# US 12,110,428 B2 · Adhesively joined structure and component for a vehicle

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- Number: US 12,110,428 B2
- Document ID: US12110428B2
- Status: Granted
- Kind: B2
- Application number: 17/279,933
- Filed: 2019-09-27
- Published: 2021-11-04
- Granted: 2024-10-08
- Earliest claimed: 2018-09-28
- Assignees: Nippon Steel Corporation
- Applicants: Nippon Steel Corporation
- Inventors: Masumi Koori; Kohei Ueda; Atsushi Morishita; Atsuo Koga
- Web page: https://patentgrep.com/patent/US12110428B2

## CPC

- B32B 3/04: characterised by {at least one} layer folded at the edge, e.g. over another layer {; characterised by at least one layer enveloping or enclosing a material}
- C09J 5/10: Joining materials by welding overlapping edges with an insertion of plastic material
- B32B 5/02: characterised by structural features of a {fibrous or filamentary} layer {(layer formed of metallic wires B32B15/02; layer formed of natural mineral fibres B32B19/02; layer formed of wood fibres B32B21/02)}
- B32B 7/12: using interposed adhesives or interposed materials with bonding properties
- B32B 9/005: {comprising one layer of ceramic material, e.g. porcelain, ceramic tile (layered products with at least two ceramic layers composed mainly of ceramic B32B18/00)}
- B32B 9/041: {of metal}
- B32B 15/01: all layers being exclusively metallic {(making layered metal workpieces by pressure cladding B23K20/22; making coatings with a metallic material characterised by its composition C23C30/00)}
- B32B 15/011: {all layers being formed of iron alloys or steels}
- B32B 15/04: 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 (next to a bituminous or tarry layer B32B11/08; next to a water-setting substance layer B32B13/06; next to a glass layer B32B17/061; next to a cellulosic plastic layer B32B23/042)}
- B32B 15/043: {of metal (B32B15/01 takes precedence)}
- B32B 15/09: comprising polyesters
- B32B 15/092: comprising epoxy resins
- B32B 15/095: comprising polyurethanes
- B32B 15/14: next to a fibrous or filamentary layer
- B32B 15/18: comprising iron or steel {(B32B15/011, B32B15/012 and B32B15/013 take precedence)}
- C23C 26/00: Coating not provided for in groups C23C2/00 - C23C24/00
- C23C 28/00: Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- B32B 2250/02: 2 layers
- B32B 2250/03: 3 layers
- B32B 2255/06: on metal layer
- B32B 2255/26: Polymeric coating
- B32B 2255/28: Multiple coating on one surface
- B32B 2260/046: Synthetic resin
- B32B 2264/02: Synthetic macromolecular particles
- B32B 2264/0278: Polyester particles
- B32B 2264/0292: Polyurethane particles
- B32B 2307/54: Yield strength; Tensile strength
- B32B 2307/732: Dimensional properties
- B32B 2605/00: Vehicles
- B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- C09J: ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES (preparation of glue or gelatine C09H)
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)

## Abstract

This adhesively joined structure includes a first member having a metal portion and a film portion disposed on at least a part of a surface of the metal portion; a second member; an adhesive layer for joining the first member and the second member to each other via the film portion. The film portion includes an organic resin phase containing one or more of a urethane group, an epoxy group, and an ester group; an organic compound phase formed of an organic silicon compound; and optionally an inorganic compound phase formed of an inorganic silicon compound. The total volume percentage of the organic compound phase and the inorganic compound phase to the total volume of the film portion is 16 vol % to 84 vol %. The volume percentage of the organic compound phase to the total volume of the film portion is 16 vol % to 84 vol %. The volume percentage of the inorganic compound phase to the total volume of the film portion is limited to 10 vol % or less. The organic silicon compound includes a Si—C bond; and a Si—O bond or a Si—OH bond or a a combination thereof.

## Claims

### Claim 1

An adhesively joined structure comprising:
a first member having a metal portion and a film portion disposed on at least a part of a surface of the metal portion;
a second member having a metal portion and a film portion disposed on at least a part of a surface of the metal portion of the second member;
an adhesive layer for joining the first member and the second member to each other via the film portion of the first member,
wherein the film portion of the first member includes
an organic resin phase containing one or more of a urethane group, an epoxy group, and an ester group;
an organic compound phase formed of an organic silicon compound; and
optionally an inorganic compound phase formed of an inorganic silicon compound,
a total volume percentage of the organic compound phase and the inorganic compound phase to a total volume of the film portion of the first member is 16 vol % to 84 vol %,
a volume percentage of the organic compound phase to the total volume of the film portion of the first member is 16 vol % to 84 vol %,
a volume percentage of the inorganic compound phase to the total volume of the film portion of the first member is limited to 10 vol % or less,
the organic silicon compound includes
a Si—C bond; and
a Si—O bond or a Si—OH bond or combination thereof.

### Claim 2 (depends on 1)

The adhesively joined structure according to claim 1,
wherein the total volume percentage of the organic compound phase and the inorganic compound phase is 20 vol % to 80 vol %.

### Claim 3 (depends on 2)

The adhesively joined structure according to claim 2,
wherein the organic resin phase is resin particles containing one or more of the urethane group, the epoxy group, and the ester group,
an average particle size of the resin particles is 20 nm or more to less than 200 nm, and
an area percentage of the resin particles is 20% to 80% with respect to a cross sectional area of the film portion of the first member in a cross section taken in a thickness direction of the film portion of the first member.

### Claim 4 (depends on 1)

An adhesively joined structure according to claim 1,
wherein when the film portion of the first member is analyzed by a time-of-flight secondary ion mass spectrometry while the film portion of the first member is Ar-spattered from the adhesive layer side toward the metal portion side in the first member to include an optional point of an interface between the metal portion of the first member and the film portion of the first member, peaks corresponding to Si—O—Me bonds, which are bonds with a metal element Me constituting the metal portion of the first member, were observed, and a value obtained by dividing a count value of the peaks indicating the Si—O—Me bonds by a total value of all the secondary ion count numbers detected in a mass scanning range m/z=0 to 300 is 1.0×10−3 or more.

### Claim 5 (depends on 1)

The adhesively joined structure according to claim 1,
wherein an average thickness of the film portion of the first member is 0.2 μm to 1.5 μm per one side of the first member.

### Claim 6 (depends on 1)

The adhesively joined structure according to claim 1,
wherein a resin of an adhesive constituting the adhesive layer has a common chemical structure with a resin constituting the organic resin phase in the film portion of the first member.

### Claim 7 (depends on 1)

The adhesively joined structure according to claim 1,
wherein the adhesive layer contains an epoxy resin-based adhesive or a urethane resin-based adhesive or combination thereof.

### Claim 8 (depends on 1)

The adhesively joined structure according to claim 1,
wherein the metal portion of the first member is a steel.

### Claim 9 (depends on 1)

The adhesively joined structure according to claim 1,
wherein the metal portion of the first member is a zinc-plated steel sheet.

### Claim 10 (depends on 1)

The adhesively joined structure according to claim 1,
wherein the metal portion of the first member is a galvannealed steel sheet having a tensile strength of 590 MPa or more.

### Claim 11 (depends on 1)

The adhesively joined structure according to claim 1,
wherein the metal portion of the first member is a galvannealed steel sheet having a tensile strength of 980 MPa or more.

### Claim 12 (depends on 1)

The adhesively joined structure according to claim 1,
wherein the first member and the second member are further joined by a second joining.

### Claim 13 (depends on 12)

The adhesively joined structure according to claim 12, wherein the second joining is spot welding.

### Claim 14 (depends on 1)

A component for a vehicle comprising:
the adhesively joined structure according to claim 1.

### Claim 15 (depends on 2)

An adhesively joined structure according to claim 2,
wherein when the film portion of the first member is analyzed by a time-of-flight secondary ion mass spectrometry while the film portion of the first member is Ar-spattered from the adhesive layer side toward the metal portion side in the first member to include an optional point of an interface between the metal portion of the first member and the film portion of the first member, peaks corresponding to Si—O—Me bonds, which are bonds with a metal element Me constituting the metal portion of the first member, were observed, and a value obtained by dividing a count value of the peaks indicating the Si—O—Me bonds by a total value of all the secondary ion count numbers detected in a mass scanning range m/z=0 to 300 is 1.0×10−3 or more.

### Claim 16 (depends on 3)

An adhesively joined structure according to claim 3,
wherein when the film portion of the first member is analyzed by a time-of-flight secondary ion mass spectrometry while the film portion of the first member is Ar-spattered from the adhesive layer side toward the metal portion side in the first member to include an optional point of an interface between the metal portion of the first member and the film portion of the first member, peaks corresponding to Si—O—Me bonds, which are bonds with a metal element Me constituting the metal portion of the first member, were observed, and a value obtained by dividing a count value of the peaks indicating the Si—O—Me bonds by a total value of all the secondary ion count numbers detected in a mass scanning range m/z=0 to 300 is 1.0×10−3 or more.