WO2020004427A1 - 温間プレス成形用樹脂被覆金属板および有機樹脂フィルム - Google Patents

温間プレス成形用樹脂被覆金属板および有機樹脂フィルム Download PDF

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WO2020004427A1
WO2020004427A1 PCT/JP2019/025260 JP2019025260W WO2020004427A1 WO 2020004427 A1 WO2020004427 A1 WO 2020004427A1 JP 2019025260 W JP2019025260 W JP 2019025260W WO 2020004427 A1 WO2020004427 A1 WO 2020004427A1
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Prior art keywords
resin layer
metal plate
resin
coated metal
warm press
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PCT/JP2019/025260
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English (en)
French (fr)
Japanese (ja)
Inventor
悦郎 堤
興 吉岡
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Toyo Kohan Co Ltd
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Toyo Kohan Co Ltd
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Priority to CN201980043228.XA priority Critical patent/CN112384365A/zh
Priority to JP2020527560A priority patent/JP7258024B2/ja
Publication of WO2020004427A1 publication Critical patent/WO2020004427A1/ja
Anticipated expiration legal-status Critical
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D22/00—Shaping without cutting, by stamping, spinning, or deep-drawing
    • B21D22/20—Deep-drawing
    • 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
    • B32B15/082—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 vinyl resins; comprising acrylic resins

Definitions

  • the present invention relates to a resin-coated metal plate for warm press forming applied on a metal plate, and more particularly to a resin-coated metal plate excellent in press formability and the like provided for warm press forming and can be applied thereto. It relates to an organic resin film.
  • a press die is heated to a high temperature of, for example, about 200 to 300 ° C. in order to reduce the load at the time of press working and improve the workability of aluminum itself. That is being done.
  • the aluminum to be subjected to the warm press forming is coated with a water-soluble acrylic resin containing colloidal silica to improve the warm press forming property of the aluminum. Is disclosed.
  • Patent Documents 1 to 4 cannot satisfy the needs of the market, and have the following problems.
  • Patent Documents 1 to 3 since a wax is contained as a lubricating film, there is a concern that the working environment is deteriorated due to the volatilization of components of the film due to heating during press molding. Further, since the lubricating film is deteriorated by heating, residues of the lubricating film may be generated after the molding, and it is undeniable that the lubricating film becomes a serious defect in a post-treatment process such as painting.
  • Patent Document 3 Although the acrylic resin contains silica to improve warm press formability, Patent Document 3 is based on the premise that the above-mentioned wax is contained in the first place, and is adopted as it is. However, Patent Document 4 does not mention a specific silica particle size.
  • the present invention has been made in view of solving such problems as an example, and has a resin-coated metal plate having excellent press formability in warm press working on difficult-to-process materials, and the resin-coated metal plate.
  • An object of the present invention is to provide an organic resin film applicable to a plate.
  • a resin-coated metal plate for warm press forming includes: (1) a metal plate, and an acrylic resin layer formed on the metal plate.
  • the acrylic resin layer is characterized in that the acrylic resin contains silica having an average particle size of less than 10 nm.
  • the acrylic resin layer preferably has a thickness of 1.5 ⁇ m or more.
  • the resin-coated metal plate for warm press molding according to the above (1) (3) further including a polyester resin layer interposed between the metal plate and the acrylic resin layer, wherein the polyester resin layer Preferably contains first carbon-based particles.
  • the polyester resin layer contains a sulfonate as a hydrophilic group, and has a glass transition temperature (Tg). Preferably it is below 100 ° C.
  • the sulfonic acid salt is preferably at least 4 mol% based on all dicarboxylic acid components in the polyester resin layer.
  • the sulfonate is preferably a sodium salt.
  • the sodium salt is preferably a sodium 5-sulfoisophthalate.
  • the first carbon-based particles are contained in an amount of 4 to 30% by weight based on the polyester resin layer. Preferably.
  • the acrylic resin layer contains less than 0.1% by weight of second carbon-based particles. Is preferred.
  • the acrylic resin layer preferably has a thickness of 0.5 ⁇ m to 3.0 ⁇ m.
  • the acrylic resin layer preferably contains 10 to 70% by weight of the silica.
  • an organic resin film according to an embodiment of the present invention is an organic resin film that is coated on a metal plate that is subjected to warm press molding, and has an acrylic resin layer having an average particle size of 10 nm. Characterized by containing less than 10% silica.
  • the present invention it is possible to provide a resin-coated metal plate capable of realizing excellent formability during warm press forming. Further, in addition to the moldability, it is also possible to provide a resin-coated metal plate which is excellent in conductivity during spot welding and in film removal after warm press forming.
  • the resin-coated metal plate for warm press forming in the present embodiment includes a metal plate 1 and an acrylic resin layer A formed on the metal plate, and the acrylic resin layer A has an average particle size in the acrylic resin. Contains less than 10 nm of silica S.
  • the present embodiment will be described with reference to the drawings.
  • the resin-coated metal plate 100 of the present embodiment is characterized in that an organic resin layer 10 is formed on at least one surface of a metal plate 1.
  • the organic resin layer 10 according to the present embodiment is characterized in that the acrylic resin layer A contains silica S.
  • a metal plate containing aluminum, iron, copper, titanium, magnesium, an alloy of the above metals such as an aluminum alloy or stainless steel, or the like is used.
  • aluminum, magnesium, titanium, alloys thereof, and stainless steel, which significantly improve workability in a temperature range of warm working (200 to 400 ° C.) are preferable.
  • aluminum alloys, magnesium alloys, titanium and titanium alloys are preferable from the viewpoint of excellent strength and lightness, and 3000, 5000, 6000, and 7000 series are preferred as aluminum alloys. Examples include AZ31, AZ61, AZ91, and Mg-Li type.
  • the thickness of the metal plate 1 is not particularly limited. That is, the thickness of the metal plate 1 can be appropriately selected depending on its use and the like. For example, the metal plate 1 having a thickness of 5 ⁇ m to 5 mm can be applied. For example, a suitable thickness is 0.5 to 3 mm for an automobile body panel and 20 ⁇ m to 1.5 mm for an electronic device, but is not limited thereto.
  • the acrylic resin used in the present embodiment is not particularly limited, and a known acrylic resin can be used.
  • examples of the monomer constituting the acrylic resin in the present embodiment include acrylic acid and methacrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth) Acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-octyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, etc.
  • Monoesters of polyhydric alcohols such as 4-hydroxybutyl (meth) acrylate and polyethylene glycol mono (meth) acrylate with acrylic acid or methacrylic acid; ⁇ -caprolactone adducts of the monoesters; maleic acid, fumaric acid, Acrylamide, acrylonitrile, vinyl acetate, styrene and the like can be exemplified.
  • the acrylic resin may be modified with an epoxy group in order to improve mechanical properties, chemical resistance, adhesiveness, and the like.
  • an epoxy group is introduced into the acrylic resin, the epoxy group can be introduced by copolymerizing with glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, or the like.
  • the acrylic resin used may be an acrylic resin obtained by polymerizing one or more of the above monomers, or a resin obtained by blending two or more of these acrylic resins. May be applied.
  • the acrylic resin may be used as a coating liquid, and in that case, any of a solvent-based, solvent-free, emulsion-based, and water-based coating liquid may be used.
  • the acrylic resin in the present embodiment it is preferable to use a resin having a sink depth of 0.3 ⁇ m to 3.0 ⁇ m when the following heat resistance test is performed.
  • a resin having a sink depth of 0.3 ⁇ m to 3.0 ⁇ m when the following heat resistance test is performed.
  • silica S described later in such an acrylic resin the silica S does not sink during warm press molding and can be held on the surface. As a result, contact between the metal mold and the metal plate 1 during warm press molding can be appropriately controlled, and good moldability can be obtained.
  • the above-mentioned heat resistance test means a test performed by the following method. First, a ring having a weight of 0.15 gf and a weight of 10 g are placed on the organic resin layer 10 of the resin-coated metal plate. Thereafter, the resin-coated metal plate is heated by a heating device so that the metal plate 1 has a temperature of 250 ° C., and is maintained for one minute. Next, the resin-coated metal plate is cooled down to room temperature, and after removing the weight from the organic resin layer 10, the depth of the dent formed on the surface of the organic resin layer 10 is measured, and the measured value is defined as the sinking depth. .
  • the organic resin layer 10 contains silica S.
  • the silica S contained in the organic resin layer 10 of the present embodiment is added to impart preferable moldability at the time of press molding or the like.
  • a silica source contained in the organic resin layer 10 of the present embodiment for example, silica powder may be used, or colloidal silica or organosilica in which silica is dispersed in a dispersion medium may be used.
  • the dispersion medium of silica may be water or an organic solvent such as alcohol, ether, and ketone.
  • the silica S contained in the organic resin layer 10 has an average particle diameter of less than 10 nm.
  • the average particle diameter of the silica S is 10 nm or more, when press molding or the like is performed, preferable moldability may not be obtained, which is not preferable.
  • the lower limit of the average particle size of the silica S is not particularly limited, but is preferably 1 nm or more from the viewpoint of easy availability.
  • the average particle diameter of the silica S in the present embodiment for example, a value measured by the Sears method can be used. Further, when a nominal value is described in a pamphlet of a manufacturer of the silica S to be used, the nominal value can be used as the average particle size of the silica S in the present embodiment.
  • the organic resin layer 10 it is not clear how the silica exists in the acrylic resin layer. However, as shown in FIG. 1, it can be estimated that single silica particles are individually dispersed or a plurality of silica particles are present in a state of being randomly aggregated. In addition, the surface of the organic resin layer 10 is not flat, and as shown in FIG. 1, it can be estimated that the surface of the organic resin layer 10 has irregularities formed by silica particles existing near the surface. Then, it can be estimated that the unevenness reduces the dynamic friction coefficient ( ⁇ ) at the time of press molding, and as a result, the above-described moldability is improved.
  • ⁇ dynamic friction coefficient
  • the reason why the moldability during press molding is excellent can be considered as follows. That is, when the average particle size of the silica S is less than 10 nm, the contact area between the contact surface between the surface of the mold and the surface of the organic resin layer 10 at each contact location becomes small due to the dispersed silica S. Therefore, since the load on each contact surface is reduced, the normal force is reduced and the frictional force is reduced. As a result, since the deformation and flow of the material of the metal plate 1 are smooth, it is considered that the formability at the time of press forming is improved.
  • the reason why preferable moldability cannot be obtained is considered as follows. That is, when the average particle size of the silica S is 10 nm or more, the contact surface between the surface of the mold at the time of molding and the surface of the organic resin layer 10 is locally present. Is thought to be larger. As a result, the normal force increases and the friction force increases. For this reason, it is expected that deformation and flow of the metal plate 1 are hindered, and in a severe case, the metal plate 1 is broken, resulting in inferior press formability.
  • the present inventors have found that, in a coating film having a thickness of 0.6 ⁇ m or more, particularly when the average particle diameter is 20 nm and 10 nm, the dynamic friction coefficient is hardly improved, whereas the average particle diameter is 10 nm.
  • the reason why the dynamic friction coefficient is remarkably improved by setting the value to be less than the above is considered as follows. That is, by setting the average particle diameter of the silica S to less than 10 nm, it is possible to suppress the sinking of the silica into the resin at the time of application, and as a result, the silica S on the surface or near the surface contributing to the molding increases.
  • the content of silica S in the present embodiment is less than 10% by weight, favorable moldability may not be obtained when the organic resin layer 10 is formed on the metal plate 1 and press-molded.
  • the content of silica S exceeds 70% by weight, the film formability when forming the organic resin layer 10 on the metal plate 1 may be reduced, and the formability during press molding may be reduced. Is not preferred.
  • the reason why the moldability may be reduced when the content of silica S exceeds 70% by weight is considered as follows. That is, when the content of silica S exceeds 70% by weight, it is considered that the flexibility of the organic resin layer 10 decreases. In that case, during press molding, the organic resin layer 10 cannot follow the deformation of the metal plate 1 and cracks occur, and as a result, the possibility that the metal mold 1 and the metal plate 1 come into direct contact increases. Therefore, it is considered difficult to obtain excellent press formability.
  • the content of the silica S contained in the organic resin layer 10 is more preferably 30 to 65% by weight, and even more preferably 45 to 60% by weight.
  • the thickness of the organic resin layer 10 of the present embodiment is preferably 1.5 ⁇ m or more when the organic resin layer 10 is directly formed on the metal plate 1 without intervening the lower layer as shown in FIG. More preferably, it is not less than 0.8 ⁇ m.
  • the thickness of the organic resin layer 10 is less than 1.5 ⁇ m, the metal plate 1 is locally exposed when molding is applied under severe conditions, and direct contact between the mold and the metal plate 1 may occur. Nature occurs. Therefore, there is a problem that it is difficult to obtain excellent press formability, which is not preferable.
  • the upper limit of the thickness of the organic resin layer 10 is not particularly limited, but from the viewpoint of cost, and from the viewpoint of easiness and workability in forming the organic resin layer 10 on the metal plate 1.
  • the thickness can be appropriately set.
  • the thickness is preferably 6.0 ⁇ m or less, more preferably 5.0 ⁇ m or less, and still more preferably 4.0 ⁇ m or less, due to difficulty in application.
  • the organic resin layer 10 is obtained by forming a film on the metal plate 1, it is easier to handle when the organic resin layer 10 has a certain thickness, and from this viewpoint, there is no problem even if the thickness is 5.0 ⁇ m to 100.0 ⁇ m.
  • the thickness is preferably 10.0 ⁇ m to 60.0 ⁇ m, and more preferably 20.0 ⁇ m to 30.0 ⁇ m.
  • the acrylic resin of the coating liquid may be any of a solvent type, a non-solvent type, an emulsion type, an aqueous type, and the like. Further, if necessary, there is no problem even if a curing agent or a photoinitiator is blended in the coating liquid within a range that does not affect the press moldability. Further, a leveling agent, an antifoaming agent, or the like may be added in order to improve applicability.
  • a known coating method such as a bar coater, a spin coater, a spray coat, a roll coater, and a squeezing roll after dipping the coating liquid can be applied.
  • a coating liquid of an acrylic resin containing silica having a particle diameter of less than 10 nm is applied to the surface of the metal plate 1 with a coater roll, and heated at a plate temperature of about 80 to 220 ° C. by a baking heating furnace. It is cooled by air cooling or a cooling device to produce a resin-coated metal plate.
  • a step of applying an adhesive with an adhesive application roll, baking and cooling to form an adhesive layer may be provided.
  • the coating film curing is not completed only by drying, the coating film curing can be completed by curing (for example, 40 ° C. for 3 days) or UV irradiation.
  • a method of manufacturing the resin-coated metal plate of the present embodiment a method of attaching an organic resin film to the metal plate 1 with or without an adhesive may be adopted.
  • a method of manufacturing the resin-coated metal plate shown in FIG. 1 by laminating an organic resin film by heat fusion will be described.
  • the metal plate 1 continuously fed from the metal plate supply means is heated to a temperature equal to or higher than the melting point of the organic resin film by using a heating means. Then, one side (or both sides) of the metal plate 1 is brought into contact with the organic resin film sent from the film supply means so as to be in contact with the metal plate 1. It is possible to produce a resin-coated metal plate by superposing between a pair of laminating rolls, pressing and laminating, and then quenching.
  • the acrylic resin layer A may contain various additives for improving moldability and corrosion resistance.
  • the additives include known silane coupling agents, lubricants, metal alkoxides, and the like.
  • the amount of the additive in the present embodiment, since it is possible to have a warm formability without containing a silane coupling agent, a lubricant, a metal alkoxide, etc., these additives are added. The amount may be less than 0.05%. Further, each of the above-mentioned additives may be contained alone, or two or more kinds may be contained.
  • the resin-coated metal plate 200 according to the present embodiment will be described with reference to FIG.
  • components having the same functions and effects as those of the above-described first embodiment are denoted by the same reference numerals, and further description thereof will be omitted as appropriate.
  • the second embodiment is characterized in that the workability of the resin-coated metal plate described in the first embodiment is improved, and a conductive function is further added.
  • the resin-coated metal plate 200 of the present embodiment shown in FIG. 2 has a polyester resin layer B formed between the acrylic resin layer A and the metal plate 1. Further, the polyester resin layer B contains carbon-based particles C (first carbon-based particles).
  • polyester resin layer B As the polyester resin used in the present embodiment, the following resins can be applied.
  • the polyvalent carboxylic acid component constituting the polyester resin layer B aromatic, aliphatic, or alicyclic dicarboxylic acids, trivalent or higher valent polycarboxylic acids, or ester derivatives thereof may be used.
  • the polyester resin layer B is preferably mainly composed of, for example, a dicarboxylic acid and a diol.
  • aromatic dicarboxylic acid examples include terephthalic acid, isophthalic acid, orthophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-dimethylterephthalic acid, biphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 1,2-bis Phenoxyethane-p, p'-dicarboxylic acid, phenylindanedicarboxylic acid and the like may be used as appropriate.
  • aliphatic and alicyclic dicarboxylic acids include succinic acid, adipic acid, sebacic acid, azelaic acid, dimer acid, dodecandionic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, , 4-cyclohexanedicarboxylic acid or the like, or an ester-forming derivative thereof may be used.
  • the glycol components constituting the polyester resin layer B include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2,4-dimethyl-2-ethyl Hexane-1,3-diol, neopentyl glycol, 2-ethyl-2-butyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-2-isobutyl-1, 3-propanediol, 3-methyl-1,5-pentan
  • polyester resin layer B examples include, for example, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene isophthalate, ethylene terephthalate, butylene terephthalate, 1,4-cyclohexanedimethyl terephthalate, ethylene isophthalate, butylene isophthalate And a polyester resin obtained by polymerizing at least one of ethylene naphthalate, ethylene adipate and butylene adipate. Further, a resin obtained by blending two or more of these polyester resins may be used.
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PBT polyethylene isophthalate
  • ethylene terephthalate ethylene terephthalate
  • butylene terephthalate 1,4-cyclohexanedimethyl terephthalate
  • ethylene isophthalate butylene isophthalate
  • the molecular weight (number average) of the polyester resin in the present embodiment is preferably 20,000 or less. If the molecular weight of the polyester resin exceeds 20,000, the polymerization time may be prolonged due to polymerization, which may lead to a disadvantage that productivity may be reduced.
  • the thickness of the polyester resin layer B of the present embodiment is not particularly limited, and various values may be applied.
  • the thickness is preferably from 0.3 ⁇ m to 5.0 ⁇ m.
  • a more preferable thickness is 0.5 ⁇ m to 4.0 ⁇ m.
  • the most preferable thickness is 0.7 ⁇ m to 3.0 ⁇ m.
  • the thickness of the acrylic resin layer A is preferably from 0.3 ⁇ m to 4.0 ⁇ m. It is preferably from 5 ⁇ m to 3.0 ⁇ m. More preferably, it is 0.8 ⁇ m to 2.5 ⁇ m.
  • the thickness of the acrylic resin layer A is preferably 0.8 ⁇ m to 9.0 ⁇ m, and more preferably 1.5 ⁇ m or more from the viewpoint of workability.
  • the thickness of the acrylic resin layer A is as described in the first embodiment.
  • the thickness [ ⁇ m] of the polyester resin layer B can be converted as follows.
  • Thickness of polyester resin layer B [ ⁇ m] weight of polyester resin layer B [g / m 2 ] ⁇ volume per unit weight of polyester resin layer B [cm 3 / g]
  • polyester resin 90 wt% in the polyester resin layer B and if the acetylene black 10 wt% is contained, the volume per unit weight of the polyester resin layer B [cm 3 / g] becomes 0.73 cm 3 / g.
  • the volume per unit weight [cm 3 / g] is 0.76 for the polyester and 0.76 for the acetylene black. 0.55.
  • [Cm 3 / g] is equivalent to [ ⁇ m / (g / m 2 )].
  • polyester resin layer B of the present embodiment it is desirable that the polyester resin does not contain an acrylic component, for example, it is not modified with acrylic.
  • the polyester resin layer B does not contain wax. This is because if wax is contained in the polyester resin layer B, the wax component is volatilized by heating during press molding and an odor is generated. From such a viewpoint, the wax contained in the polyester resin layer B is preferably less than 5 wt%, more preferably less than 1 wt%, and still more preferably less than 0.1 wt%.
  • the polyester resin layer B contains carbon-based particles C (first carbon-based particles).
  • the polyester resin layer B contains carbon-based particles C (first carbon-based particles).
  • the polyester resin layer B has a thickening effect at the warm working temperature, and the cohesive force of the film can be improved. Contact between the mold and the metal plate 1 is suppressed. Further, the lubrication effect of carbon itself is added, and the processability is synergistically improved. As a result, it is considered that the processability can be further improved as compared with the case where the single layer of the acrylic resin A is used.
  • conductive carbon black As the carbon-based particles C, so-called conductive carbon black can be used. Specifically, a conductive carbon black such as furnace black, acetylene black, and Ketjen black manufactured by a known method such as a furnace method, an acetylene method, and a gasification method can be appropriately selected and used. Further, there is no problem even if conductive carbon black to which surface treatment such as oxidation (functional group addition), porosity (activation), and graphitization is applied is applied is applied. Alternatively, a carbon nanotube, fullerene, or the like can be used. From the viewpoint of the lubricating effect, furnace black, acetylene black and Ketjen black are preferable, and furnace black and acetylene black are more preferable.
  • the average particle size of the carbon-based particles C used in the present embodiment is preferably 10 nm to 80 nm.
  • the content of the carbon-based particles C in the polyester resin layer B is preferably 4 to 30% by weight. If the content of the carbon-based particles C is less than 4%, the above effects cannot be obtained, and preferable moldability may not be obtained.
  • the present embodiment by being included in the polyester resin layer B serving as the lower layer, there is also an advantage that even when the upper layer does not include carbon-based particles, preferable conductivity can be imparted at the time of spot welding. From the viewpoint of, 5% or more is preferable.
  • the content of the carbon-based particles C exceeds 30%, it is difficult to mix the coating liquid uniformly, and it may be necessary to stir for a long time. At the time of formation, it is difficult to form a uniform thickness and to uniformly disperse the carbon-based particles, which is not preferable.
  • both the acrylic resin layer A and the polyester resin layer B may contain carbon-based particles.
  • the content of the carbon-based particles C ′ (second carbon-based particles) in the acrylic resin layer A is preferably less than 30% by weight, and is smaller than the content of the carbon-based particles C (first carbon-based particles) in the polyester resin layer B. Smaller is more preferable.
  • the acrylic resin layer A can have good workability and conductivity, so that the content of the carbon-based particles C ′ is 0.1% by weight. %.
  • a peelable protective layer such as a professional sheet may be formed on the acrylic resin layer A to protect the surface during transportation.
  • the outermost surface becomes the acrylic resin layer A.
  • the resin-coated metal plate 300 according to the present embodiment will be described with reference to FIG.
  • components having the same functions and effects as those of the above-described first embodiment or the second embodiment are denoted by the same reference numerals, and further description thereof will be appropriately omitted.
  • the third embodiment is characterized in that a film removing function is further added to the resin-coated metal plate described in the first embodiment or the second embodiment.
  • the polyester resin layer B further contains a sulfonic acid salt as a hydrophilic group.
  • examples of the sulfonic acid salt as described above include a sodium salt, a lithium salt, and a potassium salt.
  • a sodium salt is preferable as the sulfonate, and among the sodium salts, sodium 5-sulfoisophthalate (hereinafter also referred to as “SIP”) is the most preferable among the sodium salts as described later. desirable.
  • SIP sodium 5-sulfoisophthalate
  • the polyester resin layer B in the present embodiment use a resin having a glass transition temperature (Tg) of less than 100 ° C. as the polyester resin. If the glass transition temperature (Tg) exceeds 100 ° C., it becomes difficult to dissolve in the treatment liquid during alkali degreasing, and it becomes difficult to perform appropriate film removal treatment in view of cost, working environment, and the like.
  • Tg glass transition temperature
  • the glass transition temperature (Tg) exceeds 100 ° C.
  • the bath temperature of the treatment solution at the time of film removal is increased, The sulphonate content must be high.
  • the bath temperature of the processing solution at the time of film removal is increased, there is a possibility that the processing solution is volatilized and the working environment is deteriorated.
  • a sulfonate such as SIP
  • the film forming property of the polyester resin layer B on the metal plate 1 may be lowered, the film strength may be lowered, and the cost may be reduced. Undesirably high.
  • the glass transition temperature (Tg) of the polyester resin is preferably from 0 ° C. to 100 ° C., and preferably from 25 ° C. to 64 ° C. when the polyester resin contains sodium 5-sulfoisophthalate.
  • the content (mol%) of the sulfonic acid salt contained in the polyester resin layer B is preferably 4 mol% or more when the total dicarboxylic acid component is 100 mol%. If the amount of the sulfonic acid salt is less than 4 mol% based on the total amount of the dicarboxylic acid components, the film-removing property particularly after warm press molding is deteriorated.
  • the content (mol%) of the above-mentioned sulfonic acid salt is further preferably 6 to 20 mol%, more preferably 10 to 17 mol%, when the total dicarboxylic acid component is 100 mol%.
  • the content (mol%) may be 6 to 17 mol% when the total dicarboxylic acid component is 100 mol%. More preferably, it is more preferably 10 to 17 mol%.
  • the molecular weight (number average) of the polyester resin is preferably 20,000 or less. If the molecular weight of the polyester resin exceeds 20,000, the polymerization time may be prolonged due to polymerization, which may lead to a disadvantage that productivity may be reduced. In addition, if the molecular weight is too high, it may be difficult to dissolve in the processing solution at the time of alkali degreasing, and in order to dissolve appropriately, the bath temperature at the time of film removal may be increased, or the sulfonate in the polyester resin may be used. This is because there may be a problem that the content must be increased in some cases.
  • the bath temperature of the processing solution at the time of film removal is high, there is a fear that the processing solution is volatilized and the working environment is deteriorated. Further, if a large amount of a sulfonate such as SIP is put into the polyester resin layer B, there is a concern that the film forming property of the polyester resin layer B on the metal plate 1 may be deteriorated and that the film itself may be deteriorated. Undesirably high.
  • the molecular weight of the polyester resin is more preferably 10,000 to 17,000.
  • the thickness of the polyester resin layer B is preferably 0.5 ⁇ m to 5.0 ⁇ m from the viewpoint of cost when forming a coating film, and 0.7 ⁇ m to 5.0 ⁇ m when uniformity and film removal properties are required. It is more preferably 4.0 ⁇ m, and most preferably 0.9 ⁇ m to 3.0 ⁇ m in consideration of productivity.
  • the thickness of the entire organic resin layer 30 of the present embodiment is preferably 0.8 ⁇ m to 10.0 ⁇ m. From the viewpoint of workability, the thickness is more preferably 1.5 ⁇ m or more, and from the viewpoint of film removal, it is more preferably 8.0 ⁇ m or less, and still more preferably 6.0 ⁇ m or less.
  • the thickness is more preferably from 4.0 ⁇ m to 15.0 ⁇ m, and still more preferably from 5.0 ⁇ m to 12.0 ⁇ m.
  • the content is preferably less than 0.1% by weight.
  • the carbon-based particles C ′ are contained in an amount of 0.1% by weight or more, the film-depositing property may decrease, which is not preferable.
  • an example in which an organic resin layer is formed on one surface of the metal plate 1 is shown.
  • the resin-coated metal plate of the present embodiment is not limited to this, and the above-described organic resin layer may be formed on both surfaces of the metal plate 1.
  • the configuration of the organic resin layer does not need to be the same on both surfaces of the metal plate.
  • the organic resin layer 10 is formed on one surface of the metal plate 1 and the organic resin layer 20 is formed on the other surface. May be.
  • the organic resin layers 10 to 30 described in the first to third embodiments may be used as an organic resin film without being laminated on the metal plate 1.
  • the organic resin film 10 'shown in FIG. 4 has the same configuration as the organic resin layer 10 in the resin-coated metal plate shown in FIG. 1, detailed description is omitted here.
  • the organic resin film 20 'shown in FIG. 5 has the same configuration as the organic resin layer 20' in the resin-coated metal plate shown in FIG. 2, and the organic resin film 30 'shown in FIG. Since it has the same configuration as that of the organic resin layer 30 'shown in FIG. 3, detailed description is omitted here.
  • the organic resin film in the present embodiment is suitable for use as a coating on a metal plate to be press-formed (particularly, warm press-formed). That is, the resin-coated metal plate 10 'coated with the organic resin film of the present embodiment exhibits favorable moldability, for example, during warm press molding.
  • the organic resin film 20 'in the present embodiment can exhibit preferable conductivity during spot welding, in addition to more preferable formability during warm press forming, for example.
  • the organic resin film 30 'in the present embodiment can exhibit good film-removing property in removing a film after press molding in addition to the above-described moldability and conductivity.
  • the method for manufacturing the organic resin films 10 'to 30' of the present embodiment is not particularly limited, and a known film manufacturing method can be applied.
  • a coating liquid containing an organic resin is applied to a base material such as Teflon (registered trademark) and dried, and then the coating solution is peeled off from the base material to form an organic resin film 10 ′ to an organic resin film.
  • the type of the base material is not particularly limited as long as the organic resin film after the application and drying can be peeled off, and it goes without saying that various known materials may be used as the base material.
  • the organic resin film 20 'or the organic resin film 30' is a two-layer film, but is not limited to this as long as it has the features of the present invention, and may be a three-layer or more film.
  • a known method can be applied to a production method in the case of forming a film structure of two or more layers, and for example, it can be obtained by repeating a step of applying a coating liquid and drying.
  • a 0.8 mm thick aluminum alloy plate (A5052 H34) (hereinafter also referred to as an aluminum plate or an AL plate) was prepared as the metal plate 1.
  • the aluminum plate was degreased (immersed in surf cleaner E370 (5 g / L) at 60 ° C. for 20 seconds), de-smudged (sulfuric acid 70 g / L, 10 seconds), and dried by a dryer by known methods.
  • a resin-coated metal plate having a single-layer or two-layer organic resin layer portion was prepared on both surfaces of the metal plate 1 by appropriately selecting from the resin types shown in Table 1. Note that the formation of the organic resin layer on the metal plate 1 was performed by a method of applying a coating liquid on the metal plate 1.
  • the single-layer resin-coated metal plate shown in 1-1 was produced as follows. First, a coating liquid containing 50 wt% of an acrylic resin and 50 wt% of colloidal silica (silica average particle diameter: 4 nm to 6 nm) was applied on a metal plate. The coating amount was adjusted so that the thickness of the resin after drying was 2 ⁇ m. Then, the temperature of the metal plate 1 was heated to 110 ° C., and the coating solution was dried by evaporating water in the coating solution to prepare a resin-coated metal plate. In this experimental example, the following colloidal silica (all manufactured by Nissan Chemical Industries, Ltd.) was used according to the average particle diameter of silica.
  • the weight of the organic resin layer after drying was 3.2 g / m 2 .
  • the thickness and weight of the organic resin layer can be converted as follows. If the specific gravity of acrylic is 1.2 g / cm 3 and the specific gravity of silica is 2.2 g / cm 3 , the volume per unit weight [cm 3 / g] is 0.83 for acrylic and 0.45 for silica. .
  • the single-layer resin-coated metal plate shown in 1-4 was produced as follows. First, a coating liquid containing a resin of “polyester A3” among the resin types shown in Table 1 was prepared as follows.
  • Ethylene glycol and diethylene glycol were used as glycol components.
  • ethylene glycol was 56 mol% and diethylene glycol was 44 mol%.
  • Terephthalic acid (TA) and isophthalic acid (IA) were used as polycarboxylic acid components.
  • Sodium 5-sulfoisophthalate (SIP) was used as the hydrophilic group of the polycarboxylic acid component.
  • a polyester resin copolymerized so that the ratio (mol%) of TA / IA / SIP was as shown in Table 1 was used.
  • the prepared resin had a Tg of 50 ° C. and a molecular weight of 15,000. The measurement of Tg was performed with a known differential scanning calorimeter.
  • this polyester resin was dispersed in an aqueous solvent to prepare a coating liquid of the water-dispersed polyester resin.
  • the resin component extracted from this coating solution by drying was subjected to component analysis by H-NMR spectroscopy (proton-Nuclear Magnetic Resonance spectroscopy) using JMN EX-400 manufactured by JEOL Ltd.
  • the amount of SIP at this time was 16 mol% with respect to all dicarboxylic acid components in the polyester resin.
  • the sulfonic acid is not limited to the sodium salt of sulfonic acid.
  • a similar principle applies to other sulfonates such as Li salts.
  • the technical scope of the present invention is not limited to the sodium sulfonic acid salt used above, but is extended to other sulfonic acid salts.
  • a coating liquid containing 80 wt% of the polyester resin having the above-described structure and 20 wt% of colloidal silica (silica average particle diameter: 4 nm to 6 nm) was applied on a metal plate using a known # 14 bar coater.
  • the coating amount was adjusted so that the thickness of the resin after drying was 6 ⁇ m.
  • the temperature of the metal plate 1 was heated to 110 ° C., and the coating solution was dried by evaporating water in the coating solution to prepare a resin-coated metal plate.
  • the coating liquid was applied to the metal plate using a # 14 bar coater so that the thickness of the resin was 6 ⁇ m.
  • the coating liquid was applied so that the thickness of the resin after drying was 2 ⁇ m.
  • the coating was performed using a # 3 bar coater, and the coating was performed using a # 2 bar coater when coating so that the thickness of the resin after drying was 1 ⁇ m.
  • the two-layer resin-coated metal plate shown in 2-1 was produced as follows. First, a resin type “polyester A1” was selected as the polyester resin layer B, and acetylene black was mixed as carbon-based particles at a ratio shown in Table 2 to obtain a coating liquid. This coating liquid was applied on the metal plate 1 so that the thickness of the resin after drying was 1 ⁇ m. Then, a coating solution containing 50 wt% of an acrylic resin and 50 wt% of colloidal silica (silica average particle diameter: 4 nm to 6 nm) is coated on a metal plate by a known # 3 method so that the thickness of the resin after drying becomes 2 ⁇ m. It was applied using a bar coater and dried to obtain a two-layer resin-coated metal plate.
  • a resin type “polyester A1” was selected as the polyester resin layer B, and acetylene black was mixed as carbon-based particles at a ratio shown in Table 2 to obtain a coating liquid. This coating liquid was applied on the
  • the weight of the organic resin layer after drying was 1.37 g / m 2 after forming the polyester A1, and the increase after forming the acrylic resin was 3.2 g / m 2 .
  • the thickness and weight of the organic resin layer can be converted as follows. Regarding the acrylic resin layer, the experimental example No. described above was used. It is omitted because it is the same as 1-1.
  • the volume per unit weight [cm 3 / g] is 0.76 for polyester and 0.55 for acetylene black. It becomes.
  • the two-layer resin-coated metal plate shown in 3-1 was produced as follows. First, a stainless steel plate (SUS304, hereinafter also referred to as “SUS plate”) having a thickness of 0.3 mm was prepared as the metal plate 1. The SUS plate has a proof stress of 255 MPa, a tensile strength of 590 MPa, and an elongation of 60%. The SUS plate was subjected to electrolytic degreasing with an alkali, pickling, and drying with a drier by a known method. Next, the above experimental example No. was placed on a SUS plate. A resin-coated metal plate was produced by forming two organic resin layers in the same manner as in 2-1.
  • the evaluation can be made as follows. First, if the coefficient of warm kinetic friction ( ⁇ ) is high during warm press forming, it is predicted that slippage at the interface between the mold and the resin-coated metal plate is poor, and it is highly likely that warm press forming is difficult. it can. Also, if it is determined that there is tack in the tack test, the resin may adhere to the mold or the metal plate of the resin-coated plate may be exposed during warm press forming. Can be expected to be difficult. In view of this point, according to Table 2, the surface layer of the organic resin layer (the layer that comes into contact with the mold during warm press molding) is an acrylic resin, and the average particle size of the contained silica is 10 nm. In this case, both the warm dynamic friction coefficient ( ⁇ ) and the tackiness are suitable, and it can be evaluated that the composition has excellent moldability in warm press molding.
  • a three-dimensional surface roughness profile measuring device (Surfcom 1400-3DF, manufactured by Tokyo Seimitsu) was used for the measurement of the dent depth. Traces were made at arbitrary 0 ° and 90 ° directions, and the heat resistance was evaluated according to the following criteria, with the average value of the four detected dents as the dent depth. Table 3 shows the results. :: Less than 3.0 ⁇ m ⁇ : 3.0 ⁇ m or more
  • the evaluation can be made as follows. That is, when the surface layer of the organic resin layer (the layer that comes into contact with the mold at the time of warm press molding) is an acrylic resin having a dent depth of less than 3.0 ⁇ m when heated at 250 ° C., the processing during the warm press molding is performed. Even when a force is applied, it can be predicted that the contained silica hardly flows in the resin. Therefore, in the contact between the mold and the organic resin layer, a suitable frictional state can be maintained, and it can be evaluated that the moldability during warm press molding is good.
  • a forming load (F) can be represented by the following equation.
  • Molding load (F) frictional force ( ⁇ ⁇ BHF) + bending load (fb)
  • ⁇ frictional coefficient
  • BHF wrinkle suppressing force.
  • the above expression means that when the coefficient of friction ( ⁇ ) is small, molding is possible even when the wrinkle suppressing force (BHF) is increased.
  • the experimental example No. 2-2 and No. Comparison of 2-4 shows that when the organic resin layer has a two-layer structure, the polyester resin layer B contains carbon-based particles (carbon black) to improve the warm sliding property.
  • the evaluation can be made as follows. As described above, in Table 5, when the organic resin layer has a two-layer structure, the polyester resin layer B contains carbon-based particles (carbon black), whereby the warm slidability is improved. Indicated.
  • the experimental example Nos. 2-2 and Experimental Example No. In view of the comparison result of 2-4, it was shown that when the organic resin layer had a two-layer structure, the polyester resin layer B contained carbon-based particles (carbon black), thereby improving conductivity. . As a result, it was shown that the present invention provides a resin-coated metal plate having both preferable formability during warm press forming and preferable conductivity during spot welding.
  • the film-removing property was evaluated in the following manner. That is, in the evaluation of the film-removing property in the experimental example, the resin-coated metal plate after the degreasing was measured using a fluorescent X-ray apparatus (Rigaku ZSX100e). When the resin film is formed, that is, when the film is not completely removed, the intensity of C (carbon) (C-K ⁇ ray, net strength) is detected to be high. Judged from strength.
  • the C strength of the metal plate 1 is about 0.3 to 0.6 kcps. Therefore, if the C strength is 0.6 kcps or less, it can be determined that all of the resin film has been removed and there is no residue.
  • the film removal property was evaluated using the following calculation. That is, IA: C strength of metal plate 1 before application of coating liquid (after degreasing and de-smudge (pickling)) IB: C strength after applying the coating liquid to the metal plate 1 and further drying IC: C strength after performing a film removal test after applying a heat history assuming warm working, The removal rate is represented by (IB ⁇ IC + IA) / IB ⁇ 100 (%).
  • the resin-coated metal plate and the resin-coated film of the present invention exhibit excellent moldability, for example, by warm press molding.
  • both the conductivity required for spot welding and the excellent film removal property in film removal after heating at the temperature assumed in warm press molding are compatible. It can be applied to a wide range of industries including automobiles and electronic devices.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Laminated Bodies (AREA)
  • Shaping Metal By Deep-Drawing, Or The Like (AREA)
PCT/JP2019/025260 2018-06-27 2019-06-25 温間プレス成形用樹脂被覆金属板および有機樹脂フィルム Ceased WO2020004427A1 (ja)

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