WO2015125459A1 - 容器用樹脂被覆金属板およびその製造方法 - Google Patents
容器用樹脂被覆金属板およびその製造方法 Download PDFInfo
- Publication number
- WO2015125459A1 WO2015125459A1 PCT/JP2015/000717 JP2015000717W WO2015125459A1 WO 2015125459 A1 WO2015125459 A1 WO 2015125459A1 JP 2015000717 W JP2015000717 W JP 2015000717W WO 2015125459 A1 WO2015125459 A1 WO 2015125459A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin layer
- resin
- uppermost
- metal plate
- layer
- Prior art date
Links
Images
Classifications
-
- 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
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/54—No clear coat specified
-
- 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
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin 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
-
- 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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D25/00—Details of other kinds or types of rigid or semi-rigid containers
- B65D25/14—Linings or internal coatings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2202/00—Metallic substrate
- B05D2202/10—Metallic substrate based on Fe
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2252/00—Sheets
- B05D2252/10—Applying the material on both sides
-
- 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
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/402—Coloured
- B32B2307/4026—Coloured within the layer by addition of a colorant, e.g. pigments, dyes
-
- 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
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/30—Iron, e.g. steel
-
- 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
- B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
-
- 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
Definitions
- the present invention relates to a resin-coated metal plate for containers used in, for example, can bodies and lids for canned foods and a method for producing the same.
- tin free steel which is a material for metal cans used in food cans, and metal plates such as aluminum have been coated for the purpose of improving corrosion resistance, durability, weather resistance, and the like.
- this coating technique 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. Therefore, in order to solve these problems, resin-coated metal plates were developed by laminating thermoplastic resin films on heated metal plates instead of painted metal plates. Widely used.
- Patent Document 1 was filed, assuming that good characteristics could be secured.
- Patent Document 1 it is insufficient to secure good content take-out properties from the strength of the adhesiveness for the content having a high protein content such as luncheon meat and tuna. There was also.
- Patent Document 2 has a high protein content and can secure excellent take-out properties even for highly adherent contents.
- it is necessary to add about 10 to 25 mass% of a low-energy substance having many hydrophobic groups to the resin layer in direct contact with the contents. Since it is necessary to introduce a relatively large amount of additive, the composition of the resin layer is limited, and it is necessarily composed of a plurality of resin layers. Therefore, inconsistency between resin layers is inevitable, and there is room for improvement in adhesion between layers.
- Patent Document 3 is also composed of a plurality of resin layers as in Patent Document 2, and by adding 15 to 20 mass% of fatty acid amide to the uppermost resin layer in contact with the contents, As a result, excellent content takeout property is ensured, and there is room for improvement in adhesion between resin layers.
- An object of the present invention is to provide a resin-coated metal plate for containers and a method for producing the same.
- the present inventors diligently studied to solve the above problems. As a result, paying attention to the resin layer (A) on the inner surface side of the container after forming the container, the uppermost resin layer (a1) in contact with the contents of the resin layer (A). By adding a wax compound to the resin and controlling the crystal structure of the uppermost resin layer (a1), excellent content takeout properties and other required properties (adhesion, moldability, corrosion resistance, etc.) are satisfied. It has been found that a resin-coated metal plate for containers can be obtained.
- the resin layer (A) contains 85 mol% or more of terephthalic acid
- the resin layer (A) is composed of at least two layers, and the uppermost resin layer (a1) in contact with the contents contains 0% of the wax compound with respect to the uppermost resin layer (a1).
- a resin layer (B) having a multilayer structure mainly composed of polyester is provided on the side that becomes the outer surface of the container when the metal plate is formed into a container, and the uppermost layer of the resin layers (B)
- the resin in the resin layer (b1) contains a polyester (1) composed of polyethylene terephthalate or a copolymerized polyethylene terephthalate whose copolymer component content is less than 6 mol%, and a polybutylene terephthalate or copolymer component.
- the present invention it is possible to obtain a resin-coated metal plate for containers having excellent take-out properties for various contents. Moreover, the resin-coated metal plate for containers of the present invention can stably satisfy many characteristics required for food canning materials.
- FIG. 1 is a view showing a main part of a laminating apparatus for a metal plate.
- FIG. 2 is a diagram showing a cross-sectional structure of a resin-coated metal plate for containers. (Example 1)
- 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.
- a surface-treated steel sheet (so-called TFS) in which a two-layer film having a lower layer composed of metallic chromium and an upper layer composed of chromium hydroxide is formed is optimal.
- 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 water The oxide layer is desirably in the range of 10 to 30 mg / m 2 .
- Composition of resin layer (A) on inner surface of container and in this invention, when forming a metal plate in a container, it has the resin layer (A) of the multilayer structure which has polyester as a main component on the side used as the container inner surface.
- This resin layer (A) is a polymer composed of a dicarboxylic acid component and a glycol component, and is characterized by containing 85 mol% or more of terephthalic acid as the dicarboxylic acid component.
- terephthalic acid is less than 85 mol%, the melting point of the resin is lowered, and the resin is softened by frictional heat at the time of molding the container, which may cause damage such as film scraping.
- terephthalic acid is less than 85 mol%, the melting point of the resin is lowered, and the resin is softened by frictional heat at the time of molding the container, which may cause damage such as film scraping.
- the resin layer is attacked by water vapor and the adhesion in a wet environment is deteriorated.
- Dicarboxylic acid components other than terephthalic acid include aromatic dicarboxylic acids such as isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, 5-sodium sulfoisophthalic acid, phthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, dimer Examples thereof include aliphatic dicarboxylic acids such as acid, maleic acid and fumaric acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, and oxycarboxylic acids such as p-oxybenzoic acid.
- aromatic dicarboxylic acids such as isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, 5-sodium sulfoisophthalic acid, phthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, dim
- 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. Glycol and the like.
- aliphatic glycols such as ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, and neopentylglycol
- alicyclic glycols such as cyclohexanedimethanol
- aromatics such as bisphenol A and bisphenol S. Glycol and the like.
- ethylene glycol is preferable among these glycol components.
- dicarboxylic acid components and glycol components may be used in combination of two or more.
- the resin layer (A) is composed of at least two layers, and the uppermost resin layer (a1) in contact with the contents contains a wax compound as the uppermost resin layer (a1).
- the wax compound is characterized by containing 0.10 to 2.0 mass%.
- the purpose of adding the wax compound is to reduce the surface free energy of the resin layer (A). By adding the wax compound, it becomes difficult for the contents to adhere to the resin layer (A), and the contents can be taken out easily. improves.
- the reason for limiting to 0.10 mass% or more is that when the content is less than 0.10 mass%, the above-described effect becomes poor, and the contents can be easily taken out.
- the reason for limiting to 2.0 mass% or less is that if it exceeds 2.0 mass%, there is a high possibility that the adhesion between the resin layers will deteriorate, and the film formation of the resin layer (A) itself will be difficult, resulting in production. This is because the property deteriorates.
- the presence or absence of the wax addition to the resin layers other than the uppermost layer is not particularly limited, even when added, it is preferably set to 2.0 mass% or less. However, even if a wax compound is added to a resin layer other than the uppermost layer, the effect of improving the contents take-out property may not be seen, so it is effective to add it only to the uppermost layer.
- an organic / inorganic lubricant can be used as a component of the wax compound to be added.
- carnauba wax which is one of vegetable waxes and is a natural wax
- the polyester resin containing carnauba wax can be produced by a usual production method after blending a predetermined amount of wax with polyester.
- the uppermost resin layer (a1) has a Raman band intensity ratio measured with respect to the cross section of the uppermost resin layer (a1) using a laser polarization plane parallel to the resin layer (a1).
- the maximum value of (I 1720 / I 1615 ) is in the range of 0.45 to 0.80.
- I 1720 is the highest peak height of the Raman band in the range of 1720 cm -1 ⁇ 10 cm -1 derived from a carbonyl group C-O stretching by laser Raman spectroscopy.
- the Raman band intensity (I 1720 ) of the 1720 cm ⁇ 1 ⁇ 10 cm ⁇ 1 Raman band derived from the carbonyl group C—O stretch is coordinated to the trans position when the polyester crystallinity increases. It tends to grow. Therefore, when the Raman band intensity ratio (I 1720 / I 1615 ) is increased, more polyester crystals exist in the direction parallel to the surface of the resin layer (a1). On the other hand, when the Raman band intensity ratio (I 1720 / I 1615 ) is reduced, the polyester crystals existing in the direction parallel to the resin layer surface are reduced.
- the maximum value of the Raman band intensity ratio (I 1720 / I 1615 ) of the crystal structure of the resin layer (a1) is in the range of 0.45 or more and 0.80 or less. It has been found that the contents can be remarkably improved by the control. The reason is shown below. Since the crystal lattice of the wax compound such as carnauba wax added in the resin layer (a1) is larger than the crystal lattice of the polyester which is the main component of the resin layer (a1), it exists in the crystal region of the polyester. Can not. For this reason, the wax compound exists only in the amorphous region of the polyester.
- the glass transition temperature (Tg) of the polyester resin constituting the resin layer (a1) is about 70 ° C., and the movement of the molecular chain is frozen below this temperature (about 70 ° C.). Fixed inside. Therefore, in the process from container molding to filling and sealing of the contents, the structure of the resin layer (a1) is stable, and the wax compound remains in the amorphous region in the resin layer (a1). However, in the retort sterilization process, when the container is heated to about 120 to 130 ° C., the molecular chain that constitutes the amorphous region of the polyester resin starts micro-Brownian motion. Will move. Since the wax compound has a lower surface free energy than the polyester resin, it diffuses and concentrates on the surface of the resin layer (a1). Thereby, the surface free energy of the resin layer (a1) is lowered, and the contents can be easily taken out. By facilitating the concentration of the wax compound on the surface of the resin layer (a1), the content takeout property is improved.
- the amount of crystals aligned in the parallel direction with respect to the surface of the resin layer (a1) is increased, the surface concentration of the wax compound is significantly reduced. This is because the crystals are arranged in a direction perpendicular to the wax diffusion direction, so that it functions as a diffusion barrier.
- the crystals arranged in this way also have a function as a barrier layer for water vapor causing retort whitening, chlorine ions, water, oxygen, etc. causing corrosion. Therefore, the amount of crystals needs to be controlled within a range that balances the required characteristics.
- the maximum Raman band intensity ratio (I 1720 / I 1615 ) when measured using a laser polarization plane parallel to the surface of the resin layer (a 1) with respect to the cross section of the resin layer (a 1).
- the value is specified in the range of 0.45 or more and 0.80 or less. By setting it within this range, the surface concentration of the wax compound becomes smooth, excellent contents can be taken out, and sufficient barrier properties against water vapor and corrosion factors can be secured.
- the Raman band intensity ratio (I 1720 / I 1615 ) is less than 0.45, the amount of crystals is insufficient, resulting in a decrease in barrier properties, which may lead to retort whitening and corrosion resistance deterioration.
- the thickness of the resin layer (a1) is in the range of 0.5 ⁇ m to 10 ⁇ m. Since the addition amount of the wax compound is limited to 2.0 mass% or less with respect to the resin layer (a1), when the thickness of the resin layer (a1) is less than 0.5 ⁇ m, the wax content itself is insufficient. , Sufficient contents take-out property cannot be obtained.
- the thickness of the resin layer (a1) is 0.5 ⁇ m or more and 10 ⁇ m or less.
- the thickness of the resin layer (A) excluding the thickness of the uppermost resin layer (a1) is 5 ⁇ m or more and 20 ⁇ m or less.
- the resin layer (a2) ensures adhesion to the metal plate.
- the resin strength sufficient to maintain the interfacial adhesion with the resin layer (a1) cannot be maintained.
- the thickness of the resin layer (A) excluding the thickness of the uppermost resin layer (a1), that is, the thickness of the resin layer (a2) is 5 ⁇ m or more and 20 ⁇ m or less.
- the resin layer on the outer surface side of the container is required to maintain an aesthetic appearance even after container molding and after retort sterilization. Therefore, it is preferable to contain either titanium dioxide or a disazo organic pigment as a coloring pigment in order to impart design properties.
- the resin layer (B) mainly composed of polyester is a polymer composed of a dicarboxylic acid component and a glycol component, and preferably contains 85 mol% or more of terephthalic acid as the dicarboxylic acid component.
- terephthalic acid is less than 85 mol%, the melting point of the resin is lowered, the resin is softened by frictional heat at the time of container molding, and damage such as film scraping may occur.
- the resin layer is attacked with water vapor
- Dicarboxylic acid components other than terephthalic acid include aromatic dicarboxylic acids such as isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, 5-sodium sulfoisophthalic acid, phthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, dimer Examples thereof include aliphatic dicarboxylic acids such as acid, maleic acid and fumaric acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, and oxycarboxylic acids such as p-oxybenzoic acid.
- aromatic dicarboxylic acids such as isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, 5-sodium sulfoisophthalic acid, phthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, dim
- 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. Glycol and the like.
- aliphatic glycols such as ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, and neopentylglycol
- alicyclic glycols such as cyclohexanedimethanol
- aromatics such as bisphenol A and bisphenol S. Glycol and the like.
- glycol components ethylene glycol and butylene glycol are preferred.
- dicarboxylic acid components and glycol components may be used in combination of two or more.
- the resin layer (b1) excluding the uppermost layer of the resin layer (B) has a disazo type as a coloring pigment. It is preferable to add an organic pigment. These pigments are yellow, but have transparency, so that it is possible to efficiently obtain a golden bright color by utilizing the gloss of the metal plate.
- a method using an oil-soluble dye is known as a method for coloring with high transparency.
- One of these drawbacks is migration (elution of a coloring material from a colored resin). This is a phenomenon (bleeding) that floats on the resin surface when subjected to a thermal history such as retort sterilization treatment because the oil-soluble dye is dissolved in the resin to be colored.
- disazo organic pigments are generally present in the resin as particles, migration can be greatly suppressed.
- CI Pigment Yellow 180 is particularly preferable. This is because it is a pigment that has been registered by FDA (Food and Drug Administration: American Food and Drug Administration) and has excellent safety and excellent color tone. As addition amount, 0.1 mass% or more and 20.0 mass% or less are preferable with respect to the whole quantity of a resin layer (B). When it is less than 0.1 mass%, color development is poor and a preferable color tone cannot be obtained. On the other hand, if it exceeds 20.0 mass%, the transparency of the resin becomes poor, and there is a possibility that the color tone lacks in the bright color.
- the particle diameter of the pigment is preferably less than 1 ⁇ m.
- the transparency of the polyester resin may be lost.
- a higher fatty acid metal salt such as magnesium stearate can be used as a dispersant. When a dispersant is used, a more uniform and highly transparent color tone can be obtained.
- the metallic gloss 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 to be able to exhibit excellent design properties after container molding, and from this viewpoint, use of titanium dioxide is preferable. 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.
- the addition amount is preferably 10.0 mass% or more and 30.0 mass% or less with respect to the total amount of the resin layer (B). When it is less than 10.0 mass%, color development is poor and a preferable color tone cannot be obtained.
- the wax compound can be contained in both or either of the uppermost resin layer (b2) and the resin layer (b1) excluding the uppermost layer. Among them, the wax compound should be contained in the uppermost resin layer (b2) in order to prevent scratches and scraping of the resin layer (B) during high processing and to ensure moldability during high processing. Is preferred. Further, when the wax compound is contained only in the uppermost resin layer (b2), the content of the wax compound for obtaining the effect is less than that in the resin layer (B) as a whole. be able to.
- the content of the wax compound in the uppermost resin layer (b2) is relative to the resin layer (B) (when converted to the entire layer).
- 5.0 mass% or less is preferable, and the content of the uppermost resin layer (b2) is also preferably 5.0 mass% or less. If the content exceeds 5.0 mass%, the adhesiveness between the resin layer (B) and the ink deteriorates when printing or printing on the outer surface of the container, which is not preferable for printing applications. Moreover, since the film formability of the resin layer (B) becomes difficult, it is not preferable.
- the lower limit of the content of the wax compound in the uppermost resin layer (b2) is 0. With respect to the resin layer (B) (when converted to all layers) in order to obtain the effect of containing the wax compound. It is preferable to set it to 02 mass%.
- the upper limit of the content of the wax compound in each of the content of the entire resin layer (B), the content of the uppermost resin layer (b2), and the content of the resin layer (b1) excluding the uppermost layer is 5. It is preferable to set it to 0.0 mass%.
- the amount of the wax compound in terms of the total resin layer (B) is the uppermost resin layer (b2) and the resin layer (b1) excluding the uppermost layer when the wax is also included. It can be determined by dividing the mass of the wax compound contained in the resin layer (b1) excluding b2) and the uppermost layer by the mass of the entire resin layer (B).
- the wax compound is not particularly limited. Either an organic lubricant or an inorganic lubricant can be used.
- the wax component similar to the resin layer (A) can be used.
- a wax compound having a high melting point is preferred because the outer surface side of the container tends to have a higher temperature on the resin surface due to friction with the mold than the inner surface during can processing.
- the melting point of the wax compound is preferably 50 ° C. or higher, more preferably 70 ° C. or higher.
- Preferred wax compounds are natural waxes such as carnauba wax and candelilla wax, fatty acid esters such as stearic acid esters, polyolefin waxes such as polyethylene wax, and the like. These wax compounds can be used alone or in combination of two or more.
- the thickness of the resin layer (b1) is preferably 5 ⁇ m or more from the viewpoint of design. If it is less than 5 ⁇ m, the pigment content with respect to the thickness becomes excessive, the dispersibility of the pigment is poor, and a resin layer lacking transparency may be formed. Further, the mechanical properties of the resin layer (b1) may be inhibited.
- the resin layer (B) used in the present invention preferably has a multilayer structure composed of two or more resin layers, and the uppermost layer (in the case of two layers, a pigment was contained). A resin layer (b2) containing no pigment is formed on the upper layer of the resin layer (b1).
- the resin layer (b2) By forming the resin layer (b2) on the uppermost layer (in the case of two layers, the upper layer of the resin layer (b1) having a high pigment content), the bleeding of the pigment during the retorting process is surely suppressed. Can do. Since bleeding is a phenomenon in which pigment diffuses in the polyester resin, the resin layer (b2) not containing the pigment, that is, the clear layer functions as a diffusion barrier and prevents the pigment from moving to the resin layer surface. is there.
- the thickness of the resin layer (b2) is preferably 1.5 ⁇ m or more. Considering that the thermal history of the retort treatment currently applied to food cans extends to 120 ° C. or more for 1 hour or more, the elution of the pigment is concerned if it is less than 1.5 ⁇ m.
- the multilayer structure of the resin layer (B) used in the present invention is not limited to a two-layer structure.
- a three-layer structure (adhesion layer, resin layer (b1), and resin layer (b2) having an adhesion layer excellent in adhesion to the metal plate on the side that is in close contact with the metal plate, between the resin layer (b1) and the metal plate.
- the adhesion layer those having good adhesion to the metal plate and compatible with polyethylene terephthalate contained in the upper layer of the adhesion layer are preferable.
- an adhesive such as epoxy phenol can be used for the adhesion layer from the viewpoint of cost and ease of containing a dye (described later).
- composition of resin layer (b1) includes polyethylene terephthalate or copolymerized polyethylene terephthalate having a copolymer component content of less than 6 mol% (hereinafter sometimes referred to as polyester (1)), polybutylene terephthalate or copolymer.
- polyester (2) a copolymerized polybutylene terephthalate having a polymerization component content of less than 5 mol% is mixed, and the ratio of polyester (1) is 60 mass. % Or less, and the ratio of polyester (2) is preferably 40 mass% or more.
- the ratio of the polyester (2) is preferably 40 mass% or more, more preferably 40 mass to 70 mass%, further preferably 45 to 65 mass%, and still more preferably 50 to 60 mass%.
- polyester (1) may contain a copolymerization component in a range of less than 6 mol% as a range that does not impair the effects of the invention.
- the copolymer component may be an acid component or an alcohol component.
- the acid component includes aromatic dicarboxylic acids such as isophthalic acid, phthalic acid and naphthalenedicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and decanedicarboxylic acid, and alicyclic such as cyclohexanedicarboxylic acid. And dicarboxylic acid.
- isophthalic acid is most preferred from the viewpoint of moldability.
- the alcohol component examples include aliphatic diols such as diethylene glycol, propanediol, butanediol, and hexanediol, and alicyclic diols such as cyclohexanedimethanol.
- Polyester (2) is a polycondensation containing a terephthalic acid component and a 1,4-butanediol component as main components, but the other components are contained within a range of less than 5 mol% as long as the effects of the present invention are not impaired. It may be copolymerized.
- the copolymer component may be an acid component or an alcohol component.
- Copolymeric acid components include aromatic dicarboxylic acids such as isophthalic acid, phthalic acid and naphthalenedicarboxylic acid, aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and decanedicarboxylic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid.
- aromatic dicarboxylic acids such as isophthalic acid, phthalic acid and naphthalenedicarboxylic acid
- aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and decanedicarboxylic acid
- alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid.
- An acid etc. can be illustrated. Of these, isophthalic acid, 2,6-naphthalenedicarboxylic acid or adipic acid is preferred.
- the copolymerized alcohol component examples include aliphatic diols such as ethylene glycol, propanediol, and hexanediol, and alicyclic diols such as cyclohexanedimethanol. These can be used alone or in combination of two or more.
- the resin layer (b2) is a polymer composed of a dicarboxylic acid component and a glycol component, and preferably contains 85 mol% or more of terephthalic acid as the dicarboxylic acid component.
- Dicarboxylic acid components other than terephthalic acid include aromatic dicarboxylic acids such as isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, 5-sodium sulfoisophthalic acid, phthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, dimer Examples thereof include aliphatic dicarboxylic acids such as acid, maleic acid and fumaric acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, and oxycarboxylic acids such as p-oxybenzoic acid.
- aromatic dicarboxylic acids such as isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, 5-sodium sulfoisophthalic acid, phthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, dim
- glycol component examples include aliphatic glycols such as ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, and neopentylglycol, alicyclic glycols such as cyclohexanedimethanol, and aromatic glycols such as bisphenol A and bisphenol S. Etc. Of these glycol components, ethylene glycol and butylene glycol are preferred. These dicarboxylic acid components and glycol components may be used in combination of two or more. [Production method] Next, the manufacturing method of the resin-coated metal plate for containers of the present invention will be described.
- covers a metal plate is demonstrated.
- the method for producing the resin layer (film) For example, after drying each polyester resin as necessary, it is supplied to a known melt lamination extruder, extruded into a sheet form from a slit-shaped die, and brought into close contact with a casting drum by a method such as electrostatic application, and solidified by cooling. A stretched film (sheet) is obtained.
- the target resin is put into a laminating extruder to obtain an unstretched film having a multilayer structure.
- a biaxially stretched film is obtained by stretching this unstretched film in the longitudinal direction and the width direction.
- the draw ratio can be arbitrarily set according to the orientation degree, strength, elastic modulus and the like of the target film.
- it is based on the tenter method in terms of film quality, and after stretching in the longitudinal direction, a sequential biaxial stretching method that stretches in the width direction, and simultaneous biaxial stretching in which the longitudinal direction and the width direction are stretched almost the same. The method is preferred.
- a method for producing a resin-coated metal plate by laminating a resin layer (film) on a metal plate will be described.
- a laminate roll a pressure-bonding roll
- the lamination conditions are appropriately set so that the resin layer specified in the present invention is obtained.
- the surface temperature of the metal plate at the start of lamination is set to Tm (melting point) (° C.) or more of the resin layer in contact with the metal plate.
- the temperature is controlled in the range of Tm to Tm + 40 ° C. of the resin layer.
- Tm + 40 ° C. the resin layer is excessively melted and the resin layer may adhere to the laminate roll, and the crystal structure of the surface resin layer (a1) is controlled within the specified range of the present invention. It becomes difficult. Tm to Tm + 25 ° C. is preferable, and Tm to Tm + 15 ° C. is more preferable.
- the surface temperature of the laminate roll is adjusted. Specifically, the surface temperature of the laminate roll is controlled in the range of Tg to Tg + 60 ° C. of the resin layer (a1). Of course, adjustment of the contact time with the laminate roll is also an important factor. The contact time is controlled in the range of 10 to 25 msec.
- the crystal structure of the resin layer (a1) defined by the present invention can be realized by adjusting the surface temperature of the laminate roll and the contact time within the above ranges.
- the resin layers (A) and (B) are preferable to heat the resin layers (A) and (B) before laminating.
- the temperature distribution in the cross section of the resin layer at the time of lamination can be made more uniform.
- the crystal structure in the cross section of the resin layer also exhibits a more uniform performance since the structural change from the interface with the metal plate to the surface layer becomes gradual.
- the crystal structure of the resin layer is fixed by quenching.
- the time to quench is preferably within 5 seconds, and the quench water temperature may be Tg or less.
- the resin layer is preferably formed into a film and coated on a metal plate.
- the crystal structure defined in the present invention may not be achieved.
- a polyester composition obtained by polymerizing the acid component and glycol component shown in Table 1 at a ratio shown in Table 1 is blended with a wax compound to obtain a resin composition, and this resin composition is dried and melted in accordance with a conventional method. After co-extrusion from a die, it was cooled and solidified on a cooling drum to obtain an unstretched film, and then biaxially stretched and heat-set to obtain a biaxially stretched polyester film (A).
- the metal strip laminating apparatus shown in FIG. 1 is used to heat the chrome-plated steel sheet 1 obtained above with a metal band heating apparatus 2, and the container is formed on one surface of the chrome-plated steel sheet 1 with a laminating roll 3.
- the polyester film (A) that becomes the inner surface side was laminated (heat fusion), and the polyester film (B) that became the outer surface side of the container was laminated (heat fusion) on the other surface.
- the surface temperature of the metal plate is in the range of Tm to Tm + 40 ° C. of the polyester resin layer (a1) constituting the polyester film (A) except for some comparative examples. Controlled.
- the surface temperature of the laminate roll 3 was in the range of Tg to Tg + 60 ° C. of the polyester film (A), and the contact time with the metal plate was in the range of 10 to 15 msec.
- the Tg of the resins listed in Table 1 was almost no difference and was about 75 ° C.
- the laminating roll 3 is an internal water cooling type, and the cooling water is circulated in the roll to control the temperature during film bonding.
- the temperature of the resin layer before lamination was in the range of Tg + 30 ° C. to Tg + 100 ° C. of the polyester film (A), and the temperature distribution in the cross section of the resin layer was made uniform.
- water cooling was performed with the metal band cooling device 5, and the resin-coated metal plate for containers was manufactured.
- the production conditions are shown in Table 3.
- the cross-sectional structure of the resin-coated metal plate for containers manufactured as described above is shown in FIG.
- Raman band intensity ratio (I 1720 / I 1615 ) (I) when measured using a laser polarization plane parallel to the resin layer surface A sample for measurement is prepared by polishing the cross section of the laminated steel sheet, and is 1 ⁇ m from the surface of the uppermost resin layer (a1) to the thickness direction from the surface of the uppermost resin layer (a1) with a parallel laser polarization plane to the resin surface on the inner surface of the container.
- the 1720 cm -1 and 1615 cm -1 Raman band intensities were measured at intervals of, respectively, the ratio was determined, and the maximum value and the average value of the intensity ratio were determined.
- Raman band intensity at 1720 cm -1 was the height of the highest peak of the Raman band in the range of 1720cm -1 ⁇ 10cm -1.
- Raman band intensity at 1615 cm -1 was the height of the highest peak of the Raman band in the range of 1615cm -1 ⁇ 10cm -1.
- the Raman band intensity ratio (I) was calculated by the following formula.
- I I 1720 / I 1615 I 1720 : Raman band intensity of 1720 cm ⁇ 1 I 1650 : Raman band intensity measurement of 1615 cm ⁇ 1
- salted meat for luncheon meat (protein content in solid content: 60 mass%) was filled into the cup, and the lid was wound up, followed by retort sterilization (130 ° C., 90 minutes). Then, when the lid was removed and the contents were taken out with the cup upside down, the degree of ease of taking out the contents was evaluated by observing the degree of the contents remaining inside the cup.
- ⁇ The contents remain inside the cup just by turning the cup upside down, but the contents can be taken out by vibrating the cup up and down (such as shaking the cup by hand).
- the retort sterilization treatment was performed at 130 ° C. for 90 minutes, and then aged for 90 days in a constant temperature bath at 38 ° C. Then, the can was opened and a sample for peel test (width 15 mm, length 120 mm) was cut from the can body. Part of the film was peeled off from the long side end of the cut sample. The peeled film was opened in the direction opposite to the peeled direction (angle: 180 °), and a peel test was performed using a tensile tester at a tensile speed of 30 mm / min. To evaluate the adhesion per 15 mm width. .
- the evaluation target surface is a can body portion on the inner surface of the can.
- Corrosion resistance Molding is possible by the moldability evaluation in (3) above. Cans that were (O or better) were targeted. After filling the inside of the can with a commercially available ketchup (manufactured by Kagome Co., Ltd.), the lid was wrapped and sealed. Subsequently, the retort sterilization treatment was performed at 130 ° C. for 90 minutes, and then aged for 90 days in a constant temperature bath at 38 ° C. Thereafter, the iron concentration eluted in the contents (ketchup) was measured to evaluate the corrosion resistance.
- the evaluation target surface is a can body portion on the inner surface of the can. (About the score) ⁇ : Less than 1 mass ppm ⁇ : 1 mass ppm or more and less than 10 mass ppm x: 10 mass ppm or more (8)
- a disc having a diameter of 179 mm is punched out and drawn Shallow drawn cans were obtained at a ratio of 1.80.
- the drawn can was redrawn at a drawing ratio of 2.40 and 3.00 to form a deep drawn can. Paying attention to the can body portion of the deep drawn can thus obtained, the processing state of the film was visually observed.
- Metal plate manufacturing method A metal plate was produced in the same manner as in Example 1.
- the metal strip laminating apparatus shown in FIG. 1 is used to heat the chrome-plated steel sheet 1 obtained above with a metal band heating apparatus 2, and the container is formed on one surface of the chrome-plated steel sheet 1 with a laminating roll 3.
- the polyester film (A) that becomes the inner surface side was laminated (heat fusion), and the polyester film (B) that became the outer surface side of the container was laminated (heat fusion) on the other surface.
- the surface temperature of the metal plate is in the range of Tm to Tm + 40 ° C. of the polyester resin layer (a1) constituting the polyester film (A) except for some comparative examples. Controlled.
- the surface temperature of the laminate roll 3 was in the range of Tg to Tg + 60 ° C. of the polyester film (A), and the contact time with the metal plate was in the range of 10 to 15 msec.
- the Tg of the resins listed in Table 1 was almost no difference and was about 75 ° C.
- the laminating roll 3 is an internal water cooling type, and the cooling water is circulated in the roll to control the temperature during film bonding.
- the temperature of the resin layer before lamination was in the range of Tg + 30 ° C. to Tg + 100 ° C. of the polyester film (A), and the temperature distribution in the cross section of the resin layer was made uniform.
- water cooling was performed with the metal band cooling device 5, and the resin-coated metal plate for containers was manufactured.
- the production conditions are shown in Table 8.
- the cross-sectional structure of the resin-coated metal plate for containers manufactured as described above is shown in FIG.
- the resin-coated metal sheet for containers according to the present invention is suitable for container applications and packaging applications that require excellent contents removal. And it can use as a raw material for containers which perform drawing processing etc., especially a raw material for food can containers.
- Metal plate (chrome plated steel plate) 2 Metal belt heating device 3 Laminate roll 4a Polyester resin layer (A) 4b Polyester resin layer (B) 5 Metal band cooling device
Landscapes
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
- Details Of Rigid Or Semi-Rigid Containers (AREA)
- Containers Having Bodies Formed In One Piece (AREA)
Abstract
Description
そこで、これらの問題を解決するため、塗装金属板に替わり、熱可塑性樹脂フィルムを加熱した金属板に積層してなる樹脂被覆金属板が開発され、現在、飲料缶用素材を中心として工業的に広く用いられている。
[1]金属板と、該金属板を容器に成形した際に容器内面となる側に、ポリエステルを主成分とする複層構造の樹脂層(A)を有する容器用樹脂被覆金属板であって、
1)前記樹脂層(A)は、テレフタル酸を85mol%以上含み、
2)前記樹脂層(A)は、少なくとも2層から構成され、かつ内容物と接する最上層の樹脂層(a1)が、ワックス化合物を、前記最上層の樹脂層(a1)に対して、0.10~2.0mass%含有し、
3)前記最上層の樹脂層(a1)の断面に対して、樹脂層(a1)表面と平行方向のレーザー偏光面を用いて測定した時のラマンバンド強度比(I1720/I1615)の最大値が、0.45以上0.80以下の範囲であり、
4)前記最上層の樹脂層(a1)の厚みが0.5μm以上10μm以下であり、
5)前記最上層の樹脂層(a1)の厚みを除く前記樹脂層(A)の厚みが5μm以上20μm以下である
容器用樹脂被覆金属板。
[2]前記ワックス化合物は、カルナウバワックスを含有する前記[1]に記載の容器用樹脂被覆金属板。
[3]前記金属板を容器に成形した際に容器外面となる側に、ポリエステルを主成分とする複層構造の樹脂層(B)を有し、該樹脂層(B)のうちの最上層を除く樹脂層(b1)が、着色顔料として二酸化チタン、ジスアゾ系有機顔料のいずれかを含有する前記[1]または[2]に記載の容器用樹脂被覆金属板。
[4]前記樹脂層(b1)中の樹脂は、ポリエチレンテレフタレートまたは共重合成分の含有率が6mol%未満である共重合ポリエチレンテレフタレートからなるポリエステル(1)と、ポリブチレンテレフタレートまたは共重合成分の含有率が5mol%未満である共重合ポリブチレンテレフタレートからなるポリエステル(2)を混合した組成物であり、かつ、前記ポリエステル(1)の比率が60mass%以下、前記ポリエステル(2)の比率が40mass%以上である前記[3]に記載の容器用樹脂被覆金属板。
[5]前記樹脂層(B)が、ワックス化合物を、前記樹脂層(B)に対して、5.0mass%以下含有する前記[3]または[4]に記載の容器用樹脂被覆金属板。
[6]前記樹脂層(B)のうち、最上層を除く樹脂層(b1)および最上層の樹脂層(b2)に、もしくは最上層の樹脂層(b2)にワックス化合物を含有し、前記最上層の樹脂層(b2)がワックス化合物を、前記最上層の樹脂層(b2)に対して、5.0mass%以下含有する前記[5]に記載の容器用樹脂被覆金属板。
[7]前記ワックス化合物は、カルナウバワックスを含有する前記[5]または[6]に記載の容器用樹脂被覆金属板。
[8]前記[1]~[7]のいずれかに記載の容器用樹脂被覆金属板の製造方法であって、最上層の樹脂層(a1)の断面に対して、樹脂層(a1)表面と平行方向のレーザー偏光面を用いて測定した時のラマンバンド強度比(I1720/I1615)の最大値が、0.45以上0.80以下の範囲となるように樹脂層形成条件を決定する容器用樹脂被覆金属板の製造方法。
まず、本発明で用いる金属板について説明する。
本発明の金属板としては、缶用材料として広く使用されているアルミニウム板や軟鋼板等を用いることができる。特に、下層が金属クロム、上層がクロム水酸化物からなる二層皮膜を形成させた表面処理鋼板(いわゆるTFS)等が最適である。
TFSの金属クロム層、クロム水酸化物層の付着量については、特に限定されないが、加工後密着性、耐食性の観点から何れもCr換算で、金属クロム層は70~200mg/m2、クロム水酸化物層は10~30mg/m2の範囲とすることが望ましい。
[容器内面側となる樹脂層(A)の組成]
そして、本発明では、金属板を容器に成形した際に容器内面となる側に、ポリエステルを主成分とする複層構造の樹脂層(A)を有する。この樹脂層(A)は、ジカルボン酸成分とグリコール成分からなるポリマーであり、ジカルボン酸成分としてテレフタル酸85mol%以上含むことを特徴とする。テレフタル酸が、85mol%未満であった場合、樹脂の融点が低下し、容器成形時の摩擦熱で樹脂が軟化してしまい、フィルム削れ等の損傷が発生する懸念がある。また、容器成形後のレトルト殺菌処理においても、水蒸気により樹脂層がアタックされ、湿潤環境下での密着性が劣化する懸念がある。
[ワックス化合物]
また、本発明では、前記樹脂層(A)は、少なくとも2層から構成され、かつ内容物と接する最上層の樹脂層(a1)が、ワックス化合物を、前記最上層の樹脂層(a1)に対して、0.10~2.0mass%含有することを特徴とする。ワックス化合物を添加する目的は、樹脂層(A)の表面自由エネルギーを低下させることにあり、ワックス化合物を添加することにより樹脂層(A)に内容物が付着し難くなり、内容物取り出し性が向上する。0.10mass%以上に限定した理由は、0.10mass%未満となると、上記効果が乏しくなり、内容物の取り出し性が劣るためである。また、2.0mass%以下に限定した理由は、2.0mass%を超えると、樹脂層間の密着性が劣化する可能性が高く、また、樹脂層(A)の成膜そのものが困難となり、生産性が劣化してしまうためである。なお、最上層以外の樹脂層へのワックス添加の有無は特に限定するものではないが、添加する場合でも2.0mass%以下とすることが好ましい。ただし、最上層以外の樹脂層にワックス化合物を添加しても内容物取り出し性の向上効果は見られない場合があるため、最上層のみに添加することが効果的である。
[樹脂層(a1)の結晶構造]
さらに、前記最上層の樹脂層(a1)は、最上層の樹脂層(a1)の断面に対して、樹脂層(a1)と平行方向のレーザー偏光面を用いて測定した時のラマンバンド強度比(I1720/I1615)の最大値が、0.45以上0.80以下の範囲であることを特徴とする。ここで、I1720はレーザーラマン分光法によるカルボニル基C-O伸縮由来の1720cm-1±10cm-1の範囲でのラマンバンドの最も高いピーク高さである。I1615はレーザーラマン分光法によるポリエステル樹脂のベンゼン環C=C伸縮由来の1615cm-1±10cm-1の範囲でのラマンバンドの最も高いピーク高さである。
樹脂層(a1)内に添加されているカルナウバワックスなどのワックス化合物の結晶格子は、樹脂層(a1)の主成分であるポリエステルの結晶格子に比べ大きいため、ポリエステルの結晶領域内には存在できない。そのため、ワックス化合物は、ポリエステルの非晶領域内にのみ存在することとなる。樹脂層(a1)を構成するポリエステル樹脂のガラス転移温度(Tg)は、約70℃であり、この温度(約70℃)以下では分子鎖の運動が凍結されるため、ワックス化合物は非晶領域内に固定化される。従って、容器成形され、内容物が充填・密閉されるまでの工程においては、樹脂層(a1)の構造は安定であり、ワックス化合物も樹脂層(a1)内の非晶領域に留まっている。しかし、レトルト殺菌処理工程において、容器が120~130℃程度まで加熱されると、ポリエステル樹脂の非晶領域を構成する分子鎖がミクロブラウン運動を開始し、それに伴って、ワックス化合物がポリエステル樹脂内を動くようになる。ワックス化合物は、ポリエステル樹脂に比べ、表面自由エネルギーが低いため、樹脂層(a1)の表面に拡散し、濃化する。これにより、樹脂層(a1)の表面自由エネルギーが低下して内容物取り出し性が良好となる。ワックス化合物の、樹脂層(a1)表面への濃化を促進させることにより、内容物取り出し性は向上する。
[樹脂層(a1)の厚み]
樹脂層(a1)の厚みは、0.5μm以上10μm以下の範囲とする。ワックス化合物の添加量は、樹脂層(a1)に対して、2.0mass%以下に限定されるため、樹脂層(a1)の厚みが0.5μm未満となると、ワックスの含有量そのものが不足し、十分な内容物取り出し性が得られない。一方、10μm超となると、樹脂層(a1)の樹脂層(A)に対する比率が過度となり、樹脂層(A)と金属板との密着性や、樹脂層(A)の成形性、耐食性などの機能が低下する懸念がある。よって、樹脂層(a1)の厚みは、0.5μm以上10μm以下とする。
[最上層の樹脂層(a1)の厚みを除く樹脂層(A)の厚み]
最上層の樹脂層(a1)の厚みを除く樹脂層(A)の厚みは、5μm以上20μm以下とする。樹脂層(A)のうち、最上層の樹脂層(a1)を除く下層の樹脂層をa2とすると、厚みが5μm未満だと、樹脂層(a2)が金属板との密着性を確保しつつ樹脂層(a1)との界面密着性を保持するだけの樹脂強度が保てなくなる。一方、20μmを超えると、飲料缶用素材や食品缶詰用素材に求められる機能に対して、さらなる改善が望めないばかりか、樹脂コストの上昇のみを招いてしまう。よって、最上層の樹脂層(a1)の厚みを除く樹脂層(A)の厚み、すなわち、樹脂層(a2)の厚みは、5μm以上20μm以下とする。
[容器外面側となる樹脂層(B)の組成]
金属板を容器に成形した際に容器外面となる側に、ポリエステルを主成分とする複層構造の樹脂層(B)を有し、樹脂層(B)のうちの最上層を除く樹脂層(b1)が、着色顔料として二酸化チタン、ジスアゾ系有機顔料のいずれかを含有することが好ましい。容器外面側となる樹脂層には、容器成形後やレトルト殺菌処理後においても、外観上の美観を維持することが求められる。そのため、意匠性を付与するため、着色顔料として二酸化チタン、ジスアゾ系有機顔料のいずれかを含有することが好ましい。
これは、油溶性染料が被着色樹脂中に溶解しているため、レトルト殺菌処理のような熱履歴をうけると、樹脂表面へ浮き出す現象(ブリーディング)である。しかし、ジスアゾ系有機顔料は、一般的に粒子として樹脂中に存在するため、移行性を大幅に抑制することができる。
[ワックス化合物]
さらに、本発明では、高加工時の樹脂層(B)の傷や削れを防ぐために、ワックス化合物を、樹脂層(B)に対して、5.0mass%以下含有することが好ましい。含有量が5.0mass%を超えると、容器外面に印刷や印字をする際に、樹脂層(B)とインクの密着性が劣化するため、印刷用途向けには好ましくない。また、樹脂層(B)の成膜性も困難になるため、好ましくない。一方、ワックス化合物の含有量が0.02mass%未満であると、ワックス化合物添加による樹脂層(B)の疵や削れ防止の効果が得られない場合があるため、ワックス化合物を含有する場合は0.02mass%以上とすることが好ましい。
[樹脂層(b1)の厚み]
樹脂層(b1)の厚みは、5μm以上であることが意匠性の観点から好ましい。5μm未満であると、厚みに対する顔料含有量が過度となり、顔料の分散性が乏しく、透明性に欠けた樹脂層となってしまう場合がある。また、樹脂層(b1)の機械特性も阻害される可能性がある。
[樹脂層(B)の構成]
前述の通り、本発明で用いる樹脂層(B)の構成としては、2層以上の樹脂層から構成される複層構造であることが好ましく、最上層(2層の場合は、顔料を含有した樹脂層(b1)の上層)に、顔料を含有していない樹脂層(b2)を形成する。樹脂層(b2)を、最上層(2層の場合は、顔料の含有量の高い樹脂層(b1)の上層)に形成することで、レトルト処理過程での顔料のブリーディングを確実に抑制することができる。ブリーディングは、顔料がポリエステル樹脂内を拡散する現象であることから、顔料を含有していない樹脂層(b2)すなわちクリア層が拡散障壁として機能し、顔料の樹脂層表面への移動を妨げるためである。ここで、樹脂層(b2)の厚みは1.5μm以上が好ましい。現在、食缶に施されるレトルト処理の熱履歴が、120℃以上で1時間以上にも及ぶことを考慮すると、1.5μm未満では顔料の溶出が懸念される。
[樹脂層(b1)の組成]
樹脂層(b1)の組成としては、ポリエチレンテレフタレートまたは共重合成分の含有率が6mol%未満である共重合ポリエチレンテレフタレート(以下、ポリエステル(1)と記載する場合もある)と、ポリブチレンテレフタレートまたは共重合成分の含有率が5mol%未満である共重合ポリブチレンテレフタレート(以下、ポリエステル(2)と記載する場合もある)とを混合したポリエステル組成物であり、且つ、ポリエステル(1)の比率が60mass%以下、ポリエステル(2)の比率が40mass%以上であることが好ましい。このような樹脂組成とすることで、食品缶詰用途で必須となるレトルト殺菌処理において、金属板との密着性を維持し、かつ、水蒸気が樹脂層内で凝結することによる樹脂変色を抑制することが可能となる。ポリエステル(2)の比率が、40mass%未満となると、120℃以上の高温かつ長時間(1時間以上)のレトルト殺菌処理を施されると、水蒸気の凝結を抑制することができず、樹脂層内に液胞が形成される。これ(液胞)が、レトルト殺菌処理後も、樹脂層内に残留することで、可視光の散乱を招き、樹脂の外観を変化させ意匠性が低下する懸念がある。一方、ポリエステル(2)の比率が、70mass%よりも大きい場合は、上記レトルト殺菌処理時の樹脂変色は抑制できるものの、樹脂の耐熱性や機械特性が劣化傾向となり、缶加工時の応力や摩擦熱等の影響により、樹脂が傷ついてしまう懸念がある。また、ポリエステル(2)のTgは、40℃程度とポリエステル(1)に比べ低いため、常温を超える温度にさらされた場合に、樹脂のバリア性が大きく低下することで、耐食性が大きく劣化する懸念がある。このため、ポリエステル(2)の比率は40mass%以上が好ましく、より好ましくは40mass~70mass%、さらに好ましくは45~65mass%、よりさらに好ましくは50~60mass%の範囲である。
[樹脂層(b2)の組成]
樹脂層(b2)は、ジカルボン酸成分とグリコール成分からなるポリマーであり、ジカルボン酸成分としてテレフタル酸85mol%以上含むことが好ましい。テレフタル酸が、85mol%未満であった場合、樹脂の融点が低下し、容器成形時の摩擦熱で樹脂が軟化してしまい、フィルム削れ等の損傷が発生する懸念がある。また、容器成形後のレトルト殺菌処理においても、水蒸気により樹脂層がアタックされ、湿潤環境下での密着性が劣化する懸念がある。
[製造方法]
次に本発明の容器用樹脂被覆金属板の製造方法について説明する。
まず、金属板に被覆する複層構造の樹脂層(A)(B)(フィルムの場合も含む)の製造方法について説明する。
樹脂層(フィルム)の製造方法については特に限定はしない。例えば、各ポリエステル樹脂を必要に応じて乾燥した後、公知の溶融積層押出機に供給し、スリット状のダイからシート状に押出し、静電印加等の方式によりキャスティングドラムに密着させ冷却固化し未延伸フィルム(シート)を得る。複層フィルムを得る場合は、積層押出機に、目的の樹脂を投入し、複層構成の未延伸フィルムを得る。この未延伸フィルムを長手方向及び幅方向に延伸することにより二軸延伸フィルムを得る。延伸倍率は目的とするフィルムの配向度、強度、弾性率等に応じて任意に設定することができる。好ましくはフィルムの品質の点でテンター方式によるものであり、長手方向に延伸した後、幅方向に延伸する逐次二軸延伸方式、長手方向、幅方向をほぼ同じに延伸していく同時二軸延伸方式が好ましい。
本発明では、例えば、金属板をフィルムの融点を超える温度まで加熱し、圧着ロール(以後、ラミネートロールと称す)を用いて樹脂フィルムをその両面に接触させ熱融着させる方法(以後、ラミネートと称す)を用いることができる。このとき、容器成形した後に容器内面側になるフィルムについては、ワックス化合物が添加されていない樹脂層(a2)を、金属板に接触させ熱融着させる。
(金属板の製造方法)
冷間圧延、焼鈍、調質圧延を施した厚さ0.18mm、幅977mmからなる鋼板を、脱脂、酸洗後、クロムめっきを行い、クロムめっき鋼板(TFS)を製造した。クロムめっきは、CrO3、F-、SO4 2-を含むクロムめっき浴でクロムめっき、中間リンス後、CrO3、F-を含む化成処理液で電解した。その際、電解条件(電流密度・電気量等)を調整して金属クロム付着量とクロム水酸化物付着量を、Cr換算でそれぞれ120mg/m2、15mg/m2に調整した。
表1に示す酸成分とグリコール成分を、表1に示す比率にて重合したポリエステル樹脂に、ワックス化合物を配合して樹脂組成物とし、この樹脂組成物を常法に従い、乾燥・溶融させ、Tダイより共押出した後、冷却ドラム上で冷却固化させ、未延伸フィルムを得た後、ニ軸延伸・熱固定して、ニ軸延伸ポリエステルフィルム(A)を得た。
表2に示す酸成分とグリコール成分を、酸成分でテレフタル酸以外の共重合成分はすべてエチレングリコールと重合させ、ポリエチレンテレフタレートまたは共重合ポリエチレンテレフタレートとし、さらに、テレフタル酸とブチレングリコールを重合したポリブチレンテレフタレートを混合し、ポリエステル樹脂とした。このポリエステル樹脂に、着色顔料を配合して樹脂組成物とし、この樹脂組成物を常法に従い、乾燥・溶融させ、Tダイより共押出した後、冷却ドラム上で冷却固化させ、未延伸フィルムを得た後、ニ軸延伸・熱固定して、ニ軸延伸ポリエステルフィルム(B)を得た。
図1に示す金属帯のラミネート装置を用い、前記で得たクロムめっき鋼板1を金属帯加熱装置2で加熱し、ラミネートロール3で前記クロムめっき鋼板1の一方の面に、容器成形した後に容器内面側になるポリエステルフィルム(A)をラミネート(熱融着)するとともに、他方の面に容器外面側になるポリエステルフィルム(B)をラミネート(熱融着)した。
ポリエステルフィルム(A)を金属板にラミネートする際に、金属板の表面温度は、一部の比較例を除き、ポリエステルフィルム(A)を構成するポリエステル樹脂層(a1)のTm~Tm+40℃の範囲に制御した。また、ラミネートロール3の表面温度は、ポリエステルフィルム(A)のTg~Tg+60℃の範囲とし、金属板との接触時間は、10~15msecの範囲とした。なお、表1に記載の樹脂のTgは、ほとんど差はなく、75℃程度であった。ラミネートロール3は、内部水冷式であり、ロール内に冷却水を循環させることで、フィルム接着中の温度制御を図った。ラミネート前の樹脂層の温度は、ポリエステルフィルム(A)のTg+30℃~Tg+100℃の範囲とし、樹脂層断面内の温度分布の均一化を図った。その後、金属帯冷却装置5にて水冷を行い、容器用樹脂被覆金属板を製造した。製造条件を、表3に示す。
以上より製造された容器用樹脂被覆金属板の断面構造を図2に示す。
以上より得られた樹脂被覆金属板及び金属板上に有する樹脂層に対して以下の特性を測定、評価した。測定、評価方法を、下記に示す。
ラミネート鋼板の断面を研磨して測定用サンプルを作製し、容器内面側樹脂層表面に対して、平行なレーザー偏光面で、最上層の樹脂層(a1)の表面から厚み方向に対し、1μm毎の間隔で1720cm-1と1615cm-1ラマンバンド強度をそれぞれ測定し、比を求め、この強度比の最大値と平均値を求めた。なお、1720cm-1でのラマンバンド強度は、1720cm-1±10cm-1の範囲でのラマンバンドの最も高いピークの高さとした。また、同様に、1615cm-1でのラマンバンド強度は、1615cm-1±10cm-1の範囲でのラマンバンドの最も高いピークの高さとした。下記式により、ラマンバンド強度比(I)を計算した。
I=I1720/I1615
I1720:1720cm-1のラマンバンド強度
I1650:1615cm-1のラマンバンド強度
測定条件
励起光源:半導体レーザー(λ=530nm)
顕微鏡倍率:×100
露光時間 :5秒
露光回数 :2回
アパーチャ:25μmφ
(2)内容物取り出し性
絞り成形機を用いて、ラミネート金属板を、絞り工程で、ブランク径:100mm、絞り比(成形前径/成形後径):1.88でカップ成形した。続いて、ランチョンミート用の塩漬け肉(固形分中のたんぱく質含有率:60mass%)をカップ内に充填し、蓋を巻き締めた後、レトルト殺菌処理(130℃、90分間)を行なった。その後、蓋を取り外し、カップを逆さまにして内容物を取り出した時に、カップ内側に残存する内容物の程度を観察することにより、内容物の取り出し易さの程度を評価した。
(評点について)
◎:カップをさかさまにしただけで(手で振ることなく)内容物が取り出せ、取り出し後のカップ内面を肉眼で観察した際、付着物が殆ど確認できない状態になるもの。
○:カップをさかさまにしただけではカップ内側に内容物が残存するが、カップを上下に振動させる(手でカップを振るなどの動作をする)と、内容物が取り出せる。取り出し後のカップ内面を肉眼で観察した際、付着物が殆ど確認できない状態になるもの。
×:カップを上下に振動させる(手でカップを振るなどの動作をする)だけでは、内容物が取り出し難い。上下に振動させるスピードを極端に増すか、もしくはスプーンなどの器具を用いて内容物を強制的に取り出した後、カップ内面を肉眼で観察した際、付着物が明らかに確認できる状態になるもの
(3)成形性
樹脂被覆金属板にワックス塗布後、直径165mmの円板を打ち抜き、絞り比1.50で浅絞り缶を得た。次いで、この絞り缶に対し、絞り比1.80及び2.00で再絞り加工を行った。この後、常法に従いドーミング成形を行った後、トリミングし、次いでネックイン-フランジ加工を施し深絞り缶を成形した。このようにして得た深絞り缶のネックイン部に着目し、フィルムの加工状態を目視観察した。
(評点について)
◎:成形後フィルムに損傷が認められない状態
○:成形可能であるが、部分的にフィルムの変色が認められる状態
×:缶が破胴し、成形不可能
(4)耐レトルト白化性
上記(3)の成形性評価で成形可能(○以上)であった缶の、底部(缶外面側)を対象とした。缶内に常温の水道水を満たした後、蓋を巻き締めて密閉した。その後、缶底部を下向きにして、蒸気式レトルト殺菌炉の中に配置し、130℃で90分間、レトルト処理を実施した。処理後、缶底部外面の外観変化を観察した。
(評点について)
◎:外観変化なし
○:外観にかすかな曇りあり
×:外観が白濁(白化発生)
(5)耐顔料析出性
上記(3)の成形性評価で成形可能(○以上)であった缶を対象とした。缶内に常温の水道水を満たした後、蓋を巻き締めて密閉した。その後、蒸気式レトルト殺菌炉の中に配置し、130℃で90分間、レトルト処理を実施した。処理後、缶胴部を、ガーゼで拭い、顔料析出の有無を評価した。
(評点について)
◎:ふき取り後のガーゼ表面に、顔料が全く付着せず、着色が認められない
○:ふき取り後のガーゼ表面を肉眼で観察した場合には、顔料付着は認められないものの、光学顕微鏡観察(100倍)によれば、軽微な付着が認められる
×:ふき取り後のガーゼ表面に、顔料が付着し、着色が認められる
(6)成形後密着性
上記(3)の成形性評価で成形可能(○以上)であった缶を対象とした。缶の内部に、3質量%NaCl+3質量%クエン酸ナトリウム混合液を充填した後、蓋を巻き締めて密閉した。続いて、レトルト殺菌処理を130℃、90分間の条件で実施した後、38℃の恒温槽内で、90日間、経時させた。その後、缶を切り開き、缶胴部より、ピール試験用のサンプル(幅15mm、長さ120mm)を切り出した。切り出したサンプルの長辺側端部からフィルムの一部を剥離した。剥離したフィルムを、剥離された方向とは逆方向(角度:180°)に開き、引張試験機を用いて、引張速度30mm/min.でピール試験を行い、幅15mmあたりの密着力を評価した。評価対象面は、缶内面の缶胴部である。
(評点について)
◎:10.0(N)以上
○:5.0(N)以上、10.0(N)未満
×:5.0(N)未満
(7)耐食性
上記(3)の成形性評価で成形可能(○以上)であった缶を対象とした。缶の内部に、市販のケチャップ(カゴメ(株)製)を充填した後、蓋を巻き締めて密閉した。続いて、レトルト殺菌処理を130℃、90分間の条件で実施した後、38℃の恒温槽内で、90日間、経時させた。その後、内容物(ケチャップ)中に溶出した鉄濃度を計測し、耐食性を評価した。評価対象面は、缶内面の缶胴部である。
(評点について)
◎:1質量ppm未満
○:1質量ppm以上10質量ppm未満
×:10質量ppm以上
(8)成形加工時の耐傷付き性
樹脂被覆金属板にワックス塗布後、直径179mmの円板を打ち抜き、絞り比1.80で浅絞り缶を得た。次いで、この絞り缶に対し、絞り比2.40及び3.00で再絞り加工を行い、深絞り缶を成形した。このようにして得た深絞り缶の缶胴部分に着目して、フィルムの加工状態を目視観察した。
(評点について)
◎:成形後フィルムに損傷が認められない状態
○:成形可能であるが、部分的にフィルムに僅かな傷が認められる状態
△:成形可能であるが、フィルムに削れが発生し、鋼板が部分的に露出している状態
×:缶が破胴し、成形不可能
(9)印刷適性
樹脂被覆金属板を容器成形した後に容器外面側となる樹脂表面に印刷用インク(東洋インキ(株)製印刷用インキCCST39) を塗布し、乾燥させ、塗膜厚1.5μmとなるよう調整した。
その後、塗装面にニチバン(株)製セロテープ(登録商標)を密着させ、一気に剥離した。
10枚試験を行い、インクが剥がれた枚数を調査した。
○ :0枚
△ :1~3枚
× :4枚以上
以上により得られた結果を表4、5に示す。
実施例1と同様の方法にて、金属板を製造した。
表6に示す酸成分とグリコール成分を、酸成分でテレフタル酸以外の共重合成分はすべてエチレングリコールと重合させ、ポリエチレンテレフタレートまたは共重合ポリエチレンテレフタレートとし、さらに、テレフタル酸とブチレングリコールを重合したポリブチレンテレフタレートを混合し、ポリエステル樹脂とした。このポリエステル樹脂に、ワックス化合物を配合して樹脂組成物とし、この樹脂組成物を常法に従い、乾燥・溶融させ、Tダイより共押出した後、冷却ドラム上で冷却固化させ、未延伸フィルムを得た後、ニ軸延伸・熱固定して、ニ軸延伸ポリエステルフィルム(A)を得た。
表7に示す酸成分とグリコール成分を、表7に示す比率にて重合したポリエステル樹脂に、
着色顔料およびワックス化合物を配合して樹脂組成物とし、この樹脂組成物を常法に従い、乾燥・溶融させ、Tダイより共押出した後、冷却ドラム上で冷却固化させ、未延伸フィルムを得た後、ニ軸延伸・熱固定して、ニ軸延伸ポリエステルフィルム(B)を得た。
図1に示す金属帯のラミネート装置を用い、前記で得たクロムめっき鋼板1を金属帯加熱装置2で加熱し、ラミネートロール3で前記クロムめっき鋼板1の一方の面に、容器成形した後に容器内面側になるポリエステルフィルム(A)をラミネート(熱融着)するとともに、他方の面に容器外面側になるポリエステルフィルム(B)をラミネート(熱融着)した。
ポリエステルフィルム(A)を金属板にラミネートする際に、金属板の表面温度は、一部の比較例を除き、ポリエステルフィルム(A)を構成するポリエステル樹脂層(a1)のTm~Tm+40℃の範囲に制御した。また、ラミネートロール3の表面温度は、ポリエステルフィルム(A)のTg~Tg+60℃の範囲とし、金属板との接触時間は、10~15msecの範囲とした。なお、表1に記載の樹脂のTgは、ほとんど差はなく、75℃程度であった。ラミネートロール3は、内部水冷式であり、ロール内に冷却水を循環させることで、フィルム接着中の温度制御を図った。ラミネート前の樹脂層の温度は、ポリエステルフィルム(A)のTg+30℃~Tg+100℃の範囲とし、樹脂層断面内の温度分布の均一化を図った。その後、金属帯冷却装置5にて水冷を行い、容器用樹脂被覆金属板を製造した。製造条件を、表8に示す。
以上より製造された容器用樹脂被覆金属板の断面構造を図2に示す。
以上より得られた樹脂被覆金属板及び金属板上に有する樹脂層に対して以下の特性を測定、評価した。測定、評価方法は、実施例1と同様である。
(1)樹脂層表面と平行方向のレーザー偏光面を用いて測定した時のラマンバンド強度比(I1720/I1615)(I)
(2)内容物取り出し性
(3)成形性
(4)耐レトルト白化性
(5)耐顔料析出性
(6)成形後密着性
(7)耐食性
(8)成形加工時の耐傷付き性
(9)印刷適性
以上により得られた結果を表9、10に示す。
2 金属帯加熱装置
3 ラミネートロール
4a ポリエステル樹脂層(A)
4b ポリエステル樹脂層(B)
5 金属帯冷却装置
Claims (8)
- 金属板と、該金属板を容器に成形した際に容器内面となる側に、ポリエステルを主成分とする複層構造の樹脂層(A)を有する容器用樹脂被覆金属板であって、
1)前記樹脂層(A)は、テレフタル酸を85mol%以上含み、
2)前記樹脂層(A)は、少なくとも2層から構成され、かつ内容物と接する最上層の樹脂層(a1)が、ワックス化合物を、前記最上層の樹脂層(a1)に対して、0.10~2.0mass%含有し、
3)前記最上層の樹脂層(a1)の断面に対して、樹脂層(a1)表面と平行方向のレーザー偏光面を用いて測定した時のラマンバンド強度比(I1720/I1615)の最大値が、0.45以上0.80以下の範囲であり、
4)前記最上層の樹脂層(a1)の厚みが0.5μm以上10μm以下であり、
5)前記最上層の樹脂層(a1)の厚みを除く前記樹脂層(A)の厚みが5μm以上20μm以下である
容器用樹脂被覆金属板。 - 前記ワックス化合物は、カルナウバワックスを含有する請求項1に記載の容器用樹脂被覆金属板。
- 前記金属板を容器に成形した際に容器外面となる側に、ポリエステルを主成分とする複層構造の樹脂層(B)を有し、該樹脂層(B)のうちの最上層を除く樹脂層(b1)が、着色顔料として二酸化チタン、ジスアゾ系有機顔料のいずれかを含有する請求項1または2に記載の容器用樹脂被覆金属板。
- 前記樹脂層(b1)中の樹脂は、ポリエチレンテレフタレートまたは共重合成分の含有率が6mol%未満である共重合ポリエチレンテレフタレートからなるポリエステル(1)と、ポリブチレンテレフタレートまたは共重合成分の含有率が5mol%未満である共重合ポリブチレンテレフタレートからなるポリエステル(2)を混合した組成物であり、かつ、前記ポリエステル(1)の比率が60mass%以下、前記ポリエステル(2)の比率が40mass%以上である請求項3に記載の容器用樹脂被覆金属板。
- 前記樹脂層(B)が、ワックス化合物を、前記樹脂層(B)に対して、5.0mass%以下含有する請求項3または4に記載の容器用樹脂被覆金属板。
- 前記樹脂層(B)のうち、最上層を除く樹脂層(b1)および最上層の樹脂層(b2)に、もしくは最上層の樹脂層(b2)にワックス化合物を含有し、
前記最上層の樹脂層(b2)がワックス化合物を、前記最上層の樹脂層(b2)に対して、5.0mass%以下含有する請求項5に記載の容器用樹脂被覆金属板。 - 前記ワックス化合物は、カルナウバワックスを含有する請求項5または6に記載の容器用樹脂被覆金属板。
- 請求項1~7のいずれか一項に記載の容器用樹脂被覆金属板の製造方法であって、最上層の樹脂層(a1)の断面に対して、樹脂層(a1)表面と平行方向のレーザー偏光面を用いて測定した時のラマンバンド強度比(I1720/I1615)の最大値が、0.45以上0.80以下の範囲となるように樹脂層形成条件を決定する容器用樹脂被覆金属板の製造方法。
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2015530190A JP5892294B2 (ja) | 2014-02-21 | 2015-02-17 | 容器用樹脂被覆金属板およびその製造方法 |
US15/117,877 US9993998B2 (en) | 2014-02-21 | 2015-02-17 | Resin-coated metal sheet for containers and method for manufacturing the same |
NZ721898A NZ721898A (en) | 2014-02-21 | 2015-02-17 | Resin-coated metal sheet for containers and method for manufacturing the same |
CA2939469A CA2939469C (en) | 2014-02-21 | 2015-02-17 | Resin-coated metal sheet for containers and method for manufacturing the same |
EP15751613.9A EP3109178B1 (en) | 2014-02-21 | 2015-02-17 | Resin-coated metal plate for container and production method therefor |
KR1020167025761A KR101951291B1 (ko) | 2014-02-21 | 2015-02-17 | 용기용 수지 피복 금속판 및 그 제조 방법 |
AU2015220288A AU2015220288C1 (en) | 2014-02-21 | 2015-02-17 | Resin-coated metal sheet for containers and method for manufacturing the same |
CN201580009284.3A CN106029511B (zh) | 2014-02-21 | 2015-02-17 | 容器用树脂被覆金属板和其制造方法 |
PH12016501531A PH12016501531A1 (en) | 2014-02-21 | 2016-08-03 | Resin-coated metal sheet for containers and method for manufacturing the same |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014-031206 | 2014-02-21 | ||
JP2014031206 | 2014-02-21 | ||
JPPCT/JP2014/004712 | 2014-09-11 | ||
PCT/JP2014/004712 WO2015125184A1 (ja) | 2014-02-21 | 2014-09-11 | 容器用樹脂被覆金属板およびその製造方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015125459A1 true WO2015125459A1 (ja) | 2015-08-27 |
Family
ID=53877728
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/004712 WO2015125184A1 (ja) | 2014-02-21 | 2014-09-11 | 容器用樹脂被覆金属板およびその製造方法 |
PCT/JP2015/000717 WO2015125459A1 (ja) | 2014-02-21 | 2015-02-17 | 容器用樹脂被覆金属板およびその製造方法 |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/004712 WO2015125184A1 (ja) | 2014-02-21 | 2014-09-11 | 容器用樹脂被覆金属板およびその製造方法 |
Country Status (12)
Country | Link |
---|---|
US (1) | US9993998B2 (ja) |
EP (1) | EP3109178B1 (ja) |
JP (1) | JP5892294B2 (ja) |
KR (1) | KR101951291B1 (ja) |
CN (1) | CN106029511B (ja) |
AU (1) | AU2015220288C1 (ja) |
CA (1) | CA2939469C (ja) |
MY (1) | MY179155A (ja) |
NZ (1) | NZ721898A (ja) |
PH (1) | PH12016501531A1 (ja) |
TW (2) | TWI527688B (ja) |
WO (2) | WO2015125184A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016093219A1 (ja) * | 2014-12-12 | 2016-06-16 | Jfeスチール株式会社 | 缶蓋用樹脂被覆金属板 |
CN108778717A (zh) * | 2016-03-10 | 2018-11-09 | 新日铁住金株式会社 | 容器用金属板及其制造方法 |
WO2021131765A1 (ja) | 2019-12-23 | 2021-07-01 | Jfeスチール株式会社 | 樹脂被覆金属板並びに樹脂被覆絞りしごき缶およびその製造方法 |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107405881B (zh) * | 2015-03-26 | 2019-07-09 | 杰富意钢铁株式会社 | 容器用树脂被覆金属板 |
US11027523B2 (en) * | 2015-11-30 | 2021-06-08 | Toray Plastics (America), Inc. | Polyester film incorporating silicone for release of canned meat products |
JP6281668B1 (ja) * | 2016-06-17 | 2018-02-21 | Jfeスチール株式会社 | 金属容器蓋用ラミネート金属板及びその製造方法 |
US10815347B2 (en) * | 2016-08-11 | 2020-10-27 | Toray Plastics (America), Inc. | Blush-resistant film including pigments |
EP3566867B1 (en) * | 2017-01-04 | 2022-03-30 | Toray Advanced Materials Korea Inc. | Polyester-based glass texture decorative sheet |
CA3085410C (en) | 2017-12-15 | 2022-11-29 | Jfe Steel Corporation | Resin-coated metal sheet for container |
CN110920171A (zh) * | 2018-09-19 | 2020-03-27 | 宝山钢铁股份有限公司 | 一种聚酯覆铁膜的制备方法以及覆膜金属容器 |
CN110920184A (zh) * | 2018-09-19 | 2020-03-27 | 宝山钢铁股份有限公司 | 一种共混聚酯覆铁膜的制备方法及其覆膜金属板 |
CN110920172A (zh) * | 2018-09-19 | 2020-03-27 | 宝山钢铁股份有限公司 | 一种聚酯覆铁膜以及覆膜金属板 |
CN111765300A (zh) * | 2020-06-16 | 2020-10-13 | 临海伟星新型建材有限公司 | 一种阻隔复合管及其制备方法 |
KR20220054849A (ko) * | 2020-06-18 | 2022-05-03 | 미쯔이가가꾸가부시끼가이샤 | 크실릴렌디이소시아네이트가 들어간 용기, 크실릴렌디이소시아네이트의 보관 방법 및 크실릴렌디이소시아네이트의 수송 방법 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007253453A (ja) * | 2006-03-23 | 2007-10-04 | Jfe Steel Kk | 容器用樹脂被覆金属板 |
JP2008188918A (ja) * | 2007-02-06 | 2008-08-21 | Jfe Steel Kk | 容器用樹脂被覆金属板 |
WO2013030972A1 (ja) * | 2011-08-31 | 2013-03-07 | Jfeスチール株式会社 | 樹脂被膜金属板 |
WO2013157379A1 (ja) * | 2012-04-19 | 2013-10-24 | Jfeスチール株式会社 | ラミネート金属板および食品用缶詰容器 |
Family Cites Families (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3891471A (en) * | 1972-05-01 | 1975-06-24 | Robertson Bauelemente Gmbh | Method of making protected galvanized steel sheeting |
GB9423182D0 (en) * | 1994-11-17 | 1995-01-04 | Ici Plc | Polymeric film |
US20030031859A1 (en) | 2000-01-24 | 2003-02-13 | Sinsel John A. | Processing and apparatus for production of engineered composite combining continuous-strip sheet metal and thermoplastic polymers |
JP4343383B2 (ja) * | 2000-03-02 | 2009-10-14 | 東洋製罐株式会社 | 樹脂被覆シームレス缶 |
JP3692953B2 (ja) * | 2000-03-16 | 2005-09-07 | Jfeスチール株式会社 | 容器用フィルムラミネート金属板 |
CA2440334C (en) * | 2001-03-14 | 2010-08-17 | Jfe Steel Corporation | Film-laminated metal sheet for container |
TW542812B (en) * | 2001-11-26 | 2003-07-21 | Irene H Lin | Method for manufacturing a packaging container |
DE10204829C1 (de) * | 2002-02-06 | 2003-07-17 | Gerd Hugo | Flächiges Bauelement aus Metall |
WO2004065120A1 (ja) * | 2003-01-21 | 2004-08-05 | Teijin Dupont Films Japan Limited | 積層フィルム |
JP2004345232A (ja) | 2003-05-22 | 2004-12-09 | Jfe Steel Kk | 熱処理後の加工性に優れた缶用ラミネート金属板 |
CA2565277C (en) * | 2004-05-31 | 2010-04-13 | Jfe Steel Corporation | Resin-coated metal sheet |
JP4806933B2 (ja) * | 2005-01-28 | 2011-11-02 | Jfeスチール株式会社 | ポリエステル樹脂ラミネート金属容器 |
EP1688188B1 (en) * | 2005-02-02 | 2012-04-11 | Toyo Kohan Co., Ltd. | Metal plate coated with polyester resin, and can using the same |
JP5076385B2 (ja) | 2005-07-28 | 2012-11-21 | Jfeスチール株式会社 | 容器用樹脂被覆金属板および樹脂被覆金属缶 |
US7737246B2 (en) * | 2005-12-15 | 2010-06-15 | Eastman Chemical Company | Polyester compositions which comprise cyclobutanediol, cyclohexanedimethanol, and ethylene glycol and manufacturing processes therefor |
JP5082269B2 (ja) * | 2006-03-23 | 2012-11-28 | Jfeスチール株式会社 | 容器用樹脂被覆金属板 |
DE102007015393A1 (de) * | 2007-03-28 | 2008-10-02 | Henkel Ag & Co. Kgaa | Mehrfach beschichtetes Metallsubstrat und Verfahren zu seiner Herstellung |
JP4998153B2 (ja) * | 2007-08-30 | 2012-08-15 | 東レ株式会社 | 積層ポリエステルフィルム |
JP5509575B2 (ja) * | 2008-10-30 | 2014-06-04 | Jfeスチール株式会社 | 容器用樹脂被覆金属板 |
BRPI0921653A2 (pt) * | 2008-11-25 | 2016-02-10 | Valspar Sourcing Inc | artigo, método, filme, e, método para afixar o filme |
JP4787372B1 (ja) * | 2010-08-05 | 2011-10-05 | 住友軽金属工業株式会社 | 樹脂被覆アルミニウム合金板 |
EP4357264A3 (en) * | 2010-10-15 | 2024-07-31 | Swimc Llc | Polyester-based coating composition for metal substrates |
-
2014
- 2014-09-11 WO PCT/JP2014/004712 patent/WO2015125184A1/ja active Application Filing
- 2014-09-19 TW TW103132415A patent/TWI527688B/zh active
-
2015
- 2015-02-17 CA CA2939469A patent/CA2939469C/en active Active
- 2015-02-17 NZ NZ721898A patent/NZ721898A/en not_active IP Right Cessation
- 2015-02-17 CN CN201580009284.3A patent/CN106029511B/zh active Active
- 2015-02-17 AU AU2015220288A patent/AU2015220288C1/en not_active Ceased
- 2015-02-17 US US15/117,877 patent/US9993998B2/en active Active
- 2015-02-17 MY MYPI2016703004A patent/MY179155A/en unknown
- 2015-02-17 WO PCT/JP2015/000717 patent/WO2015125459A1/ja active Application Filing
- 2015-02-17 KR KR1020167025761A patent/KR101951291B1/ko active IP Right Grant
- 2015-02-17 JP JP2015530190A patent/JP5892294B2/ja active Active
- 2015-02-17 TW TW104105650A patent/TWI558549B/zh active
- 2015-02-17 EP EP15751613.9A patent/EP3109178B1/en active Active
-
2016
- 2016-08-03 PH PH12016501531A patent/PH12016501531A1/en unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007253453A (ja) * | 2006-03-23 | 2007-10-04 | Jfe Steel Kk | 容器用樹脂被覆金属板 |
JP2008188918A (ja) * | 2007-02-06 | 2008-08-21 | Jfe Steel Kk | 容器用樹脂被覆金属板 |
WO2013030972A1 (ja) * | 2011-08-31 | 2013-03-07 | Jfeスチール株式会社 | 樹脂被膜金属板 |
WO2013157379A1 (ja) * | 2012-04-19 | 2013-10-24 | Jfeスチール株式会社 | ラミネート金属板および食品用缶詰容器 |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2016093219A1 (ja) * | 2014-12-12 | 2016-06-16 | Jfeスチール株式会社 | 缶蓋用樹脂被覆金属板 |
JPWO2016093219A1 (ja) * | 2014-12-12 | 2017-04-27 | Jfeスチール株式会社 | 缶蓋用樹脂被覆金属板 |
US10399303B2 (en) | 2014-12-12 | 2019-09-03 | Jfe Steel Corporation | Resin-coated metal sheet for can lids |
CN108778717A (zh) * | 2016-03-10 | 2018-11-09 | 新日铁住金株式会社 | 容器用金属板及其制造方法 |
WO2021131765A1 (ja) | 2019-12-23 | 2021-07-01 | Jfeスチール株式会社 | 樹脂被覆金属板並びに樹脂被覆絞りしごき缶およびその製造方法 |
Also Published As
Publication number | Publication date |
---|---|
KR20160124836A (ko) | 2016-10-28 |
PH12016501531B1 (en) | 2016-10-03 |
TWI558549B (zh) | 2016-11-21 |
EP3109178A1 (en) | 2016-12-28 |
EP3109178B1 (en) | 2020-01-15 |
CA2939469C (en) | 2018-12-18 |
MY179155A (en) | 2020-10-29 |
US9993998B2 (en) | 2018-06-12 |
WO2015125184A1 (ja) | 2015-08-27 |
NZ721898A (en) | 2018-06-29 |
AU2015220288A1 (en) | 2016-07-21 |
CA2939469A1 (en) | 2015-08-27 |
US20170008256A1 (en) | 2017-01-12 |
TWI527688B (zh) | 2016-04-01 |
CN106029511B (zh) | 2018-01-12 |
EP3109178A4 (en) | 2017-03-22 |
JPWO2015125459A1 (ja) | 2017-03-30 |
PH12016501531A1 (en) | 2016-10-03 |
AU2015220288B2 (en) | 2017-12-14 |
KR101951291B1 (ko) | 2019-02-22 |
CN106029511A (zh) | 2016-10-12 |
AU2015220288C1 (en) | 2018-07-26 |
JP5892294B2 (ja) | 2016-03-23 |
TW201544310A (zh) | 2015-12-01 |
TW201532803A (zh) | 2015-09-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5892294B2 (ja) | 容器用樹脂被覆金属板およびその製造方法 | |
JP6028886B1 (ja) | 容器用樹脂被覆金属板 | |
JP5812232B1 (ja) | 容器用樹脂被覆金属板およびその製造方法 | |
WO2013099563A1 (ja) | ラミネート金属板および食品用缶詰容器 | |
FR2660240A1 (fr) | Feuille metallique stratifiee avec un film de resine copolyester et son procede de fabrication. | |
JP2005342911A (ja) | 容器用樹脂被覆金属板 | |
WO2019009108A1 (ja) | 樹脂被覆金属板、その樹脂被覆金属板を加工して成る金属缶 | |
JP4826419B2 (ja) | 容器用樹脂被覆金属板 | |
FR2653703A1 (fr) | Feuille metallique stratifiee avec un film de resine copolyester et procede pour sa production. | |
TWI686304B (zh) | 容器用金屬板及其製造方法 | |
JP2009221315A (ja) | 金属板ラミネート用フィルム、フィルムラミネート金属板、および金属容器 | |
WO2021020555A1 (ja) | 樹脂被覆金属板、容器、及びレトルト白化性改善方法 | |
WO2005095104A1 (ja) | 樹脂被覆金属板 | |
JP2018140565A (ja) | 金属板貼り合わせ成形加工用積層フィルム | |
JP2005154462A (ja) | 金属板ラミネート用フィルム、フィルムラミネート金属板、および金属容器 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2015530190 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15751613 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2015220288 Country of ref document: AU Date of ref document: 20150217 Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 12016501531 Country of ref document: PH |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15117877 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 2939469 Country of ref document: CA |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20167025761 Country of ref document: KR Kind code of ref document: A |
|
REEP | Request for entry into the european phase |
Ref document number: 2015751613 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2015751613 Country of ref document: EP |