trimethylolpropane 1 O6
Resin Number average molecular 8,000 13,500 19,000 21,000
Characteristic weight
Reduced viscocity (dg) 0.4 O.S1 O.61 O.63
Tg ( C.) 8O 90 97 85
Acid value (eq.ft) 85 3 5 15
Specific gravity (30° C.) 1.262 1.260 1.254 1.28O

TABLE 2
Comparative Comparative Comparative Comparative Comparative Comparative
Synthetic Synthetic Synthetic Synthetic Synthetic Synthetic
Example 1 Example 2 Example 3 Example 4 Example 5 Example 6
Resin Poly- Terephthalic acid 99.5 99.8 45 82 55
Composition carboxylic 2,6-Naphthalenedicarboxylic Acid 100 15 18 45
acid Isophthalic acid 40
Components Trimellitic acid O.S O.2
Sebacic acid
Trimellitic acid (post-synthesis
addition)
Polyalcohol Ethylene glycol 10 25 35 2O 15 40
(Polyol) 2-propyleneglycol 75 75 44.3 69.5 25 34.5
Components Neopentylglycol
4-Cyclohexanedimethanol 15 2O 25
2-Methyl-1,3-propanediol 60
Trimethylolpropane 0.7 O.S O.S
Resin Number average molecular weight 16,000 18,000 5,000 13,000 16,000 12,000
Characteristic Reduced viscocity (dg) 0.55 O.S8 O.32 OSO 0.55 O.47
Tg ( C.) 83 77 115 82 62 108
Acid value (eq.ft) 5 17 7 18 10 3
Specific gravity (30° C.) 1248 1.275 1.256 1.272 1246 1.28O

Production Example of Resin Varnish position was applied by the method described above and
baked, thereby obtaining a test piece of the coated metal plate
0097 Polyester resins produced in Synthetic Examples of the present invention. Tables 3 and 4 show the proportions
(1) to (9) and Comparative Synthetic Examples (1) to (6) were of the components of each coating composition, and the
dissolved in cyclohexanone/Solves.so 150=1/1 (weight ratio), evaluation results of the test pieces.
preparing resin varnish with a solids content of 40 wt %. Examples (2) to (8) and Comparative Examples (1)
Example (1) to (7)
0099. The resin composition for can coating of the present
0098 Resin varnish of Synthetic Example (1) (45 parts), invention was obtained in the same manner as in Example (1),
IPDI-based blocked isocyanate (manufactured by Bayer except that the compositions were changed to those shown in
MaterialScience, Desmodur VPLS 2078/2, solids content of Table 3 or 4. Subsequently, the application and baking were
60 wt %, 3.3 parts), and DBTL (dibutyltin dilaurate, 0.02 performed in the same manner as described above, thereby
parts) were mixed. The resulting mixture was diluted with obtaining a test piece of the coated metal plate of the present
cyclohexanone/Solves.so 150=1/1 (weight ratio) until its vis invention. Table 3 shows the proportions of the components
cosity became desirable for coating, obtaining the coating of each coating composition and the evaluation results of the
composition of the present invention. The thus-obtained com test pieces.
US 2015/OO64378 A1 Mar. 5, 2015

TABLE 3
Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9
Coating Type of polyester resin Synthetic Synthetic Synthetic Synthetic Synthetic Synthetic Synthetic Synthetic Synthetic
composition Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9
Components. Amount of polyester resin 90 83 75 85 70 65 85 8O 90
solids weight Blocked Coronate 2513 25 30
ratio isocyanate VESTANAT 15 35 2O
compound B 1370
DESMODUR 10 17 15 10
VPLS 2078.2
Catalyst DBTL O.1 O.1 O. O.1 O.1 O.1 O.1 O.1 O.1
Film Processability A. A. A. B B B B B A.
Performance Curability A. A. A. A. B A. A. B A.
Retort resistance A. A. A. B A. A. A. B A.
Content resistance A. A. A. B A. A. A. B A.
Dent resistance A. A. A. B B B B B A.

TABLE 4
Com. Ex. 1 Com. Ex. 2 Com. Ex. 3 Com. Ex. 4 Com. Ex. 5 Com. Ex. 6 Com. Ex. 7

Coating Type of polyester resin Comparative Comparative Comparative Comparative Comparative Comparative Synthetic
composition Synthetic Synthetic Synthetic Synthetic Synthetic Synthetic Example 1
Components Example 1 Example 2 Example 3 Example 4 Example 5 Example 6
solids Amount of polyester resin 8O 90 60 75 88 8O 100
weight ratio Blocked Coronate 2513 40
isocyanate VESTANAT B 1370 2O 12
compound DESMODUR 10 25 2O
VPLS 2078.2
Catalyst DBTL O.1 O.1 O.1 O.1 O.1 O.1 O.1
Film Processability D C D D B D D
Performance Curability D D B A. B A. D
Retort resistance A. B A. A. D A. C
Content resistance A. B A. A. D A. D
Dent resistance C C C D C C D

0100 Coronate 2513: manufactured by Nippon Polyure- (ii) among the polycarboxylic acid components constitut
thane Industry Co. Ltd., HDI-based blocked isocyanate com ing the polyester resin, the copolymerization ratio of
pound 2,6-naphthalenedicarboxylic acid component is 2 to 80
0101 Vestanat B 1370: manufactured by Evonik Indus mol%; and
tries AG, IPDI-based blocked isocyanate compound (iii) among the polyol components constituting the poly
0102 Desmodur VP LS 2078/2: manufactured by Bayer ester resin, the total copolymerization ratio of ethylene
MaterialScience, IPDI-based blocked isocyanate compound glycol component and 1,2-propylene-glycol component
(0103 DBTL: dibutyltin dilaurate is 50 mol% or more, wherein the copolymerization ratio
0104. As is clear from Tables 3 and 4, the coating film of 1,2-propylene-glycol component is excessive relative
obtained from the resin composition for can coating that uses to the copolymerization ratio of the ethylene glycol
the polyester resin of the present invention exhibits excellent component.
properties in ail of processability, curability, retort resistance, 2. The polyester resin according to claim 1, which has a
content resistance, and dent resistance. reduced viscosity of 0.3 to 0.7 dl/g, a glass transition tem
INDUSTRIAL APPLICABILITY perature of 70° C. or more, a specific gravity (30°C.) of 1.245
or more, and an acid value of 200 eq/t or less.
0105. The product of the present invention is a polyester 3. A resin composition for can coating comprising the
resin, a resin composition for can coating, and a coated metal polyester resin of claim 1 and a curing agent, which contains
plate for can to which the can coating was applied, the can the polyester resin and the curing agent in a weight ratio of
coating having excellent processability, curability, retort polyester resin/curing agent=98/2 to 50/50 (parts by weight).
resistance, content resistance, and dent resistance. The prod 4. The resin composition for can coating according to claim
uct of the present invention is Suitably used as a main com 3, wherein the curing agent is a blocked isocyanate com
ponent of a coating composition applied to food and beverage pound.
CanS, etc.
1. A polyester resin obtained from a polycarboxylic acid 5. A method for producing a coated metal plate for can
component and a polyol component, wherein the polyester comprising a step of applying the resin composition for can
resin meets the conditions (i) to (iii) described below: coating of claim 3 to a metal plate and curing the resin com
(i) among the polycarboxylic acid components constitut position.
ing the polyester resin, the total copolymerization ratio 6. A coated metal plate for can on which a layer comprising
of terephthalic acid component and 2,6-naphthalenedi a reactant of the polyester resin of claim 1 and a curing agent
carboxylic acid component is 80 mol % or more; is placed on the Surface of the metal plate.
US 2015/OO64378 A1 Mar. 5, 2015
10

7. A can comprising the coated metal plate for can of claim

6 as a constituting material.
8. A resin composition for can coating comprising the
polyester resin of claim 2 and a curing agent, which contains
the polyester resin and the curing agent in a weight ratio of
polyester resin/curing agent=98/2 to 50/50 (parts by weight).
9. A method for producing a coated metal plate for can
comprising a step of applying the resin composition for can
coating of claim 4 to a metal plate and curing the resin com
position.
10. A coated metal plate for can on which a layer compris
ing a reactant of the polyester resin of claim 2 and a curing
agent is placed on the Surface of the metal plate.
k k k k k