WO2002092689A2 - Materiau en feuille de resine a base de polyester et plaque metallique revetue de resine au moyen du materiau en feuille de resine - Google Patents

Materiau en feuille de resine a base de polyester et plaque metallique revetue de resine au moyen du materiau en feuille de resine Download PDF

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Publication number
WO2002092689A2
WO2002092689A2 PCT/JP2002/004599 JP0204599W WO02092689A2 WO 2002092689 A2 WO2002092689 A2 WO 2002092689A2 JP 0204599 W JP0204599 W JP 0204599W WO 02092689 A2 WO02092689 A2 WO 02092689A2
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WO
WIPO (PCT)
Prior art keywords
resin
component
metal plate
sheet
polyester resin
Prior art date
Application number
PCT/JP2002/004599
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English (en)
Japanese (ja)
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WO2002092689A3 (fr
WO2002092689A1 (fr
Inventor
Hiroshi Sakamoto
Toshiaki Ebitani
Yasuhiro Takaki
Original Assignee
Mitsubishi Plastics Inc
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Publication date
Application filed by Mitsubishi Plastics Inc filed Critical Mitsubishi Plastics Inc
Priority to KR1020037012910A priority Critical patent/KR100837254B1/ko
Priority to JP2002589566A priority patent/JP4133345B2/ja
Publication of WO2002092689A2 publication Critical patent/WO2002092689A2/fr
Publication of WO2002092689A1 publication Critical patent/WO2002092689A1/fr
Publication of WO2002092689A3 publication Critical patent/WO2002092689A3/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds

Definitions

  • the present invention relates to a polyester resin sheet-like material and a resin-coated metal plate using the same.
  • a printing layer is provided on a predetermined resin layer, and a transparent layer is further provided thereon.
  • a transparent resin film is further provided thereon.
  • the transparent resin film in this configuration include an ethylene-vinyl alcohol copolymer film having a thickness of 10 to 50 m, an acrylate copolymer film, and a biaxially stretched polyethylene terephthalate resin (PET).
  • PET biaxially stretched polyethylene terephthalate resin
  • a film or the like is generally used, and among them, a biaxially stretched PET film having an excellent balance of various physical properties and an excellent transparency of an underlying printed layer is preferably used.
  • the resin layer generally, a layer obtained by adding a pigment and coloring is used.
  • a soft vinyl chloride resin layer is generally used. This soft vinyl chloride resin is used by adding a plasticizer to the vinyl chloride resin. Since the flexibility can be changed arbitrarily, a transparent biaxially stretched PET film is laminated to form a laminated film.
  • the laminated film not only has good workability, but also soft vinyl chloride resin has excellent acid resistance, alkali resistance, and other chemical resistance, as well as heat resistance, hot water resistance (boiling water resistance), etc. This is because sufficient workability can be imparted even in the use as a so-called pre-coated steel sheet, and it can be preferably used in applications such as a bath unit.
  • polypropylene is used instead of soft vinyl chloride resin.
  • a thermoplastic resin such as styrene or copolymerized olefin as a softening component
  • a polyolefin resin such as That is used.
  • a metal plate coated with a polyester resin can have both a scratch resistance and a workability higher than that of a soft vinyl chloride resin-coated metal plate.
  • Various disadvantages can be eliminated.
  • the glass transition temperature (T g) is 1 Since the value is lower than 00, the boiling water resistance test generally included as an evaluation item of the resin-coated metal sheet for building interior cannot be satisfied.
  • polyethylene terephthalate was used as the resin for forming the colored resin layer.
  • PET polybutylene terephthalate
  • the present invention provides excellent workability and scratch resistance without using a halogen-containing resin.
  • a resin-coated metal sheet having excellent chemical resistance such as hot water resistance (boiling water resistance) and alkali resistance
  • a polyester resin sheet suitable for producing the resin-coated metal sheet The purpose is to provide things.
  • the above-mentioned problem was solved by using a polyester resin sheet having excellent alkali resistance and boiling water resistance.
  • Component (bl) a polyester resin having a heat of crystal fusion of 10 [J Zg] or less as observed by a differential scanning calorimeter.
  • Component (b 2) a polyester resin having a crystal melting peak observed by a differential scanning calorimeter and having a calorific value of 30 [J ng] or more.
  • the above-mentioned polyester resin sheet has excellent scratch resistance and workability since the entire sheet is made of a polyester resin.
  • the component (b1) ensures alkali resistance, and the component (b2) ensures boiling water resistance.
  • the component (b2) is a polybutylene terephthalate-based resin
  • the mixing ratio of the component (bl) and the component (b2) ((bl) / (b2) ) can be in the range of 60 to 80 to 40 to 20 by weight.
  • (b 2) Polyethylene terephthalate-based resin is used as a component, so that a sheet-like material is formed by extrusion molding from a polyester-based resin as compared with the case of using polyethylene terephthalate-based resin. The workability at the time is improved.
  • the component (b2) is a polypropylene terephthalate resin
  • the mixing ratio of the component (bl) and the component (b2) ((b1) / (b2 )) Can range from 60 to 80Z40 to 20 by weight.
  • the component (b 2) Polypropylene terephthalate resin is used as the component, so its workability is as good as that of polybutylene terephthalate, and its physical properties are between polyethylene terephthalate and polybutylene terephthalate. Get better. Further, in the above-mentioned polyester-based resin sheet, the component (b2) is a polybutylene terephthalate-based resin, and the mixing ratio of the component (bl) and the component (b2) ((bl) / (b2 )) Can be in the range of 50 to 65 to 50 to 35 by weight.
  • a polybutylene terephthalate-based resin is used as the component (b 2), it is extruded from a polyester-based resin as compared with the case of using a polyethylene terephthalate-based resin. The processability when molding the sheet-to-sheet in the form is improved.
  • the component (b2) is a polypropylene-terephthalate-based resin
  • the mixing ratio of the component (bl) and the component (b2) ((b1) / ( b 2)) can be in the range of 50 to 650 to 35 by weight.
  • (b 2) Polypropylene terephthalate resin is used as the component, so its workability is as good as polybutylene terephthalate, and its physical properties are between polyethylene terephthalate and polybutylene terephthalate. Get better.
  • the resin-coated metal sheet can be obtained by coating the surface of the base metal sheet (A) with any one of the above-mentioned polyester-based resin sheet (B).
  • polyester resin sheet (B) is coated on the surface of the base metal plate (A), it is excellent in workability and scratch resistance without using halogen-containing resin such as soft vinyl chloride resin. It is possible to obtain a resin-coated metal plate having excellent hot water resistance and alkali resistance.
  • a transparent resin film (C) is laminated on a colored polyester resin sheet ( ⁇ ′) in which a coloring agent is blended as a constituent component in any of the above polyester resin sheet (B).
  • the sheet-like material is coated on the surface of the base metal plate ( ⁇ ) to obtain a resin-coated metal plate.
  • a resin-coated metal plate can be obtained by coating the surface of the base metal plate (A) with a laminated sheet in which films ((C)) are sequentially laminated.
  • a coating type adhesive layer ( ⁇ ) is provided to enable lamination and integration.
  • a biaxially stretched polyethylene terephthalate-based resin sheet can be used as the transparent resin film (C).
  • FIG. 1 is a sectional view showing an example of the resin-coated metal plate according to the present invention
  • FIG. 2 is a sectional view showing another example of the resin-coated metal plate according to the present invention
  • FIG. 3 is a resin-coated metal plate according to the present invention
  • FIG. 4 is a sectional view showing another example of the plate
  • FIG. 4 is a sectional view showing another example of the resin-coated metal plate according to the present invention.
  • the polyester resin sheet (B) according to the present invention is a sheet obtained by mixing a mixture of a polyester resin composed of two kinds of predetermined components at a predetermined ratio, and the resin according to the present invention.
  • the coated metal plate is obtained by coating the surface of the base metal plate (A) with the polyester resin sheet (B).
  • the term “sheet” means a sheet or a film. This sheet and film are distinguished from each other in the same way as in the normal case, when the thickness is less than 0.25 mm (250 m), it is regarded as the film, and when the thickness is 0.225 mm or more, the sheet is considered.
  • the polyester-based resin sheet (B) is a sheet obtained by mixing a mixture of the following components (b1) and (b2).
  • the component (bl) is a polyester resin that functions to improve the alkali resistance of the polyester resin sheet (B), and has a crystal melting heat of 10 [JZg] observed by a differential scanning calorimeter. It must be: When the heat of crystal fusion exceeds 10 [J / g], the alkali resistance of the polyester resin sheet (B) cannot be improved, which is not preferable.
  • the polyester resin constituting the above-mentioned component (bl) includes ethylene glycol, propylene glycol, 1,4-cyclohexanedimethanol or the like as a diol component and ethylene terephthalate or disophthalic acid as a dicarboxylic acid component.
  • a refractory copolymer polyester is preferably used.
  • the proportion of each diol component and dicarbonic acid component is appropriately selected such that the heat of crystal fusion of the obtained polyester resin, as measured by a differential scanning calorimeter, is 10 [JZg] or less.
  • polyester resin constituting the component (b1) examples include Eastman Chemical Co., Ltd. in which about 30 to 60 mol% of ethylene glycol of polyethylene terephthalate is substituted with 1,4-cyclohexanedimethanol.
  • PET-G a copolymer containing terephthalic acid as the dicarboxylic acid component and ethylene glycol and 1,4-cyclohexanedimethanol as the diol component, with a high ratio of 1,4-cyclohexanedimethanol
  • PCTG a copolymer containing terephthalic acid as the dicarboxylic acid component and ethylene glycol and 1,4-cyclohexanedimethanol as the diol component
  • the polyester resin that constitutes the (bl) component has low crystallinity and can be used alone. It has excellent resilience, but at temperatures exceeding T g, the elastic modulus drops sharply and becomes flexible.
  • Tg of polyester resin is 100 or less, and when such a low-crystalline polyester resin is coated on a metal plate, it softens in boiling water and swells on the surface due to foaming. .
  • the component (b2) is a polyester resin that functions to improve the boiling water resistance of the polyester resin sheet (B), and has a crystal melting peak observed by a differential scanning calorimeter. It is necessary that the heat of fusion of the crystal is 30 [J / g] or more. If the heat of crystal fusion is less than 30 [J / g], the modulus of elasticity at a temperature above the glass transition temperature (T g) decreases, and the boiling water resistance decreases, which is not preferable.
  • polyester resin constituting the component (b2) ethylene glycol, propylene glycol, 1,4-cyclohexanedimethanol and the like are used as the diol component, and terephthalic acid and isophthalic acid are used as the dicarboxylic acid component.
  • Ethylene terephthalate-based copolymerized polyester is preferably used.
  • the proportion of each diol component and dicarboxylic acid component is appropriately selected such that the heat of crystal fusion of the obtained polyester resin, which is observed by a differential scanning calorimeter, is 30 [J / g] or more.
  • polyester resin constituting the component (b2) examples include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polypropylene terephthalate or polytrimethylene terephthalate (PPT), or a copolymer thereof. Polymers and the like can be mentioned.
  • the intrinsic viscosity (IV value) is preferably 0.7 or more from the viewpoint of film forming properties.
  • the polyester resin having a heat of crystal fusion of 30 [J / g] or more retains its elastic modulus at a temperature exceeding T g as long as it is at or below the melting point. Poor alkalinity.
  • the more preferable blending amount of the component (b 2) is different depending on whether or not the resin-coated metal plate using the obtained polyester resin sheet is required to have a mirror surface.
  • Z (b2) 60 ⁇ 8004 0 ⁇ 20 is more preferable for 80Z5 0 ⁇ 20, ⁇ ⁇ ⁇ and PPT, and it is necessary to make the (b 1) component excessive It is.
  • (b 2) is less than the above range, sufficient boiling water resistance may not be obtained.
  • (b 2) is more than the above range, the resin using the obtained polyester resin sheet material may be used.
  • the coated metal plate is formed and the transparent resin film (C) described later is not laminated, a problem may occur in the alkali resistance.
  • the above-mentioned resin-coated metal plate on which a transparent resin film (C) to be described later is laminated delamination of the transparent resin film (C) occurs in the deformed portion, and the durability of the processed portion may be insufficient.
  • (b 2) when (b 2) is within the above range, it has a sufficient surface hardness and is excellent in boiling water resistance. Moreover, regardless of the presence or absence of the transparent resin film (C) to be described later, it has excellent alkali resistance, especially when the transparent resin film (C) is laminated and when the transparent resin film (C) is damaged. Even so, it has excellent alkali resistance. Furthermore, the above-mentioned resin-coated metal plate on which the transparent resin film (C) described below is laminated does not easily cause delamination of the transparent resin film (C) in the deformed portion, and can sufficiently withstand use. Having.
  • (b 2) when (b 2) is within the above range, it has sufficient surface hardness and excellent boiling water resistance. Moreover, regardless of the presence or absence of the lamination of the transparent resin film (C) described later, it has alkali resistance and can sufficiently withstand use. In particular, when the transparent resin film (C) is laminated, even if the transparent resin film (C) is damaged, it has alkaline resistance and can sufficiently withstand use. Furthermore, the resin-coated metal plate on which the transparent resin film (C) ′ described below is laminated does not cause delamination of the transparent resin film (C) in the deformed portion, and is excellent in durability of the processed portion. It will be.
  • the heat of crystal fusion of the component (b1) is preferably 10 JZg or less, and the heat of crystal fusion of the component (b2) is preferably 30 Jnog or more. If the heat of crystal fusion of the component (b 1) exceeds 10 J / g, alkali resistance may not be improved. If the heat of crystal fusion of the component (b 2) is less than 30 JZg, the modulus of elasticity at or above T g may decrease, and the boiling water resistance may decrease.
  • a colorant can be added to the mixture of the component (b1) and the component (b2) constituting the polyester resin sheet (B).
  • a colored polyester resin sheet (B ′) can be obtained.
  • This colored polyester-based resin sheet ( ⁇ ′) can perform functions such as hiding the underlying base metal plate ( ⁇ ), imparting design properties, and improving the color developability of the printed layer.
  • the coloring agent used for the purpose of coloring the resin may be a conventionally known pigment for coloring the resin, and the compounding amount can be selected in a general amount when coloring the resin.
  • the mixture of the component (bl) and the component (b2) constituting the polyester resin sheet ( ⁇ ⁇ ⁇ ) contains, in addition to the colorant, various kinds of additives that do not impair the object of the present invention. It can be added in an amount that does not impair the purpose of the present invention.
  • additives include heat stabilizers, phosphorus- and phenol-based antioxidants, hydrolysis inhibitors, ultraviolet absorbers, light stabilizers, nucleating agents, metal deactivators, antibacterial and antifungal agents, Examples include antistatic agents, lubricants, flame retardants, and fillers.
  • the polyester resin sheet (B) of the present invention is produced by a known film forming method.
  • an extrusion casting method or an inflation method using a T-die can be used, and the method is not particularly limited.
  • An extrusion casting method using a is preferred.
  • the molding temperature in the extrusion casting method using a T-die is appropriately adjusted depending on the flow characteristics and film-forming properties of the composition, but is generally from the melting point to 280, preferably from 240 to 270. The range in is preferred.
  • the thickness of the sheet material other than the colored polyester resin sheet material (B ′) in the polyester resin sheet material (B) is preferably selected from the range of 50 to 50011. preferable. When the thickness is less than 50 ⁇ m, when used for a resin-coated metal plate, the performance as a protective layer on the metal plate and the suitability for embossing are poor. On the other hand, when the thickness exceeds 500 m, the secondary workability such as punching for resin-coated metal sheets tends to be poor. Further, the thickness of the colored polyester-based resin sheet ( ⁇ ′) of the polyester-based resin sheet (B) is preferably selected in the range of 30 m to 250 m.
  • the thickness is less than 30 m, it is necessary to incorporate a large amount of special pigments, which are expensive, in order to impart sufficient underlayer hiding properties, making it difficult to form a film. It is not preferable because pinholes are easily formed in the film, and the effect of protecting the base metal plate (A) is reduced. If the thickness exceeds 250 m, the concealing effect of the underlying base metal and the protective effect of the base metal will be saturated even if it is thicker, and secondary processing such as punching and bending work will be required. This is not preferable because the properties are reduced and the raw material cost is increased.
  • the resin-coated metal plate according to the present invention will be described. As shown in FIG. 1, the resin-coated metal plate 1 according to the present invention is obtained by coating the surface of the base metal plate (A) 2 with the polyester resin sheet (B) 3 as shown in FIG. is there.
  • the base metal plate (A) 2 serves as a base material for the resin-coated metal plate according to the present invention.
  • the base metal plate (A) 2 is not particularly limited, and a metal plate used as a base material of a general resin-coated metal plate can be used as it is.
  • Specific examples include various types of steel sheets such as hot-rolled steel sheets, cold-rolled steel sheets, and stainless steel sheets, and aluminum sheets.
  • the steel plate may be one whose surface has been surface treated by plating or other methods.
  • the type of plating is not particularly limited, and examples include molten zinc plating, electric zinc plating, and tin plating. Surface treatments include chromate treatment and phosphoric acid coating treatment.
  • the thickness of the base metal plate (A) is Depending on the application of the grease-coated metal plate, it can be selected in the range of 0.1 to 10 mm.
  • a method for bonding the polyester resin sheet (B) 3 to the base metal plate (A) 2 as shown in FIG. 1, a method using an adhesive 4, although not shown, an adhesive is used. There are a method of heat-sealing without using and a method of extrusion coating, and the like is not particularly limited.
  • a polyester-based or epoxy-based adhesive 4 is applied to the surface of a base metal plate (A) 2 to which a polyester-based resin sheet (B) 3 is bonded, and a polyester-based resin sheet (B) 3 is applied.
  • the resin sheet (B) 3 There is a method of coating the resin sheet (B) 3.
  • a commonly used coating equipment such as a reverse mouth and a kiss roll is used, and a base metal plate (B) 3 to which a polyester resin sheet material (B) 3 is bonded.
  • A) Apply adhesive 4 on the surface of 2 so that the thickness of the dried adhesive is about 2 to 4 m. Then, the coated surface is dried and heated by an infrared heater and a hot-air heating furnace, and immediately while the surface temperature of the base metal plate (A) 2 is maintained at a temperature equal to or higher than the melting point of the polyester resin sheet material (B) 3, the roll laminating is performed.
  • the resin-coated metal sheet can be obtained by coating the polyester-based resin sheet-like material (B) 3 with overnight and cooling.
  • the above-mentioned colored polyester-based resin sheet ( ⁇ ′) is used as a film to be laminated on the resin-coated metal plate according to the present invention, it is not necessary to laminate it alone, but to A laminated sheet-like material obtained by laminating a transparent resin film-like material (C) or the like on a colored polyester-based resin sheet-like material ( ⁇ ′) may be laminated.
  • a resin-coated metal plate As such a resin-coated metal plate, as shown in FIG. 2, a laminated sheet-like material in which a transparent resin film (C) 5 is laminated on a colored polyester-based resin sheet ( ⁇ ′) 3 ′ is used. Resin-coated metal plate 1a coated on the surface of base metal plate ( ⁇ ) 2; colored polyester resin sheet ( ⁇ ') 3' as shown in Figs. 2 and 3; printing layer (D) 6 And a resin-coated metal plate 1b or 1c in which the surface of a base metal plate ( ⁇ ) 2 is coated with a laminated sheet in which a transparent resin film (C) 5 is sequentially laminated.
  • the printed layer (D) 6 When the printed layer (D) 6 is laminated, the printed layer (D) 6 may be laminated between the printed layer (D) 6 and the colored polyester resin sheet ( ⁇ ⁇ ′) 3 ′ or the base metal plate ( ⁇ ). ) Provide a coating type adhesive layer ( ⁇ ) 4 between 2) and the colored polyester resin sheet material ( ⁇ ') 3 and integrate them to form a resin-coated metal plate 1b or 1c. Can be.
  • the following example is a structural example of a resin-coated metal plate obtained by laminating a laminated sheet-like material obtained by laminating a transparent resin film-like material (C) or the like on the above colored polyester-based resin sheet-like material ( ⁇ ′). I can give it. “No” means the interface between adjacent layers. • Transparent resin film (C) Z-colored polyester resin sheet ( ⁇ ') Base metal plate ( ⁇ ) (See Fig. 2)
  • the resin that constitutes the transparent resin film (C) achieves these objects for the purpose of further improving scratch resistance, protecting the printed layer, imparting deep design properties, and improving various physical properties of the surface.
  • a biaxially stretched polyethylene terephthalate-based resin film is preferable from the viewpoints of transparency, smoothness, surface scratch resistance, and the like.
  • the thickness of the transparent resin film (C) is preferably smaller than that of the colored polyester resin sheet ( ⁇ ⁇ ⁇ ), and is selected in the range of 15111 to 7.
  • the printed layer (D) is formed on the back surface of the transparent resin film (C), and the design of the laminated sheet material coated on the resin-coated metal plate (A) can be further improved.
  • the method for forming the print layer is not particularly limited, and may be a conventionally known gravure printing method, offset printing method, screen printing method, or the like.
  • the printed pattern is not particularly limited, and may be any of stone-grained, wood-grained, geometric horizontal, and abstract patterns.
  • the printing of the print pattern may be any of solid printing, partial printing, and printing after printing the entire surface.
  • the lamination of the colored polyester resin film ( ⁇ ') and the transparent resin film (C) is as follows: (1) The two types of raw resin are melted separately and laminated in a co-extrusion die to form two layers. (2) Two types of resin films are manufactured by separate extruders, and a thermal welding method of bonding two types of resin films while both or one type of resin film is in a molten state; 3) A dry lamination method in which two types of resin films manufactured in advance are laminated via an adhesive can be used.
  • the adhesive (E) used in the method (3) is not particularly limited as long as it can bond two kinds of resin films.
  • the method for producing the laminated sheet used for the resin-coated metal plate containing the above-mentioned printing layer (D) is not particularly limited.
  • a printing layer (D) is formed on the back surface of the transparent resin film (C), and the surface of the printing layer (D) layer or the surface of the separately prepared colored polyester resin sheet (B) is
  • a method can be used in which a layer made of a coating-type adhesive (E) is provided, and the two are superimposed, passed through a pair of heated pressure rolls and adhered to be laminated. Conditions such as the heating temperature and pressure of the pressure roll can be appropriately selected depending on the type of the laminated sheet, the type of the adhesive, and the like.
  • the resin-coated metal sheet according to the present invention is manufactured by adhering the laminated sheet material to the surface of the base metal sheet (A).
  • the manufacturing method include a method using the above-mentioned adhesive, a method of heat-sealing without using an adhesive, and a method of extrusion coating, and are not particularly limited.
  • the above-mentioned method using an adhesive is used, the surface of the base metal plate (A) is subjected to an anchor treatment in advance, and then the adhesive is applied to the surface subjected to the anchor treatment, and the laminated film is laminated.
  • Glue examples of the adhesive include an epoxy-based adhesive and a urethane-based adhesive.
  • This adhesive can be applied by a conventionally known method such as a reverse coating method or a kiss coating method.
  • the applied adhesive is dried on the coated surface by infrared heater and hot air heating furnace.
  • the adhesive-coated surface of the base metal (A) is heated to a temperature equal to or higher than the melting point of the colored polyester resin ⁇ (B) component ⁇ , and the laminated film is overlaid on the adhesive-coated surface, and a pair of pressure rolls A resin-coated metal plate can be obtained by passing through the gap and integrating the adhesive.
  • the resin-coated metal sheet according to the present invention may be used for building wall materials, ceiling materials, partition wall materials, unit bus wall materials and ceiling materials, other architectural interior materials, home appliance manufacturing housings, and various other types. Used for industrial equipment. In particular, it is suitable for use as a unit bath wall material and ceiling material.
  • PET-G glass transition temperature (Tg); 81, crystal melting peak; none (hereinafter abbreviated as "PET-G")
  • PCTG glass transition temperature (Tg): 88, crystal melting peak; none (hereinafter abbreviated as “PCTG”)
  • Component (2) (b2) (crystalline polyester resin)
  • PBT Polybutylene terephthalate
  • PET Polyethylene terephthalate
  • a 50 mm X 60 mm resin-coated metal plate was immersed in boiling water for 3 hours, and the surface condition of the resin sheet was visually judged. If there was no change ( ⁇ ), the surface was slightly roughened. The bleeding was indicated as ( ⁇ ), and the swelling due to foaming was indicated as (X).
  • the impact adhesion bending test was performed as follows. Prepare a sample of 50 mm x 150 mm from the length and width directions of the resin-coated metal plate, hold it for 2 hours or more, and then use a bending tester to make a 180 ° (inner bending radius). 2 mm), and a cylindrical weight with a diameter of 75 mm and a mass of 5 kg was dropped on the sample from a height of 50 cm.
  • the components (b 1) and (b 2) are kneaded together with a black colorant using a twin-screw kneading extruder equipped with a T-die at the mixing ratio (% by weight) shown in Table 1 so as to be homogeneous. Then, a colored polyester resin sheet ( ⁇ ') having a thickness of 150 m was formed. Then glue
  • the blend amount of the component (b 2) (crystalline polyester-based resin) is 10% or more and 50% or less by weight (Examples 1 to 5), the boiling water resistance and the alkali resistance are low. It can be seen that the characteristics can be compatible. However, in the case where the weight percentage of the amorphous polyester resin (bl) is 90% (Example 5), both the boiling water resistance and the alkali resistance are compatible, but the surface hardness is slightly lowered. It is preferable that the weight of the hydrophilic polyester resin (b 2) is 20% or more. When polybutylene terephthalate is used as the crystalline polyester resin (b 2), the crystallization speed is high. Therefore, it is preferable to suppress the weight ratio to 40%.
  • the (b1) component and the (b2) component were weighed in proportions (% by weight) shown in Table 2, and mixed with a black colorant in a blender.
  • the obtained mixture was melted and kneaded using a twin-screw kneading extruder equipped with a T die at the tip, setting the cylinder temperature to a range of 240 t: -270:
  • a 0 m colored polyester resin film (B ') was prepared.
  • a biaxially stretched polyester film manufactured by Mitsubishi Chemical Polyester
  • C thickness of 25 m
  • a polyester adhesive is applied to this printed surface.
  • a polyester adhesive is applied to the entire surface of a zinc-plated steel plate (base metal plate (A)) with a width of 50 cm, a length of 100 cm and a thickness of 0.445 mm.
  • the adhesive is applied so that the thickness of the adhesive is about 2 to 4 _im.
  • the coated surface is dried and heated by a hot air heating furnace and infrared heater, and the surface temperature is set to the value of the colored polyester resin ( ⁇ '). Fusion
  • the laminated film was laminated by using a roll laminator and cooled to produce a resin-coated steel sheet.Evaluation of each item described above, and the processed part durability test shown below were performed. went. The evaluation results are summarized in Table 2.
  • JIS-K6744 Erriksen test
  • JIS-K5400 standard testing machine
  • the resin-coated side of the 50 mm x 60 mm resin-coated metal plate is the die side of the tester, and the center of the coated metal plate is aligned with the center of the punch, die, etc., and the punch is moved at a constant speed.
  • the coated metal plate was immersed in boiling water for 1 hour, taken out, and the appearance of the processed portion was visually evaluated. “ ⁇ ” indicates that there is no change from before boiling water immersion, “X” indicates that the surface biaxially stretched PET has noticeable lifting, and “X” indicates that the surface is relatively better than “X” but slight lifting is observed. Is designated as “ ⁇ ”.
  • the content of the crystalline polyester resin (b 2) in the resin component constituting the colored polyester resin film ( ⁇ ′) is in the range of 10 to 50% by weight, resin coating is performed.
  • the steel sheet is excellent in both boiling water resistance and alkali resistance (see Examples 6 to 11).
  • the content of the crystalline polyester resin (b 2) becomes 10% by weight or less
  • the resin component constituting the colored polyester resin film ( ⁇ ′) becomes resin-coated steel sheet coating resin. Since the surface hardness of the crystalline polyester resin decreases, it is preferable that the crystalline polyester resin is 10% by weight or more (see Comparative Example 9).
  • the resin component of the colored polyester resin film ( ⁇ ') is When only the non-crystalline polyester-based resin (bl) having no black mark (see Comparative Example 5), or when the content exceeds 90% by weight (see Comparative Example 9), the processability is excellent in any of the examples. However, the influence of the non-crystalline resin is strong, the surface hardness decreases, and the boiling water resistance is poor.
  • the crystalline polyester resin (b2) is polybutylene terephthalate (PBT) and the PBT content is 10% by weight, the durability of the processed part is not sufficient, The results of the test, surface hardness, boiling water test and alkali resistance test were good (see Example 11).
  • Example 7 In Example 7, in which the crystalline polyester resin (b 2) is polybutylene terephthalate (PBT) and the range of PBT is in the range of 20 to 40% by weight. Is excellent in alkali resistance, but the durability of the processed part is slightly inferior. Further, in Example 9, in which the range of PBT is in the range of 35 to 50% by weight, the durability of the processed portion is excellent, but the durability of the alkali resistance is slightly inferior. Further, since Example 8 falls within the range of both PBT described above, both the alkali resistance and the durability of the processed portion are excellent.
  • PBT polybutylene terephthalate
  • the component (b 2) can be used properly depending on which of the alkali resistance and the durability of the processed part is important.
  • This embodiment has the following effects.
  • the resin-coated metal plate is processed without using a halogen-containing resin such as a soft vinyl chloride resin because the above-mentioned polyester resin sheet is used as a coating material. Excellent heat resistance and scratch resistance, and also excellent hot water resistance and alkali resistance.
  • a halogen-containing resin such as a soft vinyl chloride resin
  • the resin-coated metal plate has excellent secondary workability and durability.
  • the embodiment is not limited to the above, and may be embodied as follows, for example.
  • the component (bl) of the amorphous polyester resin and the component (b2) of the crystalline polyester resin are not limited to those using one type of polyester resin, but may include a plurality of polyester resins. You may mix.
  • polyethylene terephthalate and polybutylene terephthalate, polyethylene terephthalate and polypropylene terephthalate, and polybutylene terephthalate and polypropylene terephthalate may be mixed.
  • the polyester resin sheet may have a thickness of 50 to 500 im.
  • the polyester resin sheet may be attached to the surface of a metal plate using an adhesive, and the thickness of the adhesive layer may be 2 to 4 ⁇ m.
  • the polyester resin sheet (B) containing the component (bl) and the component (b2) is excellent in workability and scratch resistance, and is also excellent in hot water resistance and alkali resistance.
  • the resin-coated metal sheet according to the fifth aspect of the invention has excellent workability and corrosion resistance without using a halogen-containing resin, and also has excellent hot water resistance and alkali resistance.
  • the resin-coated metal sheet according to the present invention does not use a soft vinyl chloride resin, VOC problems due to stabilizers and plasticizers, problems of endocrine disrupting effects, hydrogen chloride gas during combustion, and other problems are caused. There is no problem of generation of chlorine-containing gas.
  • the resin-coated metal plate according to the present invention is characterized in that the coating resin has a specific composition and a specific structure. Further, since the resin-coated metal plate according to the present invention is constituted by a laminated film having a specific composition and a specific structure, the coating resin is hardly scratched on the surface (excellent in scratch resistance), and the workability is improved. And so on.
  • the resin-coated metal plate according to the present invention is excellent in hot water resistance, chemical resistance, etc., because the coating resin is constituted by a laminated film having a specific composition and a specific structure.
  • the resin-coated metal sheet according to the present invention has an excellent balance of resistance to entrapment, workability, hot water resistance, and chemical resistance since the coating resin is formed of a laminated film having a specific composition and a specific structure. ing.
  • the printed layer (D) is disposed between the transparent resin layer (C) and the colored resin layer (B). As a result, the printed layer is protected, exhibits deep design, and has excellent aesthetics.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne une plaque métallique revêtue de résine présentant une usinabilité, une résistance à la susceptibilité, une résistance à l'eau chaude (résistance à l'eau bouillante), et une résistance chimique telle qu'une résistance alcali excellentes sans utiliser de résine contenant de l'halogène, et un matériau en feuille de résine à base de polyester convenant à la fabrication de la plaque métallique revêtue de résine qui comprend ce matériau en feuille de résine à base de polyester (B) sur sa surface de base (A).
PCT/JP2002/004599 2001-05-10 2002-05-10 Materiau en feuille de resine a base de polyester et plaque metallique revetue de resine au moyen du materiau en feuille de resine WO2002092689A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
KR1020037012910A KR100837254B1 (ko) 2001-05-10 2002-05-10 폴리에스테르계 수지 시트상 물질 및 이것을 이용한 수지피복 금속판
JP2002589566A JP4133345B2 (ja) 2001-05-10 2002-05-10 樹脂被覆金属板

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2001-140626 2001-05-10
JP2001140626 2001-05-10
JP2001158594 2001-05-28
JP2001-158594 2001-05-28

Publications (3)

Publication Number Publication Date
WO2002092689A2 true WO2002092689A2 (fr) 2002-11-21
WO2002092689A1 WO2002092689A1 (fr) 2002-11-21
WO2002092689A3 WO2002092689A3 (fr) 2007-10-11

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004243576A (ja) * 2003-02-12 2004-09-02 Nippon Steel Corp 金属被覆用樹脂フィルム並びに化粧樹脂被覆金属板の製造方法
JP2005111923A (ja) * 2003-10-10 2005-04-28 Riken Technos Corp 鋼板用化粧フィルム及び鋼板用積層化粧シート
JP2006297758A (ja) * 2005-04-20 2006-11-02 Mitsubishi Plastics Ind Ltd 金属板被覆用積層シートおよび積層シート被覆金属板
JP2008307700A (ja) * 2007-06-12 2008-12-25 Mitsubishi Plastics Inc 高意匠性樹脂シート被覆金属板、およびその製造方法
JP2009226612A (ja) * 2008-03-19 2009-10-08 Toppan Printing Co Ltd 化粧シートおよび化粧材
US8145179B2 (en) 2002-10-25 2012-03-27 Qualcomm Incorporated Data detection and demodulation for wireless communication systems
JP2014162833A (ja) * 2013-02-25 2014-09-08 Riken Technos Corp ポリエステル系樹脂組成物シート

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8145179B2 (en) 2002-10-25 2012-03-27 Qualcomm Incorporated Data detection and demodulation for wireless communication systems
JP2004243576A (ja) * 2003-02-12 2004-09-02 Nippon Steel Corp 金属被覆用樹脂フィルム並びに化粧樹脂被覆金属板の製造方法
JP2005111923A (ja) * 2003-10-10 2005-04-28 Riken Technos Corp 鋼板用化粧フィルム及び鋼板用積層化粧シート
JP2006297758A (ja) * 2005-04-20 2006-11-02 Mitsubishi Plastics Ind Ltd 金属板被覆用積層シートおよび積層シート被覆金属板
JP2008307700A (ja) * 2007-06-12 2008-12-25 Mitsubishi Plastics Inc 高意匠性樹脂シート被覆金属板、およびその製造方法
JP2009226612A (ja) * 2008-03-19 2009-10-08 Toppan Printing Co Ltd 化粧シートおよび化粧材
JP2014162833A (ja) * 2013-02-25 2014-09-08 Riken Technos Corp ポリエステル系樹脂組成物シート

Also Published As

Publication number Publication date
TWI261060B (en) 2006-09-01
KR20030093295A (ko) 2003-12-06
CN1294202C (zh) 2007-01-10
KR100837254B1 (ko) 2008-06-12
JPWO2002092689A1 (ja) 2004-11-18
WO2002092689A3 (fr) 2007-10-11
CN1636034A (zh) 2005-07-06
JP4133345B2 (ja) 2008-08-13

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