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WO1992012006A1 - Plaque metallique composite d'amortissement et production de celle-ci - Google Patents

Plaque metallique composite d'amortissement et production de celle-ci Download PDF

Info

Publication number
WO1992012006A1
WO1992012006A1 PCT/JP1991/001756 JP9101756W WO9212006A1 WO 1992012006 A1 WO1992012006 A1 WO 1992012006A1 JP 9101756 W JP9101756 W JP 9101756W WO 9212006 A1 WO9212006 A1 WO 9212006A1
Authority
WO
WIPO (PCT)
Prior art keywords
adhesive
metal plate
composite metal
vibration
damping
Prior art date
Application number
PCT/JP1991/001756
Other languages
English (en)
Japanese (ja)
Inventor
Seiichi Matsuo
Takahiro Nakano
Mika Kubo
Original Assignee
Nippon Paint Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Paint Co., Ltd. filed Critical Nippon Paint Co., Ltd.
Publication of WO1992012006A1 publication Critical patent/WO1992012006A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/04—Homopolymers or copolymers of ethene
    • C09J123/08—Copolymers of ethene
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J113/00—Adhesives based on rubbers containing carboxyl groups
    • C09J113/02—Latex
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof

Definitions

  • the present invention relates to a vibration-damping composite metal plate and a method for producing the same.
  • the present invention relates to a composite metal sheet used for transportation machines, building structures, electric parts, etc., having a high vibration damping ability and capable of withstanding complicated processing, and a method for producing the same.
  • Dramping plate is made by bonding two metal plates with an adhesive having vibration damping (damping) properties.
  • this damping steel plate has been used for oil pans and outer panels of washing machines for the purpose of reducing noise in automobile interiors and reducing noise when using a washing machine in an apartment house.
  • vibration damping plates are very effective in terms of noise control, they have the disadvantage that they cannot be applied to parts that require complicated processing or thick plates that have large processing deformation force. Have. Therefore, it is currently used only for thin boxes such as oil pans and washing machine outer panels. Absent.
  • the adhesive used for the damping steel sheet a film adhesive formed by heating a resin or a liquid adhesive obtained by dissolving a resin in an organic solvent has been used.
  • this film type can be formed without difficulty if it is a film of 100 or more due to the necessity of heat-melt molding.However, it is difficult to control the film thickness of a film of 50 ⁇ or less that is actually used. The cost is also high.
  • the solvent-based liquid type has problems in working environment, air pollution, etc.
  • the present inventors have studied the problems of known adhesives for vibration damping, and found that a butadiene-based copolymer obtained by copolymerizing a carboxyl group-containing olefin copolymer emulsion (B) and an ethylenically unsaturated carboxylic acid.
  • Damping steel sheets bonded with an adhesive mainly composed of synthetic rubber latex (A) have excellent adhesion between metal plates, so they can withstand complicated processing and can be used to produce thick vibration-damping steel sheets. I found something.
  • the adhesive has good vibration damping properties in the range from normal temperature to high temperature, and since the adhesive is an aqueous dispersion, The present inventors have found that the harmful organic solvent is not generated even in the production process, and that it is easy to control the thickness of the adhesive before and after 50, thereby completing the present invention.
  • the present invention provides a vibration-damping composite metal plate having an adhesive layer between metal plates, wherein the adhesive is (A) an ethylenically unsaturated carboxylic acid-butadiene copolymer rubber and (B) A vibration-damping composite metal plate, which is a latex composition containing a carboxyl group-containing copolymer resin, and a method for producing the same.
  • the adhesive is (A) an ethylenically unsaturated carboxylic acid-butadiene copolymer rubber and (B) A vibration-damping composite metal plate, which is a latex composition containing a carboxyl group-containing copolymer resin, and a method for producing the same.
  • the vibration-damping steel sheet of the present invention has excellent workability is that the component (B) is disposed at the metal interface inside the adhesive layer, and the strong interfacial adhesive force causes the adhesive layer to peel off from the metal during processing deformation. It is thought to prevent.
  • the component (A) is mainly located in the middle of the adhesive layer and plays a role in relieving excessive adhesive stress from concentrating on the adhesive interface by easily deforming the adhesive layer during working deformation due to its strong plasticity. it is conceivable that
  • Ethylenically unsaturated carboxylic acid compounded in the adhesive used in the present invention is prepared by copolymerizing ethylenically unsaturated carboxylic acid and butadiene as essential monomers.
  • the ethylenically unsaturated carboxylic acid include maleic acid, atalylic acid, methacrylic acid and the like.
  • other polymerizable monomers may be added as needed.
  • Other polymerizable monomers include, for example, styrene, acrylonitrile, acrylate, methacrylate, and the like. Any of the above monomers may be used alone.
  • the copolymer rubber (A) is preferably obtained as a latex by emulsion polymerization in an aqueous medium in the presence of a polymerization initiator, an emulsifier and the like.
  • the ethylenically unsaturated carboxylic acid is preferably 2 to 20% by weight (particularly 5 to 15% by weight), and the butadiene is preferably 40 to 98% by weight, based on the total monomer weight. If the amount of the carboxylic acid is less than 2% by weight, the compatibility with the component (B) is poor, and phase separation occurs after mixing. Further, the workability cannot be satisfied due to a decrease in the adhesion between the component (B) and the interlayer after bonding.
  • the copolymer rubber latex (A) obtained as described above preferably has a nonvolatile content of 40 to 60% by weight.
  • the carboxyl group-containing olefin copolymer resin (B) to be incorporated into the adhesive used in the present invention is prepared by copolymerizing olefin and an ethylenically unsaturated carboxylic acid as essential monomers.
  • the olefin include ethylene and propylene.
  • the ethylenically unsaturated carboxylic acid include those exemplified for the copolymer rubber.
  • other polymerizable monomers for example, those exemplified in the above-mentioned copolymer rubber
  • Any of the above monomers may be used alone.
  • those containing 10 to 25% by weight of ethylenically unsaturated carboxylic acid have good adhesive strength and are easy to emulsify.
  • the copolymer resin (B) is preferably blended in the form of an emulsion.
  • Copolymer resin (B) Emma The preparation of lucion is carried out, for example, by preparing the above copolymer resin (B) in an aqueous medium and a base (for example, ammonia, morpholine, alkanol) in an amount sufficient for the copolymer resin (B) to form a water and oil-in-water emulsion. Or caustic soda) and stirring at 80-2003 ⁇ 4 for 0.5-2 hours.
  • a base for example, ammonia, morpholine, alkanol
  • a latex adhesive obtained by mixing the above components (A) and (B) is used, and the mixing ratio is 10:90 to 90:10, preferably 70:30 to 70, in terms of resin weight ratio. It is desirable to select arbitrarily in the range of 30:70 in accordance with the balance between workability and vibration damping required by the place where the composite metal sheet is used.
  • the resin concentration is preferably 20 to 50% by weight.
  • the adhesive thus obtained may be used as it is, but may also be used as epoxy resin (for example, bisphenol A type epoxy resin, novolak type epoxy resin, alkylene glycol type epoxy resin, etc.)
  • epoxy resin for example, bisphenol A type epoxy resin, novolak type epoxy resin, alkylene glycol type epoxy resin, etc.
  • Components that can react with carboxyl groups in the adhesive such as melamine resin and urea resin, may be added.
  • Conventional fillers, dispersants, thickeners, surfactants, flame retardants, coupling agents, and the like may be added and used as long as the object of the present invention can be achieved.
  • metal powder fine powder of iron, copper, nickel, aluminum, zinc, and alloys containing these metals
  • conductive powder in the adhesive is used.
  • the metal powder and the conductive filler are classified, and the particle size is adjusted to 0.5 to 1.5 times the thickness of the adhesive layer, and then 1 to 10 parts by weight is added to the adhesive and stirred.
  • Use of the adhesive as an adhesive provides good spot weldability.
  • the vibration-damping composite metal plate of the present invention is manufactured by bonding both metal plates with the adhesive obtained above. That is, the metal plate of the present invention has a structure having the above-mentioned adhesive layer between the metal plates. In order to obtain a stronger interfacial adhesive force, the above-mentioned olefin copolymer resin (B) layer may be further provided between the adhesive layer and the metal plate. Specific examples of such a cross-sectional structure of the metal plate of the present invention are shown in FIGS. 1 to 3 (however, these are not limited, and It is only for the purpose of more clearly explaining the structure of the present invention, and the thickness, size, shape, etc. are not shown in consideration of the structure. ).
  • the material of the metal plate (1) is not particularly limited, but may be, for example, iron, aluminum, copper, titanium, nickel, or an alloy containing these metals (eg, stainless steel, brass, etc.). .
  • the thickness of the metal plate (1) is not particularly limited, but may be, for example, 0.1 to 1 Omm.
  • the shape of the metal plate (1) is not limited to a plate shape, but may be a tubular shape or a rod shape.
  • the thicknesses of the adhesive layer (2) and the olefin copolymer resin (B) layer (3) are also appropriately selected, and may be, for example, 30 to 300 / m and 1 to 10 ⁇ ra, respectively.
  • the composite metal plate of the present invention having a T peel adhesion strength (JI SK 6854) of 10 to 30 (kg / 25 hidden), and a tensile shear bonding strength (JI SK 6850) of 180 to 240 (kg Zcra 2 ), There is no deviation in 90 ° bending as defined in the examples described below.
  • the composite metal plate of the present invention as described above is produced, for example, by applying an adhesive to one or both metal plates, drying and applying heat and pressure.
  • the adhesive is applied to one or both metal plates with a usual coating machine such as a roll coater, a curtain coater, a spray coater or the like so as to have a dry film thickness of, for example, 0.5 to 0.01.
  • a usual coating machine such as a roll coater, a curtain coater, a spray coater or the like so as to have a dry film thickness of, for example, 0.5 to 0.01.
  • the adhesive for the purpose of streamlining the production, it is preferable to apply the adhesive, then dry at, for example, 120 to 220 ° C., and press-bond directly using the temperature after drying.
  • it can be applied to a hot plate immediately after the rolling process, dried by preheating, and then immediately pressed.
  • a hot plate having a pressing temperature for example, 120 to 220 ° C.
  • a dry film of an adhesive or a composite film in which one or both surfaces of a dry film of an adhesive are coated with the above-mentioned copolymer (B) is sandwiched between metal plates, and then heated and pressed.
  • the composite metal plate of the invention can be manufactured.
  • the dried film of the adhesive is prepared by, for example, applying an adhesive on an easily peelable sheet (for example, a Teflon sheet), drying at 80 to 200 ° C. for 1 to 10 minutes, and then peeling the sheet. can get.
  • the composite film can be obtained by applying an emulsion of the resin copolymer (B) on one or both surfaces of the dried film thus obtained, for example, by using a spray coater or the like, followed by drying. Next, the dried film or composite film is sandwiched between metal plates and heated and pressed in the same manner as above to obtain the composite metal plate of the present invention.
  • one or both of the metal plates may be the same as those described above.
  • a resin which has been previously coated and dried with an emulsion copolymer resin (B) emulsion is used.
  • a coated metal plate may be used (that is, in the present invention, the “metal plate” refers to the resin-coated metal plate as well.
  • copolymer rubber latex and copolymer resin emulsion obtained as described above were mixed at a resin weight ratio of 1: 1 to prepare an adhesive.
  • the adhesive thus obtained was applied to a 0.6-thick cold-rolled steel sheet so as to have a dry film pressure of 2 ⁇ ⁇ , and kept in a drying oven at 80 ° C for 5 minutes. The water was dried. Next, the adhesive-coated surfaces were brought together, fed by a heating roll so that the temperature of the adhesive layer became 160 ° C., and the speed was adjusted to perform heat-press bonding. Table 1 shows the results of measuring the adhesiveness, vibration damping properties, and workability of the obtained composite steel sheet.
  • the adhesive was applied on a Teflon plate so as to have a dry film thickness of 50 ⁇ , and kept in a drying oven at 80 ° C for 5 minutes to dry the water.
  • the adhesive film was peeled off from the teflon plate, sandwiched between 0.6 mm thick cold-rolled steel sheets, fed by a heating roll so that the adhesive temperature became 160 ° C, and the heating speed was adjusted. Crimped. Table 1 shows the physical properties of the obtained composite steel sheet.
  • Example 1 In place of the cold-rolled steel sheet in Example 1, Then, a composite metal sheet was produced in the same manner as in Example 1 except that a cold rolled 0.6-roll steel sheet was used, which was coated with a solution to a dry film thickness of 1 mm and air-dried. Table 1 shows the results of various physical property tests of this composite metal sheet.
  • Example 2 a 0.6-thick cold-rolled steel sheet, which was previously coated with a copolymer resin emulsion to a dry film thickness of 1 and air-dried, was used.
  • a composite metal plate was manufactured in the same manner as in 2. Table 1 shows the results of various physical property tests of this composite metal sheet.
  • Example 2 a composite film was used in which a copolymer resin emulsion was applied to both surfaces of the adhesive film of Example 2 by a spray coater so as to have a dry film thickness of 1, and air-dried. Except for the above, a composite metal plate was manufactured in the same manner as in Example 2. Table 1 shows the results of various physical property tests of the obtained composite metal sheet.
  • Example 6 An aluminum sheet (Example 6) Each composite metal plate was manufactured in the same manner as in Example 3 except that a lead-plated steel plate (Example I) and a stainless steel plate (Example 8 :) were used, and the results of measuring the adhesiveness and workability were shown in the table. Shown in 1.
  • Example 3 was replaced by Example 3 except that the cold-rolled steel sheet having a thickness of 1.6 mm (Example 9) and 3.2 (Example 10) were used instead of the cold-rolled steel sheet having a thickness of 0.6.
  • Each composite metal plate was manufactured in the same manner, and the results of measuring the adhesiveness and workability are shown in Table 1.
  • Table 1 shows the results of measuring the vibration damping properties and workability of commercially available vibration-damping steel sheets for washing machines (using an organic solvent-based adhesive, with a film thickness of 50).
  • the adhesiveness was measured according to T-peel adhesive strength (JI SK6854) and tensile shear adhesive strength (JI SK68 ⁇ 0). In particular, for the latter, the test piece shown in Fig. 4 was prepared and measured to make the test piece thickness 1.6 mm.
  • Vibration damping is measured using a complex elasticity coefficient 7 ⁇ measuring device manufactured by Brüel & Kj ⁇ r. Then, the loss coefficients of the composite metal plate at 40 ° C and 80 ° C at 200 Hz were measured.
  • the workability was determined by performing 90 ° bending at the center of the test plate and measuring the average [(1 1 + 1 2 ) no 2] of the edge displacement (see Fig. 5).
  • the vibration-damping metal plate of the present invention (Examples 1 to 5) is superior to the commercially available solvent-based adhesive (Comparative Example 1) in adhesion.
  • Table 1 it became possible to produce thick laminated steel sheets with good workability (Example 7).
  • the vibration damping property is better than that of the commercially available solvent system (Comparative Example 1) in a wide temperature range of 40 to 80 ° C.
  • the adhesive of the present invention also has excellent adhesion to aluminum plate (Example 6), zinc plated steel plate (Example ⁇ ) and stainless steel plate (Example 8). It is also possible to create a laminated plate of different types.
  • the vibration-damping composite metal sheet of the present invention has excellent adhesion between metal sheets, so it can withstand complicated processing and can also produce a thick vibration-damping steel sheet. In addition, it has good vibration damping properties in the range from normal temperature to high temperature, and because the adhesive is a water-dispersing system, it does not generate harmful organic solvents during the manufacturing process. Also, it is easy to control the adhesive film thickness to around 50.
  • FIG. 1 shows a cross-sectional view of a damping composite metal plate.
  • FIG. 2 shows a cross-sectional view of another embodiment of the damping composite metal plate.
  • FIG. 3 shows a cross-sectional view of still another embodiment of the damping composite metal plate.
  • FIG. 4 shows a cross-sectional view of the tensile shear adhesive strength test piece.
  • Fig. 5 shows that when the 90 ° bending process is performed, the deviation of the end is 1! 1 and 2 show cross-sectional views of the test plate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Vibration Prevention Devices (AREA)

Abstract

Plaque métallique composite d'amortissement comportant des plaques métalliques entre lesquelles est serré un adhésif qui comporte une composition de latex comprenant un caoutchouc copolymère d'acide carboxylique/butadiène insaturé par éthylène ainsi qu'une résine copolymère oléfinique carboxylée. L'utilisation de l'adhésif contenant le constituant caoutchouc copolymère rend possible la production d'une plaque métallique composite présentant d'excellentes caractéristiques d'adhérence et d'amortissement des vibrations.
PCT/JP1991/001756 1990-12-28 1991-12-25 Plaque metallique composite d'amortissement et production de celle-ci WO1992012006A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2409208A JPH05293924A (ja) 1990-12-28 1990-12-28 制振性複合金属板とその製造法
JP2/409208 1990-12-28

Publications (1)

Publication Number Publication Date
WO1992012006A1 true WO1992012006A1 (fr) 1992-07-23

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1991/001756 WO1992012006A1 (fr) 1990-12-28 1991-12-25 Plaque metallique composite d'amortissement et production de celle-ci

Country Status (2)

Country Link
JP (1) JPH05293924A (fr)
WO (1) WO1992012006A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6770374B1 (en) 1998-06-05 2004-08-03 Basf Aktiengesellschaft Composite elements containing compact polyisocyanate polyaddition products
US6790537B1 (en) 1999-03-30 2004-09-14 Basf Aktiengesellschaft Composite elements containing polyisocyanate-polyaddition products
US6828020B2 (en) 2002-08-14 2004-12-07 Adco Products, Inc. Self-adhesive vibration damping tape and composition
US7223457B1 (en) 1999-11-04 2007-05-29 Basf Aktiengesellschaft Composite elements
US20130284152A1 (en) * 2012-04-26 2013-10-31 Robert Bosch Gmbh System having a fuel distributor and a mounting support

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003039120A (ja) * 2001-07-25 2003-02-12 Kobe Steel Ltd プレス成形用差厚テーラードブランク材

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5987148A (ja) * 1982-10-08 1984-05-19 チバ−ガイギ−・アクチエンゲゼルシヤフト 金属シ−トと熱可塑性プラスチツク材からなるラミネ−ト
JPS62101431A (ja) * 1985-10-29 1987-05-11 昭和電工株式会社 複合鋼板

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5987148A (ja) * 1982-10-08 1984-05-19 チバ−ガイギ−・アクチエンゲゼルシヤフト 金属シ−トと熱可塑性プラスチツク材からなるラミネ−ト
JPS62101431A (ja) * 1985-10-29 1987-05-11 昭和電工株式会社 複合鋼板

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6770374B1 (en) 1998-06-05 2004-08-03 Basf Aktiengesellschaft Composite elements containing compact polyisocyanate polyaddition products
US6790537B1 (en) 1999-03-30 2004-09-14 Basf Aktiengesellschaft Composite elements containing polyisocyanate-polyaddition products
US7223457B1 (en) 1999-11-04 2007-05-29 Basf Aktiengesellschaft Composite elements
US6828020B2 (en) 2002-08-14 2004-12-07 Adco Products, Inc. Self-adhesive vibration damping tape and composition
US20130284152A1 (en) * 2012-04-26 2013-10-31 Robert Bosch Gmbh System having a fuel distributor and a mounting support
US9970402B2 (en) * 2012-04-26 2018-05-15 Robert Bosch Gmbh System having a fuel distributor and a mounting support

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