WO2013046688A1 - 容器用樹脂被覆金属板 - Google Patents

容器用樹脂被覆金属板 Download PDF

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WO2013046688A1
WO2013046688A1 PCT/JP2012/006182 JP2012006182W WO2013046688A1 WO 2013046688 A1 WO2013046688 A1 WO 2013046688A1 JP 2012006182 W JP2012006182 W JP 2012006182W WO 2013046688 A1 WO2013046688 A1 WO 2013046688A1
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Prior art keywords
resin
polyester
mass
coated metal
polyester resin
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PCT/JP2012/006182
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English (en)
French (fr)
Japanese (ja)
Inventor
洋一郎 山中
祐介 中川
北川　淳一
飛山　洋一
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Ｊｆｅスチール株式会社
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Priority to JP2013535927A priority Critical patent/JP5737416B2/ja
Publication of WO2013046688A1 publication Critical patent/WO2013046688A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/308—Heat stability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/40—Closed containers
    • B32B2439/66—Cans, tins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B32B2439/70—Food packaging

Definitions

  • the present invention relates to a resin-coated metal plate for containers used for, for example, can bodies and lids for canned foods.
  • tin free steel which is a material for metal cans used for canned food, and metal plates such as aluminum have been coated for the purpose of improving corrosion resistance, durability, weather resistance and the like.
  • this coating process has a problem that not only the baking process is complicated, but also a long processing time is required and a large amount of solvent is discharged.
  • a film laminated metal sheet was developed by laminating a thermoplastic resin film on a heated metal sheet, and is currently used industrially as a food canning material. Yes.
  • the method of adding a modifier directly to the film of (1) is a method with high production efficiency and high profitability when a film having a certain function is produced in large quantities.
  • this method is not appropriate because canned foods have a wide variety of shapes and types of contents, and different functions are required for each type of canned food. This is because every time the function applied to the film is changed, it is necessary to clean the resin extrusion device, casting drum, cooling roll, etc., and the production line must be stopped for a long time, resulting in a significant reduction in production efficiency. It is because it will do.
  • the method of coating the surface of the film of (2) with a resin containing a modifier can easily meet the various needs for food canning since the addition function to the film can be easily changed. This is because the tank containing the coating liquid containing the modifying agent can be dealt with quickly by washing and replacing.
  • Patent Document 1 An example of a method for coating such a film surface with a resin containing a modifier is Patent Document 1.
  • a resin layer containing an epoxy resin as a main component and containing a melamine resin, a blocked isocyanate compound, and a colorant is formed between a metal plate and a film.
  • epoxy resin is rich in reactivity and excellent in adhesion to a metal plate, it has a disadvantage of poor deep-drawing formability, so a film that can be used as a two-piece can material cannot be obtained.
  • Patent Documents 2 to 5 disclose methods of coating a film with a resin for the purpose of improving adhesion.
  • Patent Documents 2 to 5 have a structure in which a polyester resin and an epoxy resin are combined, or an epoxy resin is a main component. Therefore, like patent document 1, there is difficulty in deep drawability, and it cannot be applied to a two-piece can application.
  • the examples described in Patent Documents 2 to 5 do not disclose examples of evaluating can manufacturing processability or deep drawing formability, and these require deep drawing. It is clear that the two-piece can application is not considered.
  • JP 2007-185915 A Japanese Patent Laid-Open No. 4-266984 JP-A-8-199147 Japanese Patent Laid-Open No. 10-183095 JP 2002-206079 A
  • an object of the present invention is to provide a resin-coated metal sheet for containers that can cope with many characteristics required for food canned materials.
  • a resin coating layer having a multilayer structure mainly composed of a polyester resin is provided on at least one surface of the metal plate.
  • the resin layer containing any one or more selected from the group consisting of (i) polyester resin, (ii) polyamine resin, polyamidoamine resin, and polyamide resin is used as an adhesive layer with the metal plate, and preferably the polyester layer is formed thereon.
  • a resin coating layer (A) having a multilayer structure mainly composed of a polyester resin is provided on at least one surface of the metal plate, and the resin coating layer (A) is in close contact with the metal plate surface and has the following (i And a resin layer (a1) containing a component (ii) and containing a polyester resin as a main component.
  • Polyester resin Any one or more selected from the group consisting of a polyamine resin, a polyamidoamine resin, and a polyamide resin
  • the resin coating layer (A) includes the resin layer (a1) and the upper layer of the resin layer (a1).
  • Polyester resin 50 to 90 mass%
  • Epoxy resin 0.5 to 30 mass%
  • Metal alkoxide compound and / or metal chelate compound 0.01 to 10 mass%
  • the polyester film (a2) is a biaxially stretched polyester film in which 85% by mass or more of structural units of the polyester resin is an ethylene terephthalate unit and / or an ethylene naphthalate unit, and the biaxially stretched polyester film is inorganic.
  • the resin-coated metal sheet for containers according to any one of the above [2] to [10], comprising particles and / or organic particles.
  • the present invention it is possible to obtain a resin-coated metal plate for containers that can cope with many characteristics required for food canning materials. It is an industrially useful invention as a new resin-coated metal plate for containers that can easily add many functions required for food canning.
  • Example 1 It is a figure which shows the principal part of the laminating apparatus of a metal plate.
  • Example 1 It is a figure which shows the cross-section of a film lamination metal plate.
  • Example 1 It is a figure which shows the position of the crosscut damage
  • Example 1 It is a figure which shows the method of measuring the maximum corrosion width from an artificial wound.
  • the resin-coated metal plate for containers of the present invention will be described in detail.
  • the metal plate used by this invention an aluminum plate or a mild steel plate widely used as a can material can be used.
  • the amount of adhesion of the metal chromium layer and chromium hydroxide layer of TFS is not particularly limited, but from the viewpoint of adhesion after processing and corrosion resistance, both are in terms of Cr, the metal chromium layer is 70 to 200 mg / m 2 , chromium The hydroxide layer is desirably in the range of 10 to 30 mg / m 2 .
  • the resin-coated metal plate for containers of the present invention has a resin coating layer (A) having a multilayer structure mainly composed of a polyester resin on at least one surface of the metal plate. As this polyester resin, the thing similar to the polyester resin demonstrated by the following resin layer (a1) can be used.
  • this resin coating layer (A) has the resin layer (a1) closely_contact
  • Polyester resin (ii) One or more selected from the group consisting of polyamine resin, polyamidoamine resin, and polyamide resin
  • the resin layer (a1) in close contact with the metal plate surface will be described.
  • Polyester resin In the present invention, a polyester resin is a main component.
  • the main component means that the resin layer (a1) contains a polyester resin of 50 mass% or more.
  • the polyester resin preferably has a number average molecular weight of 3,000 to 100,000, more preferably 5,000 to 30,000, and still more preferably 10,000 to 25,000.
  • the number average molecular weight is a conversion value by comparison with polystyrene in gel permeation chromatography analysis. If the number average molecular weight is lower than 3000, the processability is deteriorated, and if it is higher than 100,000, the viscosity at the time of coating may be increased and appropriate coating may not be performed.
  • the glass transition temperature of the polyester resin is preferably in the range of 0 ° C. or more and less than 100 ° C.
  • the flexibility, workability, and blocking resistance of the resin are appropriately balanced and suitable for food canning applications.
  • flexibility is imparted to the resin layer, so that workability is excellent.
  • the film is coated with a resin layer and then kept in a wound state at a temperature exceeding the glass transition temperature for a long time, the film may be blocked.
  • the retort resistance is slightly inferior. If a glass transition temperature is 35 degreeC or more and less than 65 degreeC, a film will not block and the aesthetics of a film will not be impaired. When the glass transition temperature is 65 ° C. or more and less than 100 ° C., the blocking property is excellent, but the film becomes hard, so that the workability is somewhat inferior. Therefore, it is more preferable to obtain a balanced and more excellent resin layer by using a plurality of resins having different glass transition temperatures in combination as a polyester resin and drawing out the good performance of each polyester resin.
  • the polyester resin preferably contains a repeating unit derived from diphenolic acid.
  • diphenol acid is contained in the monomer composition, which is a raw material component for producing a polyester resin
  • the reactivity with polyamine resin, polyamidoamine resin, and polyamide resin is increased, and the curing speed is increased.
  • retort whitening resistance is improved. improves.
  • the polyester resin preferably contains a repeating unit derived from diphenolic acid because it has a feature such that the blocking property of the coating film is excellent even when the glass transition temperature is low.
  • the polyester resin (i) is preferably linear.
  • the crosslink density of the film is lowered as compared with the polyester resin having a branched structure, and thus the processability is particularly excellent.
  • polyester resin (i) what made the esterification reaction of a polybasic acid component and a polyhydric alcohol component can be used.
  • the polybasic acid component include one or more dibasic acids such as phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, fumaric acid, adipic acid, azelaic acid, sebacic acid, dimer acid, and the like.
  • a lower alkyl esterified product is used, and a monobasic acid such as benzoic acid or crotonic acid, a tribasic or higher polybasic acid such as trimellitic anhydride, methylcyclohextricarboxylic acid, or the like is used in combination as necessary.
  • polyhydric alcohol component examples include ethylene glycol, diethylene glycol, propylene glycol, 1,4 butanediol, neopentyl glycol, 3-methylpentanediol, 1,4-hexanediol, 1,6-hexanediol, and cyclohexanedimethanol.
  • a dihydric alcohol is mainly used, and a trihydric or higher polyhydric alcohol such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol can be used in combination as necessary.
  • These polyhydric alcohols can be used alone or in admixture of two or more.
  • polyester resin examples include Byron 300, 500, 560, 600, 630, 650, 670, Byron GK130, 140, 150, 190, 330, 590, 680, manufactured by Toyobo Co., Ltd. 780, 810, 890, Elitel UE-3220, 3500, 3210, 3215, 3216, 3620, 3240, 3250, 3300 manufactured by Unitika Ltd., Aronmelt PES-310, 318, 334 manufactured by Toagosei Co., Ltd. .
  • polyamine resins One or more selected from the group consisting of polyamine resins, polyamide amine resins, and polyamide resins.
  • Polyamine resins, polyamide amine resins, and polyamide resins form a tough film with a faster curing speed than melamine resins. It is excellent in that it can be done. Compared with resin compositions composed of polyester / melamine, epoxy / melamine, etc., it exhibits excellent performance in terms of retort resistance, corrosion resistance, workability, etc. of laminated steel sheets because of its excellent curing characteristics. Is possible.
  • polyamine resin examples include diethylenetriamine, triethylenetriamine, triethylenepentamine as the aliphatic amine, and isophoronediamine as the alicyclic polyamine.
  • an epoxy resin or acrylonitrile may be added to an aliphatic polyamine or modified by reacting formaldehyde and phenol to improve workability, reduce irritation, or improve mechanical properties.
  • aromatic polyamine examples include metaphenylenediamine, diaminodiphenylsulfonic acid, and diaminodiphenylmethane.
  • commercially available products include EPICRON EXB-353 manufactured by DIC Corporation, Ancamine 2596 manufactured by Air Products Japan Co., Ltd., and Ancamine 2605.
  • Polyamide amine resin and polyamide resin are compounds synthesized by, for example, dehydration condensation reaction between fat and fatty acid and polyamine.
  • Examples of commercially available products include Sanyo Kasei Polymide L-15-3, Polymide L-45-3, Ancamide 2137 manufactured by Air Products Japan Co., Ltd., Sunmide 330, Sunmide X-2000, and the like.
  • Epoxy resin (preferred conditions) The epoxy resin mainly improves the adhesion of the film.
  • the type of the epoxy resin is not particularly limited. However, in recent years, bisphenol A type epoxy resins are concerned about endocrine disrupting action. Therefore, the resin is preferably free from such concerns and does not contain bisphenol A. It is preferable to use an epoxy resin. Examples of the epoxy resin that does not contain bisphenol A include novolak type epoxy resins and biphenyl type epoxy resins, and a novolak type epoxy resin is particularly preferable. Examples of the novolak type epoxy resin include a cresol novolak type and a phenol novolak type.
  • Examples of the biphenyl type epoxy resin include YL6121H and YX7399 manufactured by Mitsubishi Chemical Corporation.
  • the metal alkoxide compound and / or the metal chelate compound is any one or more selected from the group consisting of (i) polyester resin, (ii) polyamine resin, polyamidoamine resin, and polyamide resin, and (iii) reacts with the epoxy resin. Wake up. A crosslinking reaction proceeds between the functional group of each resin and the metal alkoxide compound and / or metal chelate compound. This cross-linking reaction has a significantly faster curing rate compared to the case where there is no metal alkoxide compound and / or metal chelate compound, and as a result, excellent adhesion, workability, Retort resistance and corrosion resistance can be expressed.
  • existing laminated cans are baked at 180 ° C. or higher for several seconds to several minutes after laminating films, and then the post-heating is used to cure the resin film to ensure the above various required performances.
  • the resin layer containing a metal alkoxide compound and / or a metal chelate compound is sufficiently cured by only heating for a short time of about 1 second when performing heat fusion lamination.
  • the performance equal to or better than that after post-heating can be obtained. Therefore, the post-heating step in the manufacturing process is not necessary, and the manufacturing efficiency is greatly improved.
  • carbon dioxide emissions can be reduced, which can be a very useful technique in practice.
  • the resin layer (a1) preferably further contains a metal alkoxide compound and / or a metal chelate compound.
  • metal alkoxide compound and / or metal chelate compound examples include alkoxide metal compounds such as aluminum, titanium, tin, and zirconium, and metal chelate compounds in which acetoacetic acid is coordinated to the metal.
  • alkoxide metal compounds such as aluminum, titanium, tin, and zirconium
  • metal chelate compounds in which acetoacetic acid is coordinated to the metal it is preferable to use a titanium alkoxide compound and / or a titanium chelate compound. The reason will be described below.
  • a three-dimensional network of molecular chains is formed in the resin layer by a continuous crosslinking reaction between the metal alkoxide compound and / or metal chelate compound and the polyester resin.
  • the discoloration due to water vapor is a phenomenon in which the resin layer itself is discolored so as to become cloudy white during retort sterilization treatment, and is called retort whitening.
  • This is a major problem that can reduce the consumer's willingness to purchase because the design of the outer surface of the can is impaired.
  • water vapor permeates into the resin layer covering the can body, thereby forming a vacuole at the interface of the resin layer and in the vicinity of the interface, and causing light to scatter at the vacuole part. It is thought that. Therefore, to improve the characteristics, it is important to suppress the formation of vacuoles at the interface of the resin layer and in the vicinity of the interface.
  • the water vapor that has entered the resin diffuses in the resin and reaches the interface with the metal plate.
  • the contents filled in the can are in a state close to room temperature, and therefore a temperature gradient is generated from the outside to the inside of the can. That is, the water vapor diffusing in the resin is cooled as it approaches the metal plate, liquefies at the interface and in the vicinity of the interface, and becomes condensed water to form a vacuole.
  • the vacuole remains at the interface and in the vicinity of the interface even after the retort treatment, which causes light scattering and makes the resin surface appear cloudy. Therefore, in order to suppress retort whitening, the formation of vacuoles at the interface and in the vicinity of the interface may be suppressed.
  • the retort processing apparatus there is a retort apparatus using hot water as a heating medium in addition to the apparatus using water vapor as a heating medium as described above.
  • a retort apparatus using hot water as a heating medium there arises a problem that the resin layer itself is discolored and the design is deteriorated by a mechanism different from the discoloration caused by water vapor. This is because, in the initial stage of the retort treatment, when the cross-linking reaction of the polyester molecular chain has not progressed sufficiently, water that has penetrated into the resin layer undergoes a hydrolysis reaction of the polyester molecular chain using the carbonyl terminal group of the polyester as a catalyst. It is believed that this is caused by the formation of large vacuoles in the resin layer.
  • Resin layer (a1) composition (mass%)
  • the ratio of the resin component forming the resin layer (a1) preferably satisfies the following.
  • Polyester resin 50 to 90 mass%
  • Epoxy resin 0.5 to 30 mass%
  • Metal alkoxide compound and / or metal chelate compound 0.01 to 10 mass%
  • the ratio of the polyester resin is lower than 50 mass%, the workability deteriorates, and when it exceeds 90 mass%, the curability is insufficient and the retort resistance may be lowered.
  • the ratio of one or more selected from the group consisting of polyamine resin, polyamidoamine resin, and polyamide resin is lower than 0.1 mass%, the curability is insufficient and the retort resistance is inferior, and if it exceeds 50 mass%, the processing is performed. Sexuality may worsen. More preferably, it is 3 to 30 mass%.
  • the ratio of the epoxy resin is lower than 0.5 mass%, the adhesiveness decreases, and as a result, the corrosion resistance deteriorates. If it exceeds 30 mass%, the retort whitening resistance may decrease. . More preferably, it is 5 to 25 mass%.
  • Adhesion Amount of Resin Layer (a1) The adhesion amount of the resin layer (a1) is preferably specified in the range of 0.1 g / m 2 to 5.0 / m 2 . If it is less than 0.1 g / m 2 , the surface of the metal plate cannot be uniformly coated, and the film thickness may be non-uniform. On the other hand, if it exceeds 5.0 g / m 2 , the cohesive strength of the resin becomes insufficient, and the strength of the resin layer may be reduced. As a result, at the time of can manufacturing, the resin layer is agglomerated and broken to peel off the film, and the can body portion is torn from that point.
  • the adhesion amount is preferably 0.1 g / m 2 or more and 5.0 g / m 2 or less, more preferably 0.1 g / m 2 or more and 3.0 g / m 2 or less, and still more preferably 0.5 g / m 2. m 2 or more and 2.0 g / m 2 .
  • the underlying metal plate can be concealed and various colors unique to the resin can be imparted.
  • a colorant such as a dye or pigment
  • carbon black as a black pigment
  • the particle size of the carbon black can be in the range of 5 to 50 nm, but the range of 5 to 30 nm is preferable in consideration of dispersibility and color developability in the polyester resin.
  • the black pigment by adding a white pigment, the metallic luster of the base can be concealed, the printed surface can be sharpened, and a good appearance can be obtained.
  • a pigment to be added it is necessary that an excellent designability can be exhibited after container molding. From this viewpoint, an inorganic pigment such as titanium dioxide can be used. Since the coloring power is strong and rich in spreadability, it is preferable because a good design property can be secured even after container molding. When a bright color is desired on the surface of the container, it is preferable to use a yellow organic pigment. Although it is excellent in transparency, it has a strong coloring power and a high spreadability, so that a bright appearance can be obtained even after the container is molded.
  • organic pigments that can be used in the present invention include a color index (abbreviation: CI) of Pigment Yellow 12, 13, 14, 16, 17, 55, 81, 83, 139, 180, 181, 183.
  • C.I. I. Pigment Yellow 180 and 214 are more preferably used.
  • the blending ratio of the above colorants is preferably 0.1 to 70 mass% in the total solid content of the resin layer constituting the resin layer (a1).
  • a curing catalyst that promotes crosslinking can be added to the curing catalyst resin layer (a1).
  • inorganic acids such as phosphoric acid, organic acids such as dodecylbenzenesulfonic acid and toluenesulfonic acid, and those blocked with an amine or the like can be used.
  • the blending ratio of the curing catalyst is preferably 0.01 to 5 mass% in the total solid content of the resin layer constituting the resin layer (a1).
  • conventionally known lubricants, antifoaming agents, leveling agents, pigments, anti-blocking agents such as silica and the like can be added to the resin layer (a1).
  • curing agents such as a melamine resin, a benzoguanamine resin, and an isocyanate resin may be used in combination as a curing auxiliary agent, and these can be used in combination with an appropriate one depending on the drying conditions and lamination conditions of the film.
  • polyester film (a2) formed on the upper layer of the resin layer (a1)
  • a resin layer (a2) containing a polyester resin as a main component on the upper layer of the resin layer (a1) as the uppermost layer, more preferably polyester as the resin layer (a2).
  • polyester film (a2) composition contains ethylene terephthalate and / or ethylene naphthalate in terms of improving the taste characteristics after retort and suppressing the generation of abrasion powder in the can making process. It is desirable to make it the main component.
  • the polyester having ethylene terephthalate and / or ethylene naphthalate as a main constituent is a polyester in which 85 mass% or more of the polyester has ethylene terephthalate and / or ethylene naphthalate as a constituent. More preferably, it is 90 mass% or more because the taste characteristics are good even if the beverage is filled for a long time in a metal can.
  • dicarboxylic acid components and glycol components may be copolymerized as long as the taste characteristics are not impaired.
  • the dicarboxylic acid component include aromatic compounds such as diphenylcarboxylic acid, 5-sodium sulfoisophthalic acid, and phthalic acid.
  • glycol component examples include aliphatic glycols such as ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, and neopentylglycol, alicyclic glycols such as cyclohexanedimethanol, and aromatics such as bisphenol A and bisphenol S.
  • examples include glycol, diethylene glycol, and polyethylene glycol.
  • bisphenol A of aromatic glycol is concerned about endocrine disrupting action, it is desirable not to use it as a glycol component.
  • dicarboxylic acid components and glycol components may be used in combination of two or more.
  • the polyester film used in the present invention can contain inorganic particles and / or organic particles.
  • the particles in the polyester film used in the present invention are not particularly limited in terms of composition regardless of organic or inorganic, but in terms of protrusion shape, wear resistance, workability, and taste characteristics when formed into a film Therefore, the volume-converted average particle diameter is preferably 0.005 to 5.0 ⁇ m, particularly preferably 0.01 to 3.0 ⁇ m. Further, from the viewpoint of wear resistance and the like, the relative standard deviation represented by the following formula is preferably 0.5 or less, and more preferably 0.3 or less.
  • the major axis / minor axis ratio of the particles is preferably 1.0 to 1.2.
  • the Mohs hardness is preferably less than 7 from the viewpoints of protrusion hardness, wear resistance, and the like. In order to fully exhibit these effects, it is preferable to contain 0.005 to 10 mass% of the particles composed of the above.
  • examples of the inorganic particles include wet and dry silica, colloidal silica, aluminum silicate, titanium oxide, calcium carbonate, calcium phosphate, barium sulfate, alumina, mica, kaolin, and clay.
  • those in which the functional group on the particle surface reacts with the polyester to form a carboxylic acid metal salt are preferable.
  • those having a functional group of 10 ⁇ 5 mol or more with respect to 1 g of the particles It is preferable in terms of the affinity, wear resistance, etc., and more preferably has a functional group of 2 ⁇ 10 ⁇ 5 mol or more.
  • organic polymer particles can be used as the organic particles, but any type of particles may be used as long as at least a part thereof is insoluble in polyester.
  • various materials such as polyimide, polyamideimide, polymethyl methacrylate, formaldehyde resin, phenol resin, cross-linked polystyrene, and silicone resin can be used as the material for such particles.
  • vinyl-based crosslinked polymer particles that have high heat resistance and can easily obtain particles having a uniform particle size distribution are particularly preferable.
  • Such inorganic particles and organic polymer particles may be used alone, but preferably used in combination of two or more, and further function by combining particles having different physical properties such as particle size distribution and particle strength.
  • a highly functional polyester resin can be obtained.
  • a polyester film is a biaxially stretched polyester film.
  • the biaxial stretching method may be simultaneous biaxial stretching or sequential biaxial stretching, but the stretching conditions and heat treatment conditions are specified, and the refractive index in the thickness direction of the film is 1.50 or more. Is preferable in terms of improving the laminating property and moldability.
  • the plane orientation coefficient is within a specific range in order to achieve both formability and impact resistance even if there is some variation during lamination. This is preferable because it can be controlled.
  • the biaxially stretched polyester film has a structure by solid high-resolution NMR in terms of workability and impact resistance when the neck portion is processed after receiving a heat history of about 200 to 230 ° C. after drawing in the can making process.
  • the relaxation time of the carbonyl moiety in the analysis is preferably 270 msec or more. More preferably, it is 280 msec or more, Most preferably, it is 300 msec or more.
  • other particles for example, various externally added externally added particles, internally precipitated particles, or various surface treatment agents may be used.
  • the thickness of the polyester film used in the present invention is preferably 5 to 100 ⁇ m.
  • the thickness of the polyester film is less than 5 ⁇ m, the covering property is insufficient and the impact resistance and the moldability cannot be ensured.
  • it exceeds 100 ⁇ m the above characteristics are saturated and no improvement effect can be obtained, and the thermal energy required for heat fusion to the metal surface increases, so the economic efficiency is impaired.
  • the more preferable thickness of the polyester film is 8 to 50 ⁇ m, and more preferably 10 to 25 ⁇ m.
  • the manufacturing method of the resin-coated metal plate for containers of the present invention will be described.
  • a method for forming the resin layer (a1) containing polyester as a main component a method for forming the polyester resin layer (a1) on the surface of the polyester film (a2) will be described.
  • a polyester resin as a main component is dissolved in an organic solvent, and an additive component and an optional additive component of the resin layer (a1) defined by the present invention are dissolved or dispersed in an organic solvent to prepare a coating liquid.
  • the coating liquid is applied to the film surface and dried at the time of film formation or after film formation of the polyester film (a2), thereby forming the resin layer (a1).
  • organic solvent for dissolving the polyester resin examples include aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone and cyclohexanone, and ester solvents such as ethyl acetate and ethylene glycol monoethyl ether acetate.
  • aromatic hydrocarbon solvents such as toluene and xylene
  • ketone solvents such as methyl ethyl ketone and cyclohexanone
  • ester solvents such as ethyl acetate and ethylene glycol monoethyl ether acetate.
  • Conventionally known lubricants, antifoaming agents, leveling agents, pigments, anti-blocking agents such as silica, and the like can be added to the coating solution.
  • curing agents such as a melamine resin, a benzoguanamine resin, and an isocyanate resin may be used in combination as a curing auxiliary agent, and these can be used in combination with an appropriate one depending on the drying conditions and lamination conditions of the film.
  • additives such as a carbon black and an azo pigment as a crosslinking agent, a curing catalyst, and a colorant specified in the present invention can be used by dispersing in an organic solvent. In this case, it is preferable to use a dispersant in combination because the uniformity of the additive can be imparted.
  • the coating liquid As a method for applying the coating liquid to the polyester film, known coating means such as a roll coater method, a die coater method, a gravure method, a gravure offset method, and a spray coating method can be applied, but a gravure roll coating method is most preferable.
  • the drying conditions after applying the coating solution are preferably 80 to 170 ° C. for 1 to 30 seconds, particularly 100 to 130 ° C. for 5 to 30 seconds.
  • the adhesion amount of the resin layer (a1) after drying is preferably in the range of 0.1 to 5.0 g / m 2 .
  • a preferred range is 0.5 to 2.5 g / m 2 .
  • a method of laminating the polyester film (a2) after coating the resin layer (a1) on the surface of the metal plate The polyester film (a2) coated with the resin layer (a1) is adhered to the surface of the metal plate. Laminate on the surface of the metal plate. For example, a metal plate is heated at a temperature exceeding the melting point of the film, and a polyester film (a2) coated with a resin layer (a1) on the surface is brought into contact with a pressure roll (hereinafter referred to as a laminate roll) and heat-sealed. Can be used. At this time, as described above, it is necessary that the polyester film surface coated with the resin layer (a1) is brought into contact with the metal plate using a laminating roll and thermally fused.
  • a pressure roll hereinafter referred to as a laminate roll
  • the laminating conditions are appropriately set so that the resin layer defined in the present invention can be obtained.
  • the temperature at the start of lamination is at least equal to or higher than the melting point of the film, and the temperature history received by the film at the time of lamination is in the range of 1 to 35 msec.
  • cooling during fusion is also necessary.
  • the pressure during lamination is not particularly specified, but the surface pressure is preferably 9.8 to 294 N / cm 2 (1 to 30 kgf / cm 2 ).
  • a chrome-plated steel plate was used as the metal plate.
  • a steel plate having a thickness of 0.18 mm and a width of 977 mm subjected to cold rolling, annealing, and temper rolling was subjected to chrome plating treatment after degreasing and pickling to produce a chromium plated steel plate.
  • electrolysis conditions adjusted to metallic chromium adhering amount and chromium hydroxide deposition amount (current density, the quantity of electricity, etc.), respectively Cr terms was adjusted to 120mg / m 2, 15mg / m 2.
  • polyester resin obtained by polymerizing the acid component and glycol component shown in Table 2 at the ratio shown in Table 2 is blended with the particles shown in Table 2 to obtain a resin composition.
  • the product was dried, melted and extruded according to a conventional method, cooled and solidified on a cooling drum to obtain an unstretched film, and then biaxially stretched and heat-set to obtain a biaxially oriented polyester film (a2).
  • each polyester resin, polyamine resin, polyamidoamine resin, polyamide resin, epoxy resin, metal alkoxide compound and / or metal chelate compound shown in Table 1 (Table 1-1 and Table 1-2, the same shall apply hereinafter)
  • a coating solution was prepared by dissolving in a mixed solvent of toluene and methyl ethyl ketone at the ratio shown in Table 1.
  • polyester resin (i-1) containing a repeating unit derived from diphenolic acid is shown.
  • an acid component 50 parts by mass of terephthalic acid, 112 parts by mass of isophthalic acid, 4.9 parts by mass of diphenolic acid, and 50 parts by mass of 2-ethyl-2-butyl-1,3-butanediol as a polyhydric alcohol component, , 99 parts by mass of 4-butanediol, 48 parts by mass of 1,4-cyclohexanedimethanol and 0.07 parts by mass of titanium tetrabutoxide were charged into a 2 L flask, and the temperature was gradually raised to 220 ° C. over 4 hours. Esterification was carried out.
  • the polymerization was carried out under reduced pressure up to 10 mmHg over 30 minutes, the temperature was raised to 250 ° C., and the latter polymerization was carried out at 1 mmHg or less for 50 minutes.
  • the polymerization under reduced pressure was stopped, the mixture was cooled to 220 ° C. under a nitrogen stream, 1.9 parts by mass of trimellitic anhydride was added, and the mixture was stirred at 220 ° C. for 30 minutes to perform carboxy group modification (post-addition), and then resin
  • the polyester resin (i-1) having a number average molecular weight of 22,000, an acid value of 5 (mgKOH / g) and a glass transition temperature of 30 ° C. was obtained.
  • polyamine resin commercially available EPICRON EXB-353 (manufactured by DIC Corporation) was used.
  • polyamide amine resin commercially available SUNMIDE 328A (manufactured by Air Products Japan, active ingredient 100%) was used.
  • polyamide resin commercially available polyamide L-15-3 (manufactured by Sanyo Kasei) was used.
  • epoxy resin commercially available epiclone N-660 (cresol novolak type epoxy resin, 50% methyl ethyl ketone solution, manufactured by DIC Corporation) and commercially available YL6121H (biphenyl type epoxy resin, manufactured by Mitsubishi Chemical Corporation) were used. .
  • TC-200 titanium octylene glycol chelate, Matsumoto Fine Chemical Co., Ltd.
  • ZA-65 zirconium butoxide, Matsumoto Fine Chemical Co., Ltd.
  • the coating liquid is applied and dried on one surface of the biaxially oriented polyester film (a2) obtained above with a gravure roll coater so as to have a predetermined dry film thickness, and the resin layer (a1) after drying The film thickness was adjusted.
  • the drying temperature was in the range of 80 to 120 ° C.
  • polyester resin obtained by polymerizing the acid component and glycol component shown in Table 4 in the ratio shown in Table 4 is blended with the particles shown in Table 4 to obtain a resin composition.
  • the product was dried, melted and extruded according to a conventional method, cooled and solidified on a cooling drum to obtain an unstretched film, and then biaxially stretched and heat-set to obtain a biaxially oriented polyester film (a2).
  • the agent was dissolved and dissolved in a mixed solvent of toluene and methyl ethyl ketone at the ratio shown in Table 3 to prepare a coating solution.
  • a synthesis example of a polyester resin (i-1) containing a repeating unit derived from diphenolic acid is shown.
  • an acid component 50 parts by mass of terephthalic acid, 112 parts by mass of isophthalic acid, 4.9 parts by mass of diphenolic acid, and 50 parts by mass of 2-ethyl-2-butyl-1,3-butanediol as a polyhydric alcohol component, , 99 parts by mass of 4-butanediol, 48 parts by mass of 1,4-cyclohexanedimethanol and 0.07 parts by mass of titanium tetrabutoxide were charged into a 2 L flask, and the temperature was gradually raised to 220 ° C. over 4 hours. Esterification was carried out.
  • the polymerization was carried out under reduced pressure up to 10 mmHg over 30 minutes, the temperature was raised to 250 ° C., and the latter polymerization was carried out at 1 mmHg or less for 50 minutes.
  • the polymerization under reduced pressure was stopped, the mixture was cooled to 220 ° C. under a nitrogen stream, 1.9 parts by mass of trimellitic anhydride was added, and the mixture was stirred at 220 ° C. for 30 minutes to perform carboxy group modification (post-addition), and then resin
  • the polyester resin (i-1) having a number average molecular weight of 22,000, an acid value of 5 (mgKOH / g) and a glass transition temperature of 30 ° C. was obtained.
  • polyamine resin commercially available EPICRON EXB-353 (manufactured by DIC Corporation) was used.
  • polyamide amine resin commercially available SUNMIDE 328A (manufactured by Air Products Japan, active ingredient 100%) was used.
  • polyamide resin commercially available polyamide L-15-3 (manufactured by Sanyo Kasei) was used.
  • epoxy resin commercially available epiclone N-660 (cresol novolak type epoxy resin, 50% methyl ethyl ketone solution, manufactured by DIC Corporation) and commercially available YL6121H (biphenyl type epoxy resin, manufactured by Mitsubishi Chemical Corporation) were used. .
  • TC-200 titanium octylene glycol chelate, Matsumoto Fine Chemical Co., Ltd.
  • ZA-65 zirconium butoxide, Matsumoto Fine Chemical Co., Ltd.
  • the coating liquid is applied and dried on one surface of the biaxially oriented polyester film (a2) obtained above with a gravure roll coater so as to have a predetermined dry film thickness, and the resin layer (a1) after drying The film thickness was adjusted.
  • the drying temperature was in the range of 80 to 120 ° C.
  • the chrome-plated steel sheet 1 obtained above is heated with a metal band heating apparatus 2, and one of the chrome-plated steel sheets 1 is formed with a laminating roll 3.
  • the resin coating layer (A) on the inner surface side of the can was laminated (heat fusion) on the surface, and the resin coating layer (A) on the outer surface side of the can was laminated (heat fusion) on the other surface.
  • the metal band cooling device 5 was used for water cooling to produce a polyester resin-coated metal plate.
  • the laminating roll 3 was an internal water-cooling type, and cooling water was forcibly circulated during the lamination to cool the film during bonding.
  • FIG. 2 shows the cross-sectional structure of the coating on one side of the resin-coated metal plate for containers (example of the present invention) produced as described above.
  • the characteristics of the resin-coated metal plate for containers produced as described above were measured and evaluated by the following methods (1) to (7).
  • (1) After applying wax to a resin-coated metal plate for formable containers, a disc having a diameter of 200 mm was punched out to obtain a shallow drawn can with a drawing ratio of 2.00. Next, the drawn can was redrawn at a drawing ratio of 2.50. Then, after performing doming forming according to a conventional method, trimming was performed, and then neck-in-flange processing was performed to form a deep drawn can. Focusing on the neck-in portion of the deep-drawn can thus obtained, the degree of film damage was visually observed.
  • the evaluation target is the inner and outer surfaces of the can.
  • the evaluation object is the can body part on the outer surface of the can.
  • Score Score
  • A 10.0 (N) / 15 (mm) or more
  • B 5.0 (N) / 15 (mm) or more, less than 10.0 (N) / 15 (mm) x: 5.0 (N) / Less than 15 (mm)
  • Adhesion after molding 2 Cans that were moldable (greater than or equal to) in the moldability evaluation of (1) above were targeted. After filling the inside of the can with tap water, the lid was wrapped and sealed. Subsequently, retort sterilization was performed at 130 ° C. for 90 minutes, and a peel test sample (width 15 mm, length 120 mm) was cut out from the can body.
  • Part of the film is peeled off from the long side end of the cut sample.
  • the peeled film is opened in the direction opposite to the peeled direction (angle: 180 °), and using a tensile tester, a tensile speed of 30 mm / min.
  • a peel test was conducted to evaluate the adhesion per 15 mm width.
  • the evaluation object is the can body part on the inner surface of the can.
  • the evaluation object is the can body part on the outer surface of the can.
  • ⁇ One side maximum corrosion width less than 0.5mm
  • ⁇ One side maximum corrosion width 0.5mm to less than 1.0mm
  • ⁇ One side maximum corrosion width 1.0mm or more (7)
  • an evaluation object is a can body part on the inner surface of the can. (About the score) :: One-side maximum corrosion width of less than 1.0 mm ⁇ : One-side maximum corrosion width of 1.0 mm to less than 3.0 mm ⁇ : One-side maximum corrosion width of 3.0 mm or more Tables 5 and 6 show the results obtained above.
  • a food canning material As a food canning material, it can be used in all markets around the world, mainly for canned food cans and lids.
  • Metal plate (chrome plated steel plate) 2 Metal Band Heating Device 3 Laminate Roll 4a, 4b Film 5 Metal Band Cooling Device

Landscapes

  • Laminated Bodies (AREA)
  • Rigid Containers With Two Or More Constituent Elements (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
PCT/JP2012/006182 2011-09-28 2012-09-27 容器用樹脂被覆金属板 WO2013046688A1 (ja)

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JP2015080938A (ja) * 2013-10-24 2015-04-27 Ｊｆｅスチール株式会社 容器用樹脂被覆金属板
JP2020084153A (ja) * 2018-11-30 2020-06-04 三菱ケミカル株式会社 粉末積層造形法用共重合ポリブチレンテレフタレート
CN115298025A (zh) * 2020-04-03 2022-11-04 东洋钢钣株式会社 层叠聚酯树脂被覆金属板、层叠聚酯树脂膜和罐盖

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JPH07207044A (ja) * 1994-01-21 1995-08-08 Toray Ind Inc 金属板ラミネート用ポリエステルフイルム
JP2001150621A (ja) * 1999-11-25 2001-06-05 Unitika Ltd 金属板ラミネート用ポリエステルフィルム
JP2009078540A (ja) * 2007-09-07 2009-04-16 Toyobo Co Ltd 絞りしごき缶被覆用フイルム
JP2010235188A (ja) * 2009-03-31 2010-10-21 Jfe Steel Corp 容器用着色ラミネート金属板
JP2012025132A (ja) * 2010-07-28 2012-02-09 Jfe Steel Corp 容器用樹脂被覆金属板

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JPH07207044A (ja) * 1994-01-21 1995-08-08 Toray Ind Inc 金属板ラミネート用ポリエステルフイルム
JP2001150621A (ja) * 1999-11-25 2001-06-05 Unitika Ltd 金属板ラミネート用ポリエステルフィルム
JP2009078540A (ja) * 2007-09-07 2009-04-16 Toyobo Co Ltd 絞りしごき缶被覆用フイルム
JP2010235188A (ja) * 2009-03-31 2010-10-21 Jfe Steel Corp 容器用着色ラミネート金属板
JP2012025132A (ja) * 2010-07-28 2012-02-09 Jfe Steel Corp 容器用樹脂被覆金属板

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Publication number Priority date Publication date Assignee Title
JP2015080938A (ja) * 2013-10-24 2015-04-27 Ｊｆｅスチール株式会社 容器用樹脂被覆金属板
JP2020084153A (ja) * 2018-11-30 2020-06-04 三菱ケミカル株式会社 粉末積層造形法用共重合ポリブチレンテレフタレート
JP7139917B2 (ja) 2018-11-30 2022-09-21 三菱ケミカル株式会社 粉末積層造形法用共重合ポリブチレンテレフタレート
CN115298025A (zh) * 2020-04-03 2022-11-04 东洋钢钣株式会社 层叠聚酯树脂被覆金属板、层叠聚酯树脂膜和罐盖

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