# US 10,307,997 B2 · Laminate film, method for manufacturing same, and melamine decorative panel

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- Number: US 10,307,997 B2
- Document ID: US10307997B2
- Status: Granted
- Kind: B2
- Application number: 15/524,020
- Filed: 2015-10-27
- Published: 2017-11-16
- Granted: 2019-06-04
- Earliest claimed: 2014-11-04
- Assignees: Mitsubishi Chemical Corporation
- Applicants: Mitsubishi Chemical Corporation
- Inventors: Fuminori Nakaya; Junichi Abe
- Web page: https://patentgrep.com/patent/US10307997B2

## CPC

- B32B 27/08: of synthetic resin
- B05D 7/02: to macromolecular substances, e.g. rubber (treatment or coating of shaped articles made of macromolecular substances C08J7/00)
- B05D 7/24: for applying particular liquids or other fluent materials
- B29C 48/18: the components being layers
- B32B 27/304: {comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF}
- B32B 27/308: {comprising acrylic (co)polymers}
- B32B 27/42: comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
- B32B 37/18: involving the assembly of discrete sheets or panels only
- C08K 5/17: Amines; Quaternary ammonium compounds
- C08L 33/06: of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L 51/06: grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
- C08L 101/00: Compositions of unspecified macromolecular compounds
- E04F 13/0885: {specially adapted for being adhesively fixed to the wall; Fastening means therefor; Fixing by means of plastics materials hardening after application}
- E04F 13/18: of organic plastics with or without reinforcements or filling materials (of plastic-bound fibres or chips E04F13/16 ){or with an outer layer of organic plastics with or without reinforcements or filling materials; plastic tiles (E04F13/0864 takes precedence)}
- B32B 2250/24: All layers being polymeric
- B32B 2264/025: Acrylic resin particles, e.g. polymethyl methacrylate or ethylene-acrylate copolymers
- B32B 2270/00: Resin or rubber layer containing a blend of at least two different polymers
- B32B 2307/536: Hardness
- B32B 2307/584: Scratch resistance
- B32B 2307/71: Resistive to light or to UV
- B32B 2307/714: Inert, i.e. inert to chemical degradation, corrosion
- B32B 2307/7265: Non-permeable
- B32B 2307/734: Dimensional stability
- B32B 2398/10: Thermosetting resins
- B32B 2405/00: Adhesive articles, e.g. adhesive tapes
- B32B 2419/00: Buildings or parts thereof
- B32B 2451/00: Decorative or ornamental articles
- B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02)
- B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00)
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- E04F: FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS (windows, doors E06B)

## Abstract

Provided is a laminate film having excellent bonding properties, resistance to water whitening, and chemical resistance, and containing a fluororesin layer comprising a fluororesin composition, and an acrylic resin layer comprising a resin composition that contains a reactive group-containing acrylic resin, acrylic rubber particles, and a thermoplastic resin.

## Claims

### Claim 1

A laminate film comprising:
a fluororesin layer (I) which is formed from a fluororesin composition (A); and
an acrylic resin layer (II) which is formed from a resin composition (B) containing a reactive group-containing acrylic resin (B-1), wherein
the resin composition (B) contains 10 to 100% by mass of (B-1), 0 to 90% by mass of acrylic rubber particles (B-2) other than (B-1), and 0 to 90% by mass of a thermoplastic resin (B-3) having a mass average molecular weight of less than 400,000 other than (B-1) and (B-2) with respect to the total 100% by mass of (B-1), (B-2), and (B-3), and further contains 0 to 50 parts by mass of an additive (C) other than (B-1), (B-2), and (B-3) with respect to the total 100 parts by mass of (B-1), (B-2), and (B-3),
a gel fraction of the resin composition (B) is in the range of 10 to 80% by mass,
the reactive group-containing acrylic resin (B-1) contains a monomer unit having a reactive substituent with respect to an amino group or methylol group, and
a content of the monomer unit having the reactive substituent is 4% by mass or more with respect to 100% by mass of the resin composition (B).

### Claim 2 (depends on 1)

The laminate film according to claim 1, wherein the reactive substituent is a hydroxyl group.

### Claim 3 (depends on 1)

The laminate film according to claim 1, wherein the reactive substituent is a secondary hydroxyl group.

### Claim 4

A laminate film comprising:
a fluororesin layer (I) which is formed from a fluororesin composition (A); and
an acrylic resin layer (II) which is formed from a resin composition (B) containing a reactive group-containing acrylic resin (B-1), wherein
the resin composition (B) contains 10 to 100% by mass of (B-1), 0 to 90% by mass of acrylic rubber particles (B-2) other than (B-1), and 0 to 90% by mass of a thermoplastic resin (B-3) having a mass average molecular weight of less than 400,000 other than (B-1) and (B-2) with respect to the total 100% by mass of (B-1), (B-2), and (B-3), and further contains 0 to 50 parts by mass of an additive (C) other than (B-1), (B-2), and (B-3) with respect to the total 100 parts by mass of (B-1), (B-2), and (B-3),
a gel fraction of the resin composition (B) is in the range of 10 to 80% by mass,
the reactive group-containing acrylic resin (B-1) contains a monomer unit having a hydroxyl group, and
a hydroxyl value of the resin composition (B) is 15 to 300 mgKOH/g.

### Claim 5 (depends on 1)

The laminate film according to claim 1, wherein a glass transition temperature of the reactive group-containing acrylic resin (B-1) is 0 to 90° C.

### Claim 6 (depends on 1)

The laminate film according to claim 1, wherein a content of an aromatic vinyl monomer unit in the reactive group-containing acrylic resin (B-1) is 0 to 3% by mass with respect to 100% by mass of the reactive group-containing acrylic resin (B-1).

### Claim 7 (depends on 1)

The laminate film according to claim 1, wherein the resin composition (B) contains 10 to 90% by mass of (B-1), 10 to 90% by mass of (B-2), and 0 to 80% by mass of (B-3) with respect to the total 100% by mass of (B-1), (B-2), and (B-3).

### Claim 8 (depends on 1)

The laminate film according to claim 1, wherein the additive (C) contains a hindered amine-based stabilizer having a molecular weight of 1,000 or more.

### Claim 9 (depends on 1)

The laminate film according to claim 1, wherein the fluororesin composition (A) contains polyvinylidene fluoride.

### Claim 10 (depends on 1)

The laminate film according to claim 1, wherein a thickness of the laminate film is 100 μm or less.

### Claim 11 (depends on 1)

The laminate film according to claim 1, wherein a thickness of the fluororesin layer (I) is 30 μm or less.

### Claim 12 (depends on 1)

The laminate film according to claim 1, wherein a fracture elongation of the laminate film is 5% or more.

### Claim 13 (depends on 1)

A method for manufacturing the laminate film according to claim 1, comprising manufacturing the laminate film by a co-extrusion method.

### Claim 14 (depends on 1)

A method for manufacturing the laminate film according to claim 1, comprising manufacturing the laminate film by a coating method.

### Claim 15 (depends on 1)

A protection film comprising the laminate film according to claim 1.

### Claim 16 (depends on 1)

A melamine decorative panel surface protection film comprising the laminate film according to claim 1.

### Claim 17 (depends on 1)

A melamine decorative panel comprising the laminate film according to claim 1 and a melamine base material laminated in order of the fluororesin layer (I), the acrylic resin layer (II), and the melamine base material.

### Claim 18 (depends on 4)

The laminate film according to claim 4, wherein a glass transition temperature of the reactive group-containing acrylic resin (B-1) is 0 to 90° C.

### Claim 19 (depends on 4)

The laminate film according to claim 4, wherein a content of an aromatic vinyl monomer unit in the reactive group-containing acrylic resin (B-1) is 0 to 3% by mass with respect to 100% by mass of the reactive group-containing acrylic resin (B-1).

### Claim 20 (depends on 4)

The laminate film according to claim 4, wherein the resin composition (B) contains 10 to 90% by mass of (B-1), 10 to 90% by mass of (B-2), and 0 to 80% by mass of (B-3) with respect to the total 100% by mass of (B-1), (B-2), and (B-3).

### Claim 21 (depends on 4)

The laminate film according to claim 4, wherein the additive (C) contains a hindered amine-based stabilizer having a molecular weight of 1,000 or more.

### Claim 22 (depends on 4)

The laminate film according to claim 4, wherein the fluororesin composition (A) contains polyvinylidene fluoride.

### Claim 23 (depends on 4)

The laminate film according to claim 4, wherein a thickness of the laminate film is 100 μm or less.

### Claim 24 (depends on 4)

The laminate film according to claim 4, wherein a thickness of the fluororesin layer (I) is 30 μm or less.

### Claim 25 (depends on 4)

The laminate film according to claim 4, wherein a fracture elongation of the laminate film is 5% or more.

### Claim 26 (depends on 4)

A method for manufacturing the laminate film according to claim 4, comprising manufacturing the laminate film by a co-extrusion method.

### Claim 27 (depends on 4)

A method for manufacturing the laminate film according to claim 4, comprising manufacturing the laminate film by a coating method.

### Claim 28 (depends on 4)

A protection film comprising the laminate film according to claim 4.

### Claim 29 (depends on 4)

A melamine decorative panel surface protection film comprising the laminate film according to claim 4.

### Claim 30 (depends on 4)

A melamine decorative panel comprising the laminate film according to claim 4 and a melamine base material laminated in order of the fluororesin layer (I), the acrylic resin layer (II), and the melamine base material.