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    • 专利摘要:
    coating composition, coated metal plate, metal container and metal closure. The present invention relates to a polyester coating composition used in forming a film on a coated metal plate, metal container, metal lid or the like. a mixed polyester resin comprises a polyester resin (a) with an acid value of 2 to 50 mg koh/g and a glass transition temperature (tg) of 35 to 100°C and a polyester resin (b) with an acid value from 0 to 50 mg of koh/g and a glass transition temperature (tg) of -20 to 25°C and by forming a coating composition comprising said mixed polyester resin containing a crosslinking agent and a curing catalyst, a Coating composition can be supplied which has excellent resistance to weathering brittleness, corrosion resistance, scratch resistance, retort resistance and blockage resistance.
    公开号:BR112014029736B1
    申请号:R112014029736-3
    申请日:2013-05-27
    公开日:2022-01-11
    发明作者:Naoyuki Takagi；Keizou Kanzaki；Nobuaki Sano；Mayumi Arai
    申请人:Toyo Seikan Group Holdings, Ltd；Valspar Rock Co., Ltd.；
    IPC主号:
    专利说明:

    Technical Field
    [001] This invention relates to a polyester-based coating composition. More particularly, the invention relates to a polyester-based coating composition excellent in weathering resistance, processability, corrosion resistance, scratch resistance, retort resistance and clogging resistance and a coated metal plate, a metal closure and a metal container, each coated with the coating composition. Fundamental Technique
    [002] Organic coating films to protect metal containers or closures to prevent corrosion of metal substrate due to contents, etc. In addition, metal containers undergo machining such as neck-in processing, bead processing, or fastener joining. Metal fasteners with an easy open end (may be referred to hereinafter as “EOE”) are also subjected to severe processing such as cutting and riveting. Thus, excellent corrosion resistance and processability are required of coating compositions used for metal containers or metal closures.
    [003] To satisfy the above mentioned requirements, various polyester-based coating compositions have been proposed.
    [004] Patent Document 1 to be indicated later, for example, proposes a coating composition comprising a hydroxyl group-containing polyester resin, a phenolic resin specific crosslinking agent and acid catalyst mixed in predetermined amounts. . This coating composition is described as being able to form a coating film that has a good balance between processability and hardness and is excellent in adhesion, curability, hygiene and resistance to boiling water. Patent Documents 2 and 3 shown below describe coating resin compositions prepared using molecules that contain polyester resins having pendant carboxyl groups introduced within the molecular chains. The aqueous resin composition of Patent Document 2 is described as excellent in curability, processability, retort resistance, hygiene, spray coatability and water dispersibility, while the coated resin composition of Patent Document 3 is described as being particularly superior in adhesion to metal surfaces and high performance processability and high corrosion resistance.
    [005] Furthermore, polyester-based coating compositions involve the characteristic problem that the processability of the film after coating degenerates with time during storage.
    [006] Patent Document 4 indicated below proposes a polyester resin composition which contains a polyester resin having a low Tg and a crosslinking agent, the polyester resin consisting essentially of 2-methyl-1,3-propanediol, 1,4-butanediol and 1,4-cyclohexanedimethanol as a polyalcohol component. This polyester resin composition is described as having processability, retort strength, flavor properties, content strength, smoothing strength and sulfur resistance. The polyester resin composition is also described as having the high processability and smoothing resistance required for an inner surface coating for EOE and as being able to suppress deterioration in processability with time. Patent Document 5 proposes a coating composition with a moderately branched polymeric polyester resin and containing a vertically asymmetric dihydric alcohol component. This coating composition is described as showing a decline over time in the processability of the coated film and as being excellent in adhesion to materials and having a good balance between hardness and processability.
    [007] Patent Document 4 describes that the preferred polyester resin has a glass transition temperature (Tg) of 20 to 50°C, whereas Patent Document 5 does not mention any glass transition temperature. Prior Art Documents Patent Document Patent Document 1: JP-A-2001-131470 Patent Document 2: JP-A-2003-89746 Patent Document 3: JP-A-2003-213201 Patent Document 4: JP- A-2004-346131 Patent Document 5: JP-A-2002-201411 summary
    [008] Problems to be solved by the invention
    [009] Decreasing the glass transition temperature (Tg) as in the coating composition of Patent Document 4 shortened the deterioration over time in the processability (weather embrittlement) of the film after coating and improved its processability. However, a mere drop in the glass transition temperature has not been successful in fully satisfying all of the required coating film performance characteristics of metal containers or closures, such as corrosion resistance, scratch resistance, clogging resistance, and corrosion resistance. retort. Thus, such a coating composition with only a lowered Tg was not sufficiently satisfactory as a coating composition applicable to metal containers or metal closures (Comparative Examples 13 and 14).
    [0010] An object of the present invention is to provide a coating composition which gives a coating film further improved in resistance to age embrittlement and excellent in all performance characteristics of the coating film such as processability, corrosion resistance, strength scratch resistance, clogging resistance and retort resistance.
    [0011] Another object of the present invention is to provide a coated metal plate having excellent coating film performance characteristics and preferably usable for forming metal containers or metal closures.
    [0012] Yet another object of the present invention is to provide a metal container or metal closure excellent in corrosion resistance and retort resistance. Means to Solve Problems
    [0013] In accordance with the present invention, there is provided a coating composition which contains a crosslinking agent and a curing catalyst in combination with a mixed polyester resin which comprises a blend of a polyester resin (A) having a value acid of 2 to 50 mg KOH/g and a glass transition temperature (Tg) of 35 to 100°C and a polyester resin (B) having an acid value of 0 to 50 mg KOH/g and a glass transition temperature (Tg ) from -20 to 25°C.
    [0014] In the coating composition of the present invention, the following traits are preferred: 1. Polyester resin (A) is a polyester resin supplied with the acid value of the resin in the ring-opening addition reaction of a compound having one or more carboxylic acid anhydride structures in the molecule; 2. The weight ratio of polyester resin (A) to polyester resin (B) is (A):(B) = 99:1 to 50:50; 3. The glass transition temperature (Tgmix) of the mixed polyester resin calculated from equation (1) below is 35°C or higher
    where Tgmix represents the glass transition temperature (K) of the mixed polyester resin, Tga represents the glass transition temperature (K) of the polyester resin (A), Tgb represents the glass transition temperature (K) of the polyester resin ( B), Wa represents the weight fraction of the polyester resin (A) and Wb represents the weight fraction of the polyester resin (B); 4. The crosslinking agent comprises a resol-like phenolic resin and/or an amino resin and is incorporated in an amount of 1 to 30 parts by weight based on 100 parts by weight of the resin solids content of polyester resins ( A) and (B); and 5. The curing catalyst is incorporated in an amount of 0.1 to 3.0 parts by weight based on 100 parts by weight of the total solids content of the resin.
    [0015] In accordance with the present invention, a coated metal plate coated with the above-described coating composition is also provided.
    [0016] The coated metal plate of the present invention preferably has the coil baked coating composition.
    [0017] In accordance with the present invention, furthermore, a metal container or a metal closure provided with a coating film comprising the coating composition is provided. Effects of the invention
    [0018] The cause of embrittlement with time, one of the problems to be solved by the coating composition of the present invention, has not been accurately elucidated, but is assumed to be as follows:
    [0019] Enthalpy relaxation begins in the coating particle immediately after curing and progresses with time to cause molecular reorientation (change to an equilibrium state). As a result, the coating film may become brittle and its processability may deteriorate. To suppress this time embrittlement phenomenon, two methods are conceivable: One of the methods is to increase the crosslink density of the cured coating film to reduce molecular movement, thereby reducing enthalpy relaxation. The other method is to maintain molecular motion (non-equilibrium state retention) even at a temperature during storage with time, thereby causing no enthalpy relaxation.
    [0020] With the first method, however, the raw coating film may not achieve adequate early stage processability. With the latter method, time embrittlement of the cured coating film can be suppressed, but corrosion resistance to the contents, resistance to scratching during formation, resistance to clogging of the coated metal plate and resistance to retort at the time of sterilization are insufficient. Thus, both methods were found to be unsuccessful in achieving sufficient coating film performance for practical use.
    [0021] Against the above plea, a polyester resin (A) to increase crosslink density, which can suppress molecular movement to inhibit enthalpy relaxation as the cause of embrittlement over time and a polyester resin (B) with a low Tg capable of retaining molecular motion even at temperature during storage with time the cured coating film are used in combination in the coating composition of the present invention. This has led to an invention of a coating composition that can form a coating film excellent in all coating film performance characteristics, such as resistance to age embrittlement, processability, corrosion resistance, scratch resistance, obstruction and resistance to retort.
    [0022] The coated metal plate obtained by coating the coating composition of the present invention has the above-mentioned excellent coating film performance characteristics and can be suitably used for metal containers or metal closures.
    [0023] In addition, the metal container and metal closure of the present invention have superior corrosion resistance and retort resistance.
    [0024] The above-described effects of the present invention are clear from the results of Examples to be described later.
    [0025] That is, the coated metal plate and metal closure prepared using the coating composition of the present invention were excellent in both initial processability after formation and processability after the passage of time and excellent in all corrosion resistance. , retort resistance, clogging resistance, and scratch resistance (Examples 1 to 20). Failure to meet any of the requirements of the present invention, on the other hand, has been found to be unsuccessful in meeting all of these coating film performance characteristics (Comparative Examples 1 to 14).
    [0026] In the Examples and Comparative Examples, evaluations were made only on metal fasteners for the following reasons: The metal fastener is formed by processing the coated metal plate. On the other hand, the coated metal container is formed by molding the container and then coating the container. As mentioned herein, the degree of processing is higher for the coating film on the coated metal closure. If satisfactory evaluation results are obtained on the metal closure, therefore, it goes without saying that satisfactory evaluation results are also obtained on the metal container. Thus, evaluations were conducted only on metal fasteners. Method for Carrying Out the Invention
    [0027] The coating composition of the present invention will be described in more detail below. [Polyester resin (A)]
    [0028] The polyester resin (A) used for the coating composition of the present invention is not limited and any polyester resin comprising various carboxylic acid components and alcohol components can be used as long as its acid value is in the range range from 2 to 50 mg KOH/g, especially from 5 to 30 mg KOH/g and its glass transition temperature (Tg) is in the range from 35 to 100°C, especially from 50 to 90°C.
    [0029] It is important that the acid value of the polyester resin (A) of the present invention is within the above range, whereby adhesion to a metallic substrate is increased and processability is enhanced. The increase in adhesion to the substrate, in particular, makes it difficult for corrosion-inducing substances (salts and acids) to reach the metal, thus leading to excellent corrosion resistance. The crosslink density also increases, helping to suppress the embrittlement of the cured coating film with the designated time for enthalpy relaxation. If the acid value is below the range mentioned above, sufficient adhesion to the substrate is not obtained and it may become difficult to satisfy both processability and corrosion resistance. Furthermore, the crosslink density increases minimally and the effect of suppressing embrittlement over time of the cured coating film may be insufficient. If the acid value is above the range mentioned above, the water resistance of the coating film may decrease.
    [0030] If the glass transition temperature (Tg) of the polyester resin (A) is lower than the range mentioned above, clogging resistance may be lower. If the Tg is higher than the above range, on the other hand, the solubility of the coating composition in a solvent may be insufficient.
    [0031] As the carboxylic acid component used in the polyester resin (A), aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid and naphthalenedicarboxylic acid can be mentioned; aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, azelaic acid, sebaceous acid, dodecanedioic acid and dimeric acid; unsaturated dicarboxylic acids such as maleic acid (anhydride), fumaric acid, dodecenyl succinic anhydride and terpene-maleic acid adduct; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, tetrahydrophthalic acid, hexahydroisophthalic acid and 1,2-cyclohexanedicarboxylic acid; trivalent or higher valence carboxylic acids such as trimellitic acid (anhydride), pyromellitic acid (anhydride) and methylcyclohexenetricarboxylic acid; and monocarboxylic acids such as 4,4-bis(4'-hydroxyphenyl)-pentanoic acid, 4-mono(4'-hydroxyphenyl)-pentanoic acid and p-hydroxybenzoic acid. One or more of these carboxylic acids may be arbitrarily selected and used.
    [0032] Examples of the alcohol component used in the polyester resin (A) are aliphatic glycols such as ethylene glycol, propylene glycol (1,2-propanediol), 1,3-propanediol, 1,4-butanediol, 1,2 -butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-ethyl-2- butyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1-methyl-1,8-octanediol, 3-methyl-1,6-hexanediol, 4-methyl-1,7-heptanediol, 4-methyl-1,8-octanediol, 4-propyl-1,8-octanediol and 1,9-nonanediol; ether glycols such as diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol and polytetramethylene glycol; alicyclic polyalcohols such as 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, tricyclodecane glycols and hydrogenated bisphenols; and trivalent or higher valent polyalcohols such as trimethylolpropane, trimethylolethane and pentaerythritol. One or more of these alcohols may be arbitrarily selected and used.
    [0033] In the polyester resin (A) used in the present invention, the crosslink density of the coating film must be increased to suppress molecular movement, thereby preventing the relaxation of enthalpy which is the cause of the phenomenon of embrittlement with time. . From this point of view, it is particularly preferred that a molecule having a carboxyl group introduced in a pendant state in the molecular chain is contained in the polyester (A).
    [0034] An example of a method for obtaining such a polyester is, but not limited to, the ring opening addition reaction of a compound having one or more carboxylic anhydride groups in the molecule, the reaction described in JP-A -2003-213201.
    [0035] In the polyester resin (A) provided with the acid value of resin as a result of the ring opening addition reaction of the compound having one or more carboxylic anhydride structures in the molecule, when the total content of carboxylic anhydrides used for the ring opening addition reaction is 100 mol %, it is preferred that 10 mol % or more of the carboxylic anhydrides to be used is a compound having two or more carboxylic anhydride groups in the molecule.
    [0036] The compound having the two or more carboxylic anhydride groups in the molecule is capable of introducing the carboxyl groups into the molecular chain of the resin, as well as into the terminal polyester resin, for modification. By introducing carboxyl groups into the molecular chain of the resin for modification, it becomes possible to communicate an acid value independent of molecular weight. Furthermore, probably because of a low molecular weight between the carboxyl groups, adhesion to the substrate is further increased, so that a coating film with even higher corrosion resistance can be obtained.
    [0037] Synthesis methods by publicly known technologies can be used for the ring opening addition reaction of the compound having one or more carboxylic anhydride structures in the molecule and, as described in JP-A-2003-213201 mentioned above, the following methods are named as the examples: (1) a method which comprises adding a required amount of a carboxylic anhydride when the polyester resin prior to the addition of the carboxylic anhydride is in a molten state (150 to 280°C) immediately afterwards achieving a target molecular weight (Mn = 3,000 to 100,000); (2) a method comprising adding the carboxylic anhydride when the polyester resin has a molecular weight (Mn < 3000) less than the target molecular weight, followed by increasing the molecular weight to the target value under an atmosphere of nitrogen; and (3) a method comprising mixing the polyester resin having no acid added thereto and the carboxylic anhydride in a melt extruder, then batch melting the mixture and reacting by adding an acid to the system.
    [0038] Examples of the compound having two or more carboxylic anhydride groups in the molecule are pyromellitic anhydride, 1,2,3,4-butanetetracarboxylic anhydride, 1,2,3,4-pentanetetracarboxylic anhydride, 3 ,4,3',4'-benzophenatetracarboxylic acid, cyclopentanetetracarboxylic dianhydride, 2,3,6,7-naphthalene-tetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, ethylene glycol bistrimelitate dianhydride, 2 ,3,2',3'-diphenyltetracarboxylic acid, thiophene-2,3,4,5-tetracarboxylic dianhydride, ethylene tetracarboxylic anhydride, 4,4'-oxydiphthalic dianhydride and 5-(2,5-dioxotetrahydro- 3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid. One or more of these compounds can be selected and used. Of these, ethylene glycol bistrimellitate dianhydride is preferred from the aspects of efficiency, weatherability and ease of reaction control.
    [0039] Examples of the carboxylic acid monoanhydride compound that can be used in combination with the compound having two or more carboxylic anhydride groups in the molecule are monoanhydrides such as phthalic anhydride, maleic anhydride, succinic anhydride, maleic anhydride, trimellitic anhydride, itaconic anhydride and citraconic anhydride; phthalic hexahydroanhydride; and phthalic tetrahydro anhydride. One or a combination of two or more of them can be selected and used. From a versatility standpoint, phthalic anhydride and trimellitic anhydride are preferred.
    [0040] The number average molecular weight of the polyester resin (A) used in the present invention is in the range of 3,000 to 100,000, preferably 8,000 to 50,000, more preferably 10,000 to 30,000. If the number average molecular weight is less than 3000, the resulting coating film may become brittle, resulting in insufficient processability. If the number average molecular weight exceeds 100,000, on the other hand, the coating efficiency may be low. [Polyester resin (B)]
    [0041] The polyester resin (B) used for the coating composition of the present invention is not limited and any polyester resin comprising various carboxylic acid components and alcohol components can be used as long as its acid value is in the range range from 0 to 50 mg KOH/g, especially from 0 to 20 mg KOH/g and its glass transition temperature (Tg) is in the range from -20 to 25°C, especially from 0 to 15°C. It is important that the acid value is within the above range. If the acid value is higher than the above range, the water resistance of the coating film may be decreased. It is also important that the glass transition temperature (Tg) is within the above range. If the Tg is higher than the range above, sufficient resistance to time embrittlement fails to be obtained. If the Tg is lower than the above range, corrosion resistance, clogging resistance and retort resistance may be insufficient.
    [0042] As the carboxylic acid component and the alcohol component, the carboxylic acid component and the alcohol component exemplified for the polyester resin (A) can be used.
    [0043] Preferably, the polyester resin (B) in the present invention contains 2-methyl-1,3-propanediol, 1,4-butanediol and 1,4-cyclohexanedimethanol among the alcohol components mentioned above.
    [0044] As in the case of polyester resin (A), the number average molecular weight of the polyester resin (B) used in the present invention is in the range from 3,000 to 100,000, preferably from 8,000 to 50,000, more preferably from 10,000 to 30,000 . If the number average molecular weight of the polyester resin is less than 3000, the resulting coating film may become brittle, leading to insufficient processability. If the number average molecular weight exceeds 100,000, the coating efficiency may be decreased.
    [0045] The polyester resin (B) may be selected, as appropriate, from commercially available polyester resins. They include, for example, Vilaon 300 (manufactured by TOYOBO CO., LTD., molecular weight (Mn) 23,000, acid value 2 or less, Tg 7°C), Vilaon 516 (manufactured by TOYOBO CO., LTD., weight molecular weight (Mn) 30,000, acid value 2 or less, Tg -17°C), Vilaon 560 (manufactured by TOYOBO CO., LTD., molecular weight (Mn) 19,000, acid value 2 or less, Tg 7°C), Vilaon 630 (manufactured by TOYOBO CO., LTD., molecular weight (Mn) 23,000, acid value 2 or less, Tg 7°C), Vilaon GK180 (manufactured by TOYOBO CO., LTD., molecular weight (Mn) 10,000, acid value 5, Tg 0°C), Vilaon GK330 (manufactured by TOYOBO CO., LTD., molecular weight (Mn) 17,000, acid value 2 or less, Tg 16°C) and Eritel UE-3223 (UNITIKA, LTD. , molecular weight (Mn) 21,000, acid value 1, Tg 1°C). [Crosslinking agent]
    [0046] In the present invention, it is preferred to use a resol-type phenolic resin and/or an amino resin as a crosslinking agent.
    [0047] For resol-type phenolic resin, examples of a phenol monomer include o-cresol, p-cresol, p-tert-butylphenol, p-ethylphenol, 2,3-xylaenol, 2,5-xylaenol, phenol, m-cresol, m-ethylphenol, 3,5-xylaenol and m-methoxyphenol. They can be used alone or in combination of two or more. Such a phenol monomer and formaldehyde are reacted in the presence of an alkyl catalyst to produce the resole-type phenolic resin. Resol-type phenolic resins in which some or all of the contained methylol groups have been etherified with alcohols having from 1 to 12 carbon atoms can also be used. Of these, m-cresol resins are preferred. For example, commercially available products such as RESIN SUMILITEPR-53893A (50% solids content) produced by Sumitomo Durez Co., Ltd. and CKS-3898 (50% solids content) by Showa Denko K.K. can be used.
    [0048] Such as amino resin, urea resin, melamine resin and benzoguanamine resin, for example, can be used. Specific examples are methylated urea resin, methyl etherified urea resin, butyl etherified urea resin, mixed methyl ether-butyl ether urea resin; melamine resins such as methylated melamine resin, methyl etherified melamine resin, butyl etherified melamine resin and blended methyl ether-butyl ether melamine resin; methylated benzoguanamine resin, methyl etherified benzoguanamine resin, butyl etherified benzoguanamine resin etherified benzoguanamine resin and methyl ether-butyl ether etherified benzoguanamine resin mixed together.
    [0049] As commercially available products, e.g. Cymel 303 (100% solids content), Cymel 235 (100% solids content), Mycoat 506 (100% solids content), Cymel 1123 (100% solids content) can be used. solids 100%), UFR 65 (solids content 100%) and UFR 300 (solids content 60%) produced by Nihon Cytec Industries Inc. [Healing Catalyst]
    [0050] By using a curing catalyst in the present invention, a crosslinking reaction can be accelerated and denser crosslinking can be carried out efficiently in a shorter time at a low temperature.
    [0051] As the curing catalyst, organic sulfonic acid compounds such as p-toluenesulfonic acid, dodecylbenzenesulfonic acid and camphorsulfonic acid, amine-neutralized compounds thereof, phosphate compounds, etc. can be used.
    [0052] Among the commercial products, NACURE4054J (phosphoric acid, produced by King Industries, Inc.), NACURE5076 (dodecylbenzenesulfonic acid, produced by King Industries, Inc.), Cicat 4040 (aromatic sulfonic acid, produced by Nihon Cytec Industries Inc. ), Cicat 4050 (amine-blocked aromatic sulfonic acid, produced by Nihon Cytec Industries Inc.), Cicat 600 (aromatic sulfonic acid, produced by Nihon Cytec Industries Inc.), and Cicat 602 (amine-blocked aromatic sulfonic acid, produced by Nihon Cytec Industries Inc.), for example, can be used. [Coating Composition]
    [0053] The coating composition of the present invention is obtained by incorporating a crosslinking agent and a curing catalyst within a mixed polyester resin composed of the aforementioned polyester resin (A) and polyester resin (B).
    [0054] The mixing ratio, as a weight ratio, of the polyester resin (A) and the polyester resin (B) is preferably in the range of (A):(B) = 99:1 to 50:50, particularly from 98:2 to 70:30. If the proportion of the polyester resin (B) with a low Tg is less than 1, a marked reduction in embrittlement strength with time occurs and the initial processability of the coated board may not be retained with the passage of time. If the proportion of the polyester resin (B) is higher than 50, the clogging resistance becomes so low that practical application may be impossible.
    [0055] In the coating composition of the present invention, furthermore, it is desirable that the glass transition temperature of the mixed polyester resin composed of the polyester resin (A) and the polyester resin (B), calculated from Equation ( 1) mentioned above, is 35°C or higher, particularly in the range of 40 to 80°C. If the Tg is lower than the above range, the clogging resistance becomes insufficient. When the coating composition is used as a can inner surface coating, the Tg is preferably 40°C or above because of the need for flavor properties. From the point of view of, say, solubility of the coating composition in a solvent, the preferred upper limit of Tg is 80°C or below.
    [0056] The proportion of the crosslinking agent is preferably in the range of 1 to 30 parts by weight, especially 5 to 20 parts by weight, based on 100 parts by weight of the resin content of the mixed polyester resin obtained by mixing of polyester resin (A) and polyester resin (B). If the amount of crosslinking agent added is less than 1 part by weight, the curability becomes insufficient and the time embrittlement strength, processability, content strength, retort strength and clogging strength may become inferior. . If the amount added is greater than 30 parts by weight, the curing may be excessive to render the processability insufficient.
    [0057] The proportion of the curing catalyst is preferably in the range of 0.1 to 3.0 parts by weight, particularly from 0.1 to 2.0 parts by weight, with respect to 100 parts by weight of the solids content of the total resin including the resin content of the mixed polyester resin and other resin content including the crosslinking agent. If the amount of the incorporated curing catalyst is less than the range mentioned above, the effect of accelerating the curing reaction obtained by incorporating the curing catalyst is insufficient. If the amount of curing catalyst incorporated is greater than the above range, on the other hand, the curing acceleration effect may be so high as to render the processability insufficient.
    [0058] To the coating composition of the present invention, publicly known additives such as lubricants, anti-foaming agents, leveling agents and pigments can be added by known formulations.
    [0059] The coating composition of the present invention can be used, with the polyester resin (A), polyester resin (B), crosslinking agent and curing catalyst mentioned above being dissolved in a known organic solvent. Examples of the organic solvent used are aromatic hydrocarbons such as toluene, xylene and solvent; esters such as ethyl acetate, butyl acetate and basic acid ester; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and isophorone; ether alcohols such as butyl cellosolve and butyl carbitol; alcohol ketones such as diacetone alcohol; and alcohols such as isopropyl alcohol, n-butanol, amyl alcohol and n-hexanol. Any of these solvents is selected in consideration of solubility, coating efficiency, etc.
    [0060] Furthermore, the coating composition of the present invention can be made aqueous by a publicly known method and used as a water-based coating composition. For example, a basic compound such as ammonia or an organic amine compound, water, or another organic solvent are combined together with the polyester resins (A) and (B), crosslinking agent and curing catalyst mentioned above to prepare a water-based coating composition.
    [0061] For the coating composition of the present invention, still other resins may be used, in amounts such as not to detract from the excellent characteristics of the coating composition of the present invention, for the purpose of modifications such as imparting flexibility and adhesion of the present invention. coating film. Examples of the other resins are ethylene polymerizable unsaturated carboxylic acid copolymer, ethylene polymerizable carboxylic acid copolymer ionomer and non-aqueous polyester resin. By incorporating at least one resin selected from these resins, it may be possible to communicate flexibility and adhesion to the coating film effectively. [coated metal plate]
    [0062] The coated metal plate of the present invention is obtained by coating a metal plate with the coating composition of the present invention.
    [0063] Examples of usable sheet metal are hot rolled steel sheet, cold rolled steel sheet, galvanized steel sheet, electrogalvanized steel sheet, alloy galvanized steel sheet, steel sheet galvanized with aluminium-zinc alloy, an aluminum plate, a tinned steel sheet, a stainless steel sheet, a copper plate, a copper galvanized steel sheet, tin-free steel, a nickel-galvanized steel sheet , a thin tin galvanized steel sheet and a chrome plated steel sheet. These metal plates are subjected, if required, to various surface treatments and priming treatments before use.
    [0064] The coated metal plate of the present invention can be obtained by coating a metal plate with the coating composition of the present invention by a publicly known coating method such as roller coating or spray coating and baking the plate. coated metal by a heating means such as a coil oven. A cured coating film of the coating composition of the present invention is effectively inhibited from embrittlement with time. Thus, the coating composition of the present invention can be used effectively, particularly when formed into a coating film by coil cooking which is carried out at a high temperature in a short time and is particularly susceptible to embrittlement with time.
    [0065] The coating film thickness is not limited, but is preferably in the range of 3 to 18 m, more preferably 3 to 12 m as a dry film thickness. Dry film thickness is appropriately determined by the intended uses of the coated metal plate. Baking conditions for the coating film are adjusted, as appropriate, depending on the types of polyester resins used, the type of crosslinking agent used, the type of solvent used, the type of metallic material to be coated, the thickness, coating speed, etc. [Metal container and metal clasp]
    [0066] The metal container of the present invention has a coating film of the coating composition of the present invention formed on the inner surface and/or outer surface of a metal container. The coating composition of the present invention has exceptional corrosion resistance and flavor properties, so that a coating film comprising the coating composition of the present invention is desirably formed on at least the inner surface of the metal container.
    [0067] As the metal container to be supplied with the coating film, all publicly known metal containers can be used. Examples of the metal container include, but are not limited to, three-piece cans having side seams and seamless cans (two-piece cans).
    [0068] The metal container of the present invention can be formed from the coated metal plate mentioned above. However, a metal container such as a seamless can, which is formed by severe processing, can also be formed by applying the coating composition of the present invention to a pre-formed metal container.
    [0069] Furthermore, the metal fastener of the present invention can be formed from the aforementioned coated metal plate of the present invention by an arbitrary publicly known method of fastening production. In general, the metal closure is formed as a stay-on type flip-open can closure or a fully open-type flip-open can closure. Examples
    [0070] The present invention will be described more specifically with reference to the examples, in which parts refer to parts by weight.
    [0071] The respective items were measured by the following methods: (1) Numerical average molecular weight of polyester resin
    [0072] Measured by gel permeation chromatography (GPC) using standard polystyrene calibration curve. (2) Glass transition temperature
    [0073] Measured at a temperature increase rate of 20 °C/min using a differential scanning calorimeter (DSC). (3) Acid value
    [0074] 0.2 g of polyester was dissolved in 20 ml of chloroform, titrated with a solution of 0.1 N KOH-ethanol to obtain the acid value of the resin (mg KOH/g). Phenolphthalein was used as an indicator. (4) Preparing the coated test plate
    [0075] The coating composition of each of the Examples and Comparative Examples was coated onto a 0.28 mm thick #5182 aluminum sheet using a bar coater to form a film (dry film weight 100 mg /100 cm2) and the film was baked in a reel oven. The cooking conditions were a peak metal temperature (PMT) of 260 °C for the aluminum foil and a total cook time (TOT) of 28 seconds. The resulting coated plates were each subjected to the various tests in accordance with the test methods explained below. (4)-1 Resistance to embrittlement over time
    [0076] Resistance to time embrittlement was evaluated in terms of initial processability versus time processability. Processability:
    [0077] The coated test plate was cut to a size of 3 x 5 cm such that the side of the aluminum plate in its rolling direction would be the long side of the resulting test piece. The test piece was then folded parallel to its short side such that its coated surface faced outward. Two sheets of 0.28 mm thick aluminum were interposed within the bend in an atmosphere of 25°C and subjected to impact bending using a Du Pont bending seam type impact tester. An iron weight weighing 3.5 kg and having a flat contact surface for impact bending was dropped from a height of 12.5 cm. A 2 cm wide portion at the end leading to the bend was brought into contact with a sponge immersed in a 1% aqueous solution of sodium chloride, a voltage of 6.2 V was applied and the current value (mA) of the 2 cm portion was measured 4 seconds later.
    [0078] Initial Processability: Assessed within 8 hours of coated test plate preparation.
    [0079] Processability over time: The coated test plate was placed in a thermostatic chamber at 40°C within 8 hours after preparation, stored there for 1 month and then evaluated for initial processability.
    [0080] The evaluation criteria were as follows: © (Excellent): Less than 0.5 mA. (Good): 0.5 mA less than 1.0 mA. (Moderate): 1.0 mA less than 3 mA. x (Insufficient): 3 mA or more. (4)-2 Corrosion resistance
    [0081] The coated plate having convexities formed by the Du Pont impact tester (1/4 inch (0.64 cm) impact bar, 300 g weight was dropped from the height of 12.5 cm) was soaked in a content simulation liquid (citric acid/ethanol/water = 5/10/85) at 40°C for 7 days and the degree of corrosion was visually evaluated. ©: No corrosion. : Little corrosion. : Mild corrosion. x: Marked corrosion. (4)-3 Retort strength
    [0082] The coated test plate was soaked in water, treated at 125°C for 30 minutes in an autoclave and then evaluated for redness.
    [0083] Redness: Visually assessed by observing the redness state of the coating film. ©: No redness. : Little redness. : Mild redness. x: Marked redness. (4)-4 Resistance to clogging
    [0084] The coated surfaces of the coated boards each cut to a size of 8 x 8 cm were superimposed on top of each other. The plates coated in this superimposed state were placed under a pressure of 0.36 MPa at a temperature of 50°C for 2 minutes using a thermocompression press and then cooled to room temperature. Then, the degree of blocking between the respective coated surfaces was evaluated by peeling the coated plates from one another, starting at their ends. : No blocking. : Light blocking. x: Strong blocking. (4)-5 Scratch resistance
    [0085] HEIDON-14DR slide tester (produced by Shinto Scientific Co., Ltd.) was used. A ball bearing under a load was slid over the surface of the coating film and the number of times the ball bearing was slid until the coating film was scraped to expose the aluminum substrate was counted for evaluation. The test conditions were a stainless steel ball with a diameter of 10 mm, a sliding speed of 6000 mm/min, a sliding distance of 10 mm, a load of 1 kg and a coated plate temperature of 25 °C. . ©: 1,000 times or more. : 500 times less than 1,000 times. : 100 times less than 500 times. x: Less than 100 times. (5) Closing preparation
    [0086] A diameter shell 206 (a closure prior to mounting an opening flap is referred to as a shell) having a depth, of a radius portion of an annular groove reinforced from the central panel, of 2.5 mm and a radius of curvature of the radius portion of 0.50 mm was formed from the above-mentioned coated plate by a shell molding machine. The shell was scored (thickness remaining at the 95 m marking), riveted and fitted with an opening flap, on the outside of the clasp, to prepare a clasp. (5)-1 Closure resistance to embrittlement over time
    [0087] Processability with time: The coated plate after 1 month of storage at 40°C was formed into a shell. The shell was coated with a compound, then stored for 2 weeks at 40°C and then subjected to the end-forming steps (marking, flap assembly, etc.).
    [0088] The closure obtained as above was evaluated in the following manner:
    [0089] Five of the fasteners coated immediately after coating (within 8 hours at room temperature) and those after 1 month of storage (40°C) were measured for current value and the difference between the averages of the measured values was used for the assessment. The measurement conditions were energizing at a voltage of 6.2 V for 4 seconds, followed by measurement of current values. ©: Within 0.2 mA (no increase in value). : Within 0.5 mA (no increase in value). : Within 1.0 mA (no increase in value). x: Increase in value. (5)-2 Corrosion resistance of the lock
    [0090] A 350 g can formed by stretching and smoothing a tin-free steel material having both surfaces laminated with PET was cold packed with Coca Cola (liquid temperature: 5 °C, amount of air inside the can : 2 ml or less) under the following conditions: gas volume of 3.75 and amount of contents 345 g. Then the packaged can was heated (40°C, 10 minutes). The sample thus obtained was stored in an inverted posture (clasp facing downwards) in a thermostatic chamber at 37°C for 6 months. Afterwards, the clasp was opened and the inner surface of the clasp was observed. Observation was made by a stereoscopic microscope and a metallurgical microscope and the presence of corrosion stains and the presence of perforations on the inner surface of the closure were examined (n = 5 for each item). : No or little corrosion (except marking and riveting). x: Perforations or possibility of perforations. (5)-3 Retort resistance of the clasp
    [0091] A 350 g can formed by pulling and smoothing a tin-free steel material laminated on both surfaces with PET was charged with 340 g of water. Liquid nitrogen was added to the drops to create an internal pressure of 0.1 kgf/cm2 and then the can sewn with an aluminum closure. The sewn can was subjected to stationary retort treatment with steam at 125°C for 30 minutes and cooled such that the temperature of the liquid inside dropped to below 40°C within 10 minutes after completion of heating.
    [0092] The closure was then removed and the state of redness on the inner surface of the closure was assessed (n = 3 for each condition). ©: No redness. : Little redness. : Mild redness. x: Marked redness. (5)-4 Closure Scratch Resistance
    [0093] Continuous processing was performed for 50 of the samples at each level by a converting press and the condition of the rivet sidewall coating film was visually observed. As for damage to the coating film, the presence of metal exposure was judged by immersing the sample in a 20% aqueous solution of copper sulfate for 1 minute and examining the precipitation of Cu. : No damage to the coating film. : Surface damage (no metal exposure). x: Scratching has occurred (exposed metal). [Synthesis of Polyester Resin (A)]
    [0094] Synthesis Example: Polyester resin (A)-a
    [0095] 446 parts of dimethylterephthalic acid, 2.2 parts of trimellitic acid, 57 parts of ethylene glycol, 246 parts of propylene glycol, 66 parts of 1,4-cyclohexanedimethanol and 0.2 parts of titanium tetrabutoxide were charged into a 3 L four-neck bottle to build a polymerization system. The system was gradually heated to 220 °C over 4 hours to carry out the ester exchange. The pressure was reduced in 30 minutes at 10 mm Hg for initial polymerization and the temperature was increased to 250°C. Under these conditions, post-polymerization was carried out for 90 minutes at 1 mm Hg or lower. When the target molecular weight was reached, the contents were cooled to 220°C in a nitrogen atmosphere. Then, 20 parts of ethylene glycol bistrimellitate dianhydride and 5 parts of trimellitic anhydride were successively loaded into the system and stirring was continued at 200 to 230°C for 1 hour under a nitrogen atmosphere. The contents were then stripped to produce the polyester resin (A)-a of the present invention. The Tg, acid value and numerical average molecular weight of this resin are shown in Table 1. [Example of Polyester Resin Synthesis (B)]
    [0096] Synthesis Example: Polyester resin (B)-a
    [0097] 106 parts terephthalic acid, 225 parts isophthalic acid, 4 parts trimellitic anhydride, 143 parts 2-methyl-1,3-propanediol, 86 parts 1,4-butanediol, 92 parts 1,4- cyclohexanedimethanol and 0.13 parts of titanium tetrabutoxide were charged into a 2 L four-neck flask and the temperature was gradually raised to 220°C in 4 hours to distill off the water and carry out the esterification. After a predetermined amount of water was distilled off, the pressure was reduced in 30 minutes to 10 mmHg to carry out initial polymerization and the temperature was raised to 250°C. Under these conditions, post-polymerization was carried out for 50 minutes at 1 mm Hg or lower. Then, the polymerization under reduced pressure was terminated and the resulting resin was removed to obtain the polyester resin (B)-a of the present invention. The Tg, acid value and numerical average molecular weight of the resin are shown in Table 2.
    [0098] Similarly, polyester resins (A)-ba(A)-i having the acid values and Tgs shown in Table 1 and Table 2 were prepared, except that carboxylic anhydride was used as an indispensable material, its amount was changed and the types or amounts of the other monomers were changed. Also similarly, polyester resins (B)-ba (B)-g having the acid values and Tgs shown in Table 1 and Table 2 were prepared, except that the types or amounts of the monomers were switched. Table 1
    Table 2 Polyester resin (B)

    [Preparation of coating composition]
    [0099] Predetermined amounts of the polyester resin (A), the polyester resin (B) and a solvent were charged into a flask, heated and carefully stirred at 100°C or lower until dissolved. After complete dissolution, the resulting polyester resin solution was cooled to room temperature and, with careful stirring, a predetermined crosslinking agent and predetermined curing catalyst were added to prepare a coating composition. The crosslinking agents used were Sumilite Resin PR-53893A (resol-type m-cresol phenolic resin) from Sumitomo Durez Co., Ltd. and Mycoat 506 (butylated melamine resin) from Nihon Cytec Industries Inc. The curing catalyst used was Cicat 602 (blocked with amino dodecylbenzenesulfonic acid) from Nihon Cytec Industries Inc. Coated metal plates and coated metal closures were produced using the respective coating compositions and evaluated. The results are shown in Table 3 and Table 4. Table 3
    Table 4
    Industrial Applicability
    [00100] The coating composition of the present invention is excellent in all coating film performance characteristics such as processability, resistance to age embrittlement, corrosion resistance, scratch resistance, clogging resistance and retort resistance. In particular, the coating composition can be used preferably for a coated metal plate which is subjected to baking in a coil oven where the baking is carried out at a high temperature in a short time to cause marked time embrittlement.
    [00101] In addition, the coated metal plate having a coating film of the coating composition of the present invention is excellent in processability, resistance to age embrittlement, scratch resistance and clogging resistance and can be used preferably for forming of a metal container or a metal closure that involves severe processing.
    [00102] In addition, the metal container or metal closure of the present invention has excellent corrosion resistance, retort resistance and aroma properties and thus can be used preferably for a metal container to store corrosive contents or contents that require sterilization. in retort.
    权利要求:
    Claims (9)
    [0001]
    1. Coating composition, characterized in that it contains a crosslinking agent and a curing catalyst in combination with a mixed polyester resin comprising a mixture of: a polyester resin (A) which is a polyester resin supplied with a acid value of the resin by a ring opening addition reaction of a compound having one or more carboxylic acid anhydride structures in a molecule, the polyester resin (A) having an acid value of 2 to 50 mg KOH/g and a glass transition temperature (Tg) of 35 to 100°C and a polyester resin (B) having an acid value of 0 to 50 mg KOH/g and a glass transition temperature (Tg) of -20 to 25°C.
    [0002]
    2. Coating composition according to claim 1, characterized in that a weight ratio between the polyester resin (A) and the polyester resin (B) is (A):(B) = 99:1 to 50:50.
    [0003]
    3. Coating composition according to claim 1 or 2, characterized in that a glass transition temperature (Tgmix) of the mixed polyester resin calculated from equation (1) below is 35°C or more,
    [0004]
    Coating composition according to any one of claims 1 to 3, characterized in that the crosslinking agent comprises a resol-type phenolic resin and/or an amino resin and is incorporated in an amount of 1 to 30 parts in weight relative to 100 parts by weight of resin solids content of polyester resins (A) and (B).
    [0005]
    5. Coating composition according to any one of claims 1 to 4, characterized in that the curing catalyst is incorporated in an amount of 0.1 to 3.0 parts by weight with respect to 100 parts by weight of a total resin solids content.
    [0006]
    6. Coated metal plate, characterized in that it is coated with the coating composition as defined in any one of claims 1 to 5.
    [0007]
    7. Coated metal plate according to claim 6, characterized in that it has the coating composition cooked in a coil.
    [0008]
    8. A metal container, characterized in that it has a coating film formed thereon, the coating film comprising the coating composition as defined in any one of claims 1 to 5.
    [0009]
    9. Metal closure, characterized in that it has a coating film formed thereon, the coating film comprising the coating composition as defined in any one of claims 1 to 5.
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    同族专利:
    公开号 | 公开日
    BR112014029736A2|2021-07-06|
    CN104379687B|2017-11-10|
    KR101752958B1|2017-07-11|
    EP2857465A1|2015-04-08|
    US20150125643A1|2015-05-07|
    CA2873357A1|2013-12-05|
    CN104379687A|2015-02-25|
    EP2857465B1|2019-09-11|
    EP2857465A4|2016-02-10|
    CA2873357C|2018-05-22|
    KR20150016950A|2015-02-13|
    WO2013180067A1|2013-12-05|
    IN2014DN09899A|2015-08-07|
    JP5462318B2|2014-04-02|
    US10508214B2|2019-12-17|
    JP2013249376A|2013-12-12|
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    法律状态:
    2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |
    2018-03-27| B15K| Others concerning applications: alteration of classification|Ipc: C09D 167/00 (2006.01), B05D 7/14 (2006.01), B05D 7 |
    2019-09-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-11-30| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2022-01-11| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 27/05/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    JP2012-124819|2012-05-31|
    JP2012124819A|JP5462318B2|2012-05-31|2012-05-31|COATING COMPOSITION AND COATED METAL PLATE, METAL CONTAINER, AND METAL LID COMPRISING THE COATING|
    PCT/JP2013/064659|WO2013180067A1|2012-05-31|2013-05-27|Coating composition, and coated metal plate, metal container and metal lid formed by coating with said coating composition|
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