JP2003291261A - Embossed decorative metallic sheet and method for manufacturing the same, and resin film to be laminated on monolayer embossed decorative metallic sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an embossed decorative metallic sheet which uses a resin material free from an environmental load and shows outstanding properties in terms of adhesion with a base metallic sheet, moldability, resistance to flaw and boiling water, and a resin film to be laminated on the embossed decorative metallic sheet, and a method for manufacturing the embossed decorative metallic sheet. <P>SOLUTION: The embossed decorative metallic sheet has a polyester resin layer, coated on the surface, in which an expansion stress relaxation agent is finely dispersed with an embossed surface. Also the resin film to be laminated on the embossed decorative metallic sheet is provided. The polyester resin layer (A) is preferably structured of a rubber-like elastic body resin (B) which is finely dispersed as the expansion stress relaxation agent, in the polyester resin (A) which is a matrix and is at least partially encapsulated by a vinyl polymer (C) having a polar group. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an embossed decorative metal plate, a resin film for laminating a single-layer embossed decorative metal plate, and a method for manufacturing an embossed decorative metal plate, and more specifically, to an inner wall of a unit bath or a door of an electric refrigerator, Embossed decorative metal plate suitable for applications requiring an embossed pattern design, such as home appliance exteriors such as air conditioner covers, steel furniture, elevators, interiors of buildings, etc. The present invention relates to a method for producing a resin film and an embossed decorative metal plate.

[0002]

2. Description of the Related Art A steel sheet having an embossed design is used for an inner wall material for construction, etc., and the steel sheet surface is mainly covered with a vinyl chloride resin layer and the surface is embossed. The decorative steel plate or other decorative metal plate having such an embossed design can be used for various purposes other than the interior material for construction.

Although such an embossed decorative metal plate has been put into practical use, recently, since vinyl chloride resin contains chlorine,
It has been withheld from the viewpoint of environmental load. Therefore, it has been proposed to use a polyolefin resin layer as an alternative material. Embossing is possible with polyolefin resins. Further, in the case of a polyester resin, a biaxially stretched film has a large shrinkage during embossing and has a problem of being difficult to process, and thus the productivity is low. Therefore, a polyester resin obtained by copolymerizing polyethylene terephthalate with cyclohexanedimethanol and isophthalic acid is used. That (Japanese Patent Laid-Open No.
0-301662), using a polyester resin having a specific crystallinity (Japanese Patent Laid-Open No. 2001-2873).
No. 26) is proposed.

[0004]

However, although the polyolefin resin can be embossed, the polyolefin resin is poor in stretchability, so that stress is locally concentrated particularly during processing at low temperatures such as in winter. There are drawbacks such as whitening and cracking, and low scratch resistance. Further, in the case of polyester resin film, the method disclosed in
With the configuration of 0-301662, shrinkage during embossing can be reduced, but there is a problem that it cannot be used under severe conditions such as a unit bath because it deforms in a high temperature and high humidity environment. The decorative film disclosed in JP 2001-287326 A has a drawback that an adhesive resin layer is required between the decorative film and the metal plate of the substrate, resulting in insufficient adhesion.

Further, it has been proposed to solve these problems by using a resin film having a multilayer structure,
Not only not enough things have been provided yet, but the cost is high.

The present invention has been made in view of the current state of the art as described above, and is made of a resin material having no environmental load, such as adhesion to a metal plate of a substrate, moldability, flaw resistance, and resistance to scratches. An object of the present invention is to provide an embossed decorative metal plate having excellent properties such as boiling water, a resin film for laminating an embossed decorative metal plate therefor, and a method for producing an embossed decorative metal plate.

[0007]

The present invention is achieved by the above object by coating a metal plate with a polyester resin layer in which a stretching stress relaxation agent is finely dispersed in a polyester resin, and embossing the surface. It was made by finding that. The present invention thus provides:

(1) An embossed decorative metal which is formed by coating the surface of a metal plate with a colored polyester resin layer in which a stretching stress relaxation agent is finely dispersed, and the surface of the polyester resin layer is embossed. Board.

(2) The polyester resin layer is a polyester resin (A) as a matrix in which a rubber-like elastic resin (B) is finely dispersed as a stretching stress relaxation agent, and at least a rubber-like elastic resin. The embossed decorative metal plate according to (1), which has a structure in which a part of (B) is encapsulated with a vinyl polymer (C) having a polar group.

(3) The embossed decorative metal sheet according to (1) or (2), wherein the equivalent spherical equivalent diameter of the stretching stress relaxation agent finely dispersed in the polyester resin is 1 μm or less.

(4) The embossed decorative metal plate of (1) to (3), wherein the matrix resin of the polyester resin layer is polyethylene terephthalate, modified polyethylene terephthalate, polybutylene terephthalate, modified polybutylene terephthalate or a combination thereof.

(5) A resin film for laminating embossed decorative metal plates, characterized in that the surface of a colored polyester resin film in which a stretching stress relaxation agent is finely dispersed is embossed.

(6) The polyester resin film comprises
A polyester resin (a) as a matrix, in which a rubber-like elastic resin (B) is finely dispersed as a stretching stress relaxation agent, and at least a part of the rubber-like elastic resin (B) has a polar group. The resin film for laminating embossed decorative metal plates according to (5), which has a structure encapsulated with a polymer (C).

(7) The resin film for laminating embossed decorative metal sheets according to (5) and (6), wherein the equivalent spherical equivalent diameter of the stretching stress relaxation agent finely dispersed in the polyester resin is 1 μm or less.

(8) For the lamination of the embossed decorative metal plates of (5) to (7), wherein the matrix resin of the polyester resin film is polyethylene terephthalate, modified polyethylene terephthalate, polybutylene terephthalate, modified polybutylene terephthalate or a combination thereof. Resin film.

(9) The polyester resin film has a shrinkage of 20% at a temperature 100 to 10 ° C. lower than the melting point.
(5) to (7) embossed decorative metal plate laminating resin film composed of the following resin films.

(10) The resin film for laminating embossed decorative metal plates according to (5) to (9), which is an amorphous resin film in which the glass transition temperature of the polyester resin film is 100 ° C. or higher.

(11) The polyester resin film is made of a crystalline resin, and the crystalline resin has a glass transition temperature of 1
The resin film for laminating embossed decorative metal plates according to (5) to (9), which has a crystallization rate of 00 ° C. or higher or a crystallization rate of 10% or higher of a saturated crystallization rate.

(12) A colored polyester resin film in which a stretching stress relaxation agent is finely dispersed is laminated on a metal plate, and the surface of the polyester resin film is embossed during or after the lamination. The method for producing an embossed decorative metal plate according to any one of 1 to 4.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION According to the present invention, the surface of a metal plate is covered with a polyester resin layer in which a stretching stress relaxation agent is finely dispersed in a polyester resin, and the surface of the polyester resin layer is embossed. It is characterized by.

Polyester resin has no problem of whitening and scratching property at low temperature processing unlike polyolefin resin, and has impact resistance and other mechanical properties, chemical resistance, insulation property, heat resistance,
It has excellent gas barrier properties and adhesion to metals.
However, the biaxially stretched polyester resin film undergoes thermal deformation in order to obtain properties such as impact resistance, anti-fluffing water resistance, water resistance, and chemical resistance, so it is deformed by the heat of embossing or baking on a metal plate. However, there is a problem that the adhesiveness to the metal plate cannot be obtained and the physical properties are deteriorated. In addition, there is a problem that when it is used in a hot and humid environment where it is exposed to boiling water like an interior material of a unit bath, it is easily deformed. The present invention, surprisingly, the one in which the stretching stress relaxation agent is finely dispersed in the polyester resin can prevent thermal deformation, so that it can withstand the heat treatment such as embossing and thermal lamination thermocompression bonding, and also has boiling water. The present invention has been found to provide an embossed decorative metal plate that can be used practically because it does not deform even in a hot and humid environment.

From the viewpoint of productivity, the present invention was developed with the intention of laminating a polyester resin film on a metal plate for production, and hereinafter, the resin film for laminating metal plates will be mainly described. However, the present invention is not limited to this.

In order to finely disperse the stretching stress relaxation agent in the polyester resin, a rubber-like elastic resin (B) and / or a vinyl polymer is used as the stretching stress relaxation agent, and especially the rubber is contained in the polyester resin (A). It is particularly preferable that the elastic resin (B) is finely dispersed and at least a part of the elastic rubber resin (B) is encapsulated by the vinyl polymer (C) having a polar group. By using a vinyl polymer (C), a part of which has a polar group, it is easy to finely disperse the rubber-like elastic resin (B) in the polyester resin (A), and at the same time, the metal of the polyester resin layer It also has the effect of improving the adhesion to the plate.

In the following, a rubber-like elastic resin (B) is used as a stretching stress relaxation agent in the polyester resin (A) in order to finely disperse the stretching stress relaxation agent in the polyester resin.
An embodiment in which at least a part of the rubber-like elastic resin (B) is encapsulated by the vinyl polymer (C) having a polar group, that is, a preferred embodiment of the present invention will be mainly described.

Here, the fine dispersion means a rubber-like elastic resin.
(B) is a polyester resin with an equivalent spherical equivalent diameter of 100 μm or less (A)
It is in a dispersed state. If the equivalent spherical equivalent diameter of the rubber-like elastic resin (B) exceeds 100 μm, it becomes difficult to process the resin composition of the present invention into a film. The equivalent spherical equivalent diameter is preferably 1 μm or less, more preferably 0.5 μm or less. If it exceeds 1 μm, sufficient impact resistance may not be exhibited.

The rubber-like elastic resin (B) encapsulated with the vinyl polymer (C) means that 80% or more, preferably 95% or more of the rubber-like elastic resin (B) interface is vinyl polymer. The structure is such that the area covered by (C) and the direct contact area between the polyester resin (A) and the rubber-like elastic resin (B) is less than 20%. With such a structure, even if the rubber-like elastic resin (B) is in contact with the metal plate, the vinyl polymer (C) has adhesiveness with the metal plate, and thus the polyester resin layer and the metal plate are in close contact with each other. You can secure the sex.

It is not necessary that all of the rubber-like elastic resin (B) is encapsulated with the vinyl polymer (C), and at least 70% by volume or more of the rubber-like elastic resin (B) is a vinyl polymer.
It only needs to be encapsulated in (C). When the rubber-like elastic resin (B) which is not encapsulated is present in an amount of more than 30% by volume, when the polyester resin composition is coated on the metal plate, the rubber-like elastic resin directly contacting the metal plate ( The ratio of B) increases, and it becomes impossible to secure the adhesion between the polyester resin composition and the metal plate. The equivalent spherical equivalent diameter of the non-encapsulated rubber-like elastic resin (B) is not particularly specified, but is preferably 0.5 μm or less from the viewpoint of impact resistance and workability.

The excess amount of the vinyl polymer (C) may be dispersed alone in the polyester resin (A) without encapsulating the rubber-like elastic resin (B). The amount of the vinyl polymer (C) not encapsulated, the diameter is not particularly limited, but the volume ratio of the total vinyl polymer (C) is 20% or less, and the equivalent spherical equivalent diameter may be 0.5 μm or less. desirable. By volume ratio
If it exceeds 20%, the basic properties such as heat resistance of the polyester resin layer may change. If the equivalent spherical equivalent diameter exceeds 0.5 μm, the workability may decrease.

The polyester resin layer of the present invention is not particularly limited as long as it has the above-mentioned structure, and the composition is not particularly limited, but with respect to 100 parts by mass of the polyester resin (A), the rubber-like elastic resin ( B) is 1 to 50 parts by mass, and the vinyl polymer (C) is 1
It is preferably a resin composition for coating a metal plate, which comprises ˜50 parts by mass. If the rubber-like elastic resin (B) is less than 1 part by mass, sufficient impact resistance may not be imparted, and if it exceeds 50 parts by mass, heat resistance may decrease. If the vinyl polymer (C) is less than 1 part by mass, the rubber-like elastic resin (B) may not be fully encapsulated, and if it exceeds 50 parts by mass, the heat resistance may decrease.

The intrinsic viscosity of the polyester resin (A) used in the present invention is preferably 0.5 to 2.0 dl /, more preferably 0.6.
It is 5 to 1.7 dl / g, and more preferably 0.8 to 1.5 dl / g. When the intrinsic viscosity is less than 0.5 dl / g, the mechanical strength and impact resistance are low because the rubber-like elastic resin (B) and polar monomer-containing vinyl polymer (C) are not mixed uniformly, while the intrinsic viscosity is 2.0d
When it exceeds 1 / g, the moldability becomes poor, which is not preferable.

The above-mentioned intrinsic viscosity is determined by the following formula (i) by measuring at a concentration of 0.5% in o-chlorophenol at 25 ° C. In the formula, C represents the concentration of the resin expressed in g per 100 ml of the solution, t ₀ represents the solvent flowing time, and t represents the solution flowing time.

Intrinsic viscosity = {ln (t / t ₀ )} / C (i) The polyester resin (A) used in the present invention means only a hydroxycarboxylic acid compound residue, a dicarboxylic acid residue and a diol. It is a thermoplastic polyester having a compound residue, or a hydroxycarboxylic acid compound residue, a dicarboxylic acid residue and a diol compound residue as constituent units, respectively. Also, a mixture of these may be used.

Examples of the hydroxycarboxylic acid compound as a raw material for the hydroxycarboxylic acid compound residue include p-hydroxybenzoic acid, p-hydroxyethylbenzoic acid and 2- (4-
(Hydroxyphenyl) -2- (4'-carboxyphenyl) propane and the like, these may be used alone, also,
You may mix and use 2 or more types.

Examples of dicarboxylic acid compounds forming a dicarboxylic acid residue include terephthalic acid, isophthalic acid, orthophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,
Aromatic dicarboxylic acids such as 3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenic acid, diphenyldicarboxylic acid, diphenoxyethanedicarboxylic acid and adipic acid, vimelic acid, sebacic acid, Azelaic acid, decanedicarboxylic acid, malonic acid, succinic acid, malic acid, aliphatic dicarboxylic acids such as citric acid, alicyclic carboxylic acids such as cyclohexanedicarboxylic acid and the like, these may be used alone, ,
You may mix and use 2 or more types.

Next, exemplifying a diol compound which forms a diol residue is 2,2'-bis (4-hydroxyphenyl).
Propane (hereinafter abbreviated as "bisphenol A"), bis (4-hydroxyphenyl) methane, bis (2-hydroxyphenyl) methane, o-hydroxyphenyl-p-hydroxyphenylmethane, bis (4-hydroxyphenyl) ether , Bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) diphenylmethane, bis (4- (Hydroxyphenyl) -p-diisopropylbenzene, bis (3,5-dimethyl-4-hydroxyphenyl) methane, bis (3-methyl-4-hydroxyphenyl) methane, bis (3,5-dimethyl-4-hydroxyphenyl) Ether, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfide,
1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (3,5
-Dimethyl-4-hydroxyphenyl) ethane, 1,1-bis (4-
Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,
1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1
-Bis (4-hydroxyphenyl) -1-phenylmethane, 2,2-
Bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (3,5-dimethyl-4-
Hydroxyphenyl) propane, 2,2-bis (3,5-difluoro-4-hydroxyphenyl) propane, 2,2-bis (3,5-difluoro-4-hydroxyphenyl) propane, 2,2-bis (3
-Methyl-4-hydroxyphenyl) propane, 2,2-bis (3-
Fluoro-4-hydroxyphenyl) propane, 2,2-bis (3
-Fluoro-4-hydroxyphenyl) propane, 1,1,1,3,
3,3-hexafluoro-2,2-bis (4-hydroxyphenyl)
Propane, 4,4'-biphenol, 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxybiphenyl, aromatic diol such as 4,4'-dihydroxybenzophenone and ethylene glycol, trimethylene glycol, Fats such as propylene glycol, tetramethylene glycol, 1,4-butanediol, pentamethylene glycol, neopentyl glycol, hexamethylene glycol, dodecamethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, hydrogenated bisphenol A Examples thereof include group diols and alicyclic diols such as cyclohexanedimethanol, and these can be used alone or as a mixture of two or more kinds. Further, the polyester resins obtained from these may be used alone or in combination of two or more.

Polyester resin (A) used in the present invention
May be composed of these residues or a combination thereof. Among them, an aromatic polyester resin composed of an aromatic dicarboxylic acid residue and a diol residue is preferable in terms of processability and thermal stability. It is preferable from the viewpoint.

The polyester resin used in the present invention
(A) is a small amount of a structural unit derived from a polyfunctional compound such as trimesic acid, pyromellitic acid, trimethylolethane, trimethylolpropane, trimethylolmethane, and pentaerythritol, for example, containing an amount of 2 mol% or less. You may stay.

From the viewpoint of heat resistance and processability, the most preferable combination of these dicarboxylic acid compounds and diol compounds is 50 to 95 mol% of terephthalic acid, 50 to 5 mol% of isophthalic acid and / or orthophthalic acid. And a diol compound of a glycol having 2 to 5 carbon atoms.

Examples of the preferred polyester resin (A) used in the present invention include polyethylene terephthalate, modified polyethylene terephthalate, polybutylene terephthalate, modified polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexylene dimethylene terephthalate, polyethylene-2, 6-naphthalate, polybutylene-2,6-naphthalate and the like, but among them, suitable mechanical properties, gas barrier properties, and polyethylene terephthalate having metal adhesion, polybutylene terephthalate, polyethylene-2,6-naphthalate,
Most preferred is polybutylene-2,6-naphthalate.

Polyester resin (A) used in the present invention
Is the glass transition temperature (Tg, sample amount about 10 mg, heating rate 1
(Measured with a differential thermal analyzer (DSC) at 0 ° C / min) is usually 30 to 1
It is desirable that the temperature is 20 ° C, preferably 60 to 100 ° C. This polyester resin (A) may be amorphous or crystalline, and when it is crystalline, the crystal melting temperature (T
m) is usually 210 ~ 265 ℃, preferably 210 ~ 245 ℃,
Low temperature crystallization temperature (Tc) is usually 110 ~ 220 ℃, preferably 12
It is preferably 0 to 215 ° C. If Tm is less than 210 ° C or Tc is less than 110 ° C, the heat resistance may be insufficient and the film shape may not be retained during drawing. If Tm is higher than 265 ° C or Tc is higher than 220 ° C, the resin may not sufficiently enter the surface irregularities of the metal plate, resulting in poor adhesion.

Next, the stretching stress relaxation agent used in the present invention is generally a rubber elastic body, but it is sufficient as long as it has the same function and it is caused by tension or heat in the polyester resin. Any material can be used as long as it can absorb or reduce the variation in expansion and contraction.

As the rubber-like elastic resin (B) which is a stretching stress relaxation agent which can be preferably used in the present invention, known rubber-like elastic resin can be widely used. Among them, the glass transition temperature (Tg, sample amount about 10 mg, temperature rising rate 10 ° C / min measured with a differential thermal analyzer (DSC)) of the rubber elasticity developing part is 50 ° C or lower, and Young's modulus at room temperature is 1000 MPa or lower. And a rubber-like elastic resin having a breaking elongation of 50% or more is preferable. Tg of rubber elasticity expression part is 50
Above ℃, Young's modulus at room temperature is over 1000 MPa, and elongation at break is 5
If it is less than 0%, sufficient impact resistance cannot be exhibited. In order to secure impact resistance at low temperatures, Tg is preferably 10 ° C or lower, more preferably -30 ° C or lower. In order to secure more reliable impact resistance, Young's modulus at room temperature is
100 MPa or less, more preferably 10 MPa or less,
The breaking elongation is preferably 100% or more, more preferably 300% or more.

Specific examples of the rubber-like elastic resin (B) used in the present invention include polyolefin resin, butadiene-styrene copolymer (SBR), acrylonitrile-butadiene copolymer (NBR), polyisoprene ( IPR), diene elastomer such as polybutadiene (BR), styrene-butadiene-styrene copolymer (SBS) and its hydrogenated product (SEBS), rubber modified styrene (HIPS), acrylonitrile-styrene-butadiene copolymer (ABS ) Styrene-based elastomers such as
Examples include silicone elastomers containing dimethylsiloxane as a main component, polyester elastomers such as aromatic polyester-aliphatic polyester copolymers or aromatic polyester-polyether copolymers, and nylon elastomers.

Of these, polyolefin resins are preferable because they have low water vapor permeability. The polyolefin resin has the following general formula (a) -R ₁ CH-CR ₂ R _3- (a) (In the formula, R ₁ and R ₃ each independently represent an alkyl group having 1 to 12 carbon atoms or hydrogen, R ₂ is a resin having a repeating unit represented by an alkyl group having 1 to 12 carbon atoms, a phenyl group or hydrogen).

The polyolefin resin used in the present invention is
It may be a homopolymer of these constituent units, a copolymer of two or more kinds, or a copolymer of resin units formed of these units.

Examples of repeating units include propylene,
1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene and other repeating units that appear when addition-polymerizing α-olefins and isobutene were added. In addition to aliphatic olefins such as repeating units and styrene monomers, alkylated styrenes such as o-, m-, p-methylstyrene, o-, m-, p-ethylstyrene and t-butylstyrene, monofluorostyrene Aromatic olefins such as halogenated styrenes such as, and addition polymer units of styrene-based monomers such as α-methylstyrene, and the like.

Examples of the polyolefin resin include polyethylene, polypropylene, polybutene, polypentene, polyhexene, polyoctenylene and the like, which are homopolymers of α-olefin. Further, as the copolymer of the above units, ethylene / propylene copolymer, ethylene / butene copolymer, ethylene / propylene / 1,6-hexadiene copolymer, ethylene / propylene / 5-ethylidene-2-norbornene copolymer Examples thereof include aliphatic polyolefins such as coalesced products, aromatic polyolefins such as styrene-based polymers, and the like. However, the present invention is not limited to these, and the above repeating units may be satisfied. Further, these resins may be used alone or in combination of two or more kinds.

Further, the polyolefin resin may be composed of the above-mentioned olefin unit as a main component, and a vinyl monomer, a polar vinyl monomer, which is a substitution product of the above-mentioned unit,
The diene monomer may be copolymerized with a monomer unit or a resin unit. The copolymer composition is 50 mol% or less, preferably 30 mol% or less, based on the unit. If it exceeds 50 mol%, the properties of the polyolefin resin such as dimensional stability will deteriorate.

Examples of polar vinyl monomers are acrylic acid, methyl acrylate, acrylic acid derivatives such as ethyl acrylate, methacrylic acid derivatives such as methacrylic acid, methyl methacrylate, ethyl methacrylate, acrylonitrile, maleic anhydride, and anhydrous. Examples thereof include imide derivatives of maleic acid.

Examples of the diene monomer include butadiene, isoprene, 5-methyleidene-2-norbornene, 5-ethylidene-2-norbornene, jinglopentadiene and 1,4-hexadiene.

The most preferable resin for imparting impact strength as the polyolefin resin is ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-pentene-1 copolymer, ethylene-3-ethylpentene. Copolymer, ethylene-copolymer of ethylene and octacene-1 copolymer and the like α-olefin having 3 or more carbon atoms, or the above
Ethylene obtained by copolymerizing a binary copolymer with butadiene, isoprene, 5-methylidene-2-norbornene, 5-ethylidene-2-norbornene, jinglopentadiene, 1,4-hexadiene, and α-olefins having 3 or more carbon atoms. And a terpolymer of non-conjugated dienes. Among them, from the ease of handling, a binary copolymer of ethylene-propylene copolymer and ethylene-butene-1 copolymer, or ethylene-propylene copolymer and ethylene-butene-1 copolymer, 5-methylidene-2-norbornene, 5-ethylidene-2-norbornene, jinglopentadiene and 1,4-hexadiene are used as non-conjugated dienes, and the amount of α-olefin is 2
A resin in which 0 to 60 mol% and a non-conjugated diene of 0.5 to 10 mol% are copolymerized is most preferable.

Next, the vinyl polymer (C) containing 1% by mass or more of the unit having a polar group used in the present invention is bound to an element having a Pauling electronegativity difference of 0.9 (eV) ^0.5 or more. It is a vinyl polymer containing 1% by mass or more of a unit having the above group. When the unit having a polar group is less than 1% by mass, sufficient adhesion to the metal plate cannot be exhibited even when the rubber-like elastic resin (B) is encapsulated with the vinyl polymer (C).

The difference in Pauling's electronegativity is 0.9 (eV) ^0.5
Specific examples of the groups to which the above-mentioned elements are bound include -CO
-, - C = O, -COO- , epoxy _{group, C 2 O 3, C 2} O 2 N -, - CN, -NH
₂ , -NH-, -X (X; F), -SO _3- , and the like.

An example of a unit having a polar group is -C
Vinyl alcohol as an example having -O- group, vinyl fluoromethyl ketone as an example having -C = O group, acrylic acid as an example having -COO- group, methacrylic acid, vinyl acetate, vinyl acid such as propionic acid and the like. Metal salts or ester derivatives, examples having an epoxy group include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itacrylate, and the like, α-β-
Glycidyl ester of unsaturated acid, maleic anhydride as an example having a C ₂ O ₃ group, imide derivative of maleic anhydride as an example having a C ₂ O ₂ N- group, acrylonitrile as an example having a -CN group, -NH ₂ Acrylic amine as an example having a group,
Examples include acrylamide as an example having an -NH- group, vinyl fluoride as an example having an -X group, styrene sulfonic acid as an example having an -SO ₃ -group, and the like. It may be contained in C). The unit having a polar group contained in the vinyl polymer (C),
The unit is not limited to the above specific examples as long as it is a unit having a group to which an element having a Pauling electronegativity difference of 0.9 (eV) ^0.5 or more is bonded.

Examples of the vinyl polymer (C) used in the present invention are represented by the above-mentioned polar group-containing unit alone or two or more kinds of polymers, and the polar group-containing unit and the following general formula (b). Examples thereof include copolymers with non-polar vinyl monomers.

-R ₁ CH = CR ₂ R _3- (b) (In the formula, R ₁ and R ₃ are each independently an alkyl group having 1 to 12 carbon atoms or hydrogen, and R ₂ is an alkyl group having 1 to 12 carbon atoms. An alkyl group, a phenyl group or hydrogen is shown.) When the nonpolar vinyl monomer represented by the general formula (b) is specifically shown,
Ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1
-In addition to α-olefins such as dodecene, aliphatic vinyl monomers such as isobutene and isobutylene, and styrene monomers
Aromatic aromatic compounds such as alkylated styrenes such as o-, m-, p-methylstyrene, o-, m-, p-ethylstyrene and t-butylstyrene, addition polymer units of styrene monomers such as α-methylstyrene Examples thereof include vinyl monomers.

Examples of the homopolymer of the polar group-containing unit include polyvinyl alcohol, polymethyl methacrylate, polyvinyl acetate and the like. Examples of copolymers of polar group-containing units and non-polar vinyl monomers include ethylene-methacrylic acid copolymers, ethylene-acrylic acid copolymers, ethylene-vinyl acetate copolymers and copolymers thereof. Ionomer resin obtained by neutralizing a part or all of the carboxylic acid with a metal ion, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate Copolymer, ethylene-glycidyl methacrylate copolymer, ethylene-maleic anhydride copolymer, butene-ethylene-glycidyl methacrylate copolymer, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-anhydrous Examples thereof include maleic acid copolymers. From the viewpoint of ensuring barrier properties, a copolymer of α-olefin and a unit having a polar group is a preferred combination. The vinyl polymer (C) used in the present invention is not limited to the above specific examples as long as it is a vinyl polymer containing 1% by mass or more of a unit having a polar group. Also vinyl polymers
The molecular weight of (C) is not particularly limited, but a number average molecular weight of 2000 or more and 500000 or less is preferable. Less than 2000 or 5000
If it exceeds 00, the rubber-like elastic resin (B) may not be sufficiently encapsulated in some cases.

Vinyl polymer (C) in polyester resin (A)
In order to finely disperse the rubber-like elastic resin (B) encapsulated in, the balance of the interfacial tension between the vinyl polymer (C) and the polyester resin (A) and the rubber-like elastic resin (B) is made appropriate. This is very important. Preferably, the _{spread parameter} (λ ₍ Resin _n ) for the rubber-like elastic resin (B) of the vinyl polymer (C)
It is desirable to control the content of the unit having a polar group so that _{C) / (Resin B)} ) becomes positive. λ _{(Resin
By making C) / (Resin B)} positive, vinyl polymer (C)
Thus, thermodynamic stability can be secured even if the rubber-like elastic resin (B) is encapsulated. Spread Parameter between different kinds of polymers is a parameter defined in SY Hobbs; Polym., Vol.29, p1598 (1989), and the following formula (ii) λ _{(Resin C) / (Resin B) = Υ (resin B) / (} resin A) - Υ (resin C) / (resin B) - Υ (R esin C) / (resin A) (ii) [ in the formula, resin A polyester resin (A ), Resin
B represents the rubber-like elastic resin (B), Resin C represents the vinyl polymer (C), and Υ _{i / j} is the interfacial tension between the resin i and the resin j. It is proportional to the 0.5th power of the parameter Χ _{i / j} indicating the compatibility between resin i and resin j (the smaller the better compatibility is, the smaller the value). ] Is given.

Polyester resin (A) and rubber-like elastic resin
Since the compatibility with (B) is low and Υ _{(Resin B) / (Resin A)} > 0, the non-polar vinyl monomer (Monome) of vinyl polymer (C) is
r V) and the polar group-containing unit (Monomer U) by adjusting the compounding ratio, and the following formulas (iii) and (iv) Χ _{A / C} = φ Χ _{(Resin A) / (Monomer V)} + (1-φ ) Χ _{(Resin A) / (Monomer U)} -φ (1-φ) Χ _{(Monomer V) / (Monomer U)} (iii) Χ _{B / C} = φΧ _{(Resin B) / (Monomer V)} + (1- φ) Χ _{(Resin B) / (Monomer U)} -φ (1-φ) Χ _{(Monomer V) / (Monomer U)} (iv) (where φ represents the compounding ratio (volume ratio) of non-polar vinyl monomer) . ], Which shows the compatibility between the rubber-like elastic resin (B) and the vinyl polymer (C), and _{B / C} and polyester resin (A)
It is possible to make λ _{(Resin C) / (Resin B)} positive by setting Χ _{A / C} , which indicates the compatibility between the polymer and vinyl polymer (C), close to 0.

Therefore, the preferred vinyl polymer (C)
Is determined according to the types of the polyester resin (A) and the rubber-like elastic resin (B), taking into consideration the compatibility with these resins. Illustrating a specifically preferable combination, when the polyester resin (A) is an aromatic polyester resin composed of an aromatic dicarboxylic acid residue and a diol residue, and the rubber-like elastic resin (B) is a polyolefin resin, As the vinyl polymer (C), a copolymer of ethylene and a unit having a polar group, or SEBS in which 1% by mass or more of maleic anhydride or glycidyl methacrylate is introduced is preferable, and among them, copolymerization of a unit having ethylene and a polar group is carried out. In the combination, it is easy to positively control λ _{(Resin C) / (Resin B)} by appropriately controlling the compounding ratio between the units having ethylene and the polar group. More preferably, a functional group having a chemical action such as covalent bond with polyester resin (A), a coordinate bond, a hydrogen bond, an ionic bond is introduced into the copolymer of ethylene and a unit having a polar group, It is desirable because the interface between the polyester resin (A) and the vinyl polymer (C) can be thermodynamically stabilized when encapsulated.

More specifically, a copolymer of ethylene and a unit having a polar group will be described. An ethylene-vinyl acid copolymer, an ethylene-vinyl acid ester copolymer and ionomer resins thereof, ethylene and α, β -Unsaturated acid glycidyl ester copolymer, terpolymer of ethylene and vinyl acid or vinyl acid ester and α, β-unsaturated glycidyl ester, and the like. Among them, ionomer resins, copolymers of ethylene and glycidyl ester of α, β-unsaturated acid, ethylene and vinyl acid or vinyl acid ester and α, β-unsaturated acid glycidyl ester of 3
A terpolymer is preferred. These resins show a relatively strong chemical interaction with the polyester resin (A) and form a stable capsule structure with the rubber-like elastic resin (B). Among them, the ionomer resin is the most preferable from the viewpoint of moldability because the strength of the chemical action with the polyester resin (A) changes depending on the temperature.

As the ionomer resin, well-known ionomer resins can be widely used. In particular,
It is a copolymer of a vinyl monomer and an α, β-unsaturated carboxylic acid in which some or all of the carboxylic acid in the copolymer is neutralized with a metal cation.

As an example of the vinyl monomer, the above α-
Examples of the olefin and styrene monomers are α, β-unsaturated carboxylic acids, and more specifically, α, β-unsaturated carboxylic acids having 3 to 8 carbon atoms, more specifically acrylic acid, methacrylic acid,
Maleic acid, itaconic acid, maleic acid monomethyl ester, maleic anhydride, maleic acid monoethyl ester and the like can be mentioned.

Examples of neutralizing metal cations include N
a ⁺ , K ⁺ , Li ⁺ , Zn ²⁺ , Mg ²⁺ , Ca ²⁺ , Co ²⁺ , Ni ²⁺ , Pb ²⁺ , C
^Examples include monovalent or divalent metal cations such as u ²⁺ and Mn ²⁺ . Further, a part of the remaining carboxyl group which is not neutralized with a metal cation may be esterified with a lower alcohol.

Specific examples of the ionomer resin are:
A copolymer of ethylene and an unsaturated monocarboxylic acid such as acrylic acid or methacrylic acid, or a copolymer of ethylene and an unsaturated dicarboxylic acid such as maleic acid or itaconic acid, wherein the carboxyl group in the copolymer is Examples of the resin include a resin in which a part or all of is neutralized with a metal ion such as sodium, potassium, lithium, zinc, magnesium and calcium. Among these, the most preferable for the purpose of improving the compatibility between the polyester resin (A) and the rubber-like elastic resin (B) is a copolymer of ethylene and acrylic acid or methacrylic acid (a structure having a carboxyl group. (Unit is 2 to 15 mol%)
The resin is a resin in which 30 to 70% of the carboxyl groups in the polymer are neutralized with metal cations such as Na and Zn.

Rubber-like elastic resin used in the present invention
(B) and vinyl polymer (C) to form a core-shell type rubber-like elastic body, the rubber-like elastic resin (B) is the core portion, the vinyl polymer (C) is the shell portion, The dispersed structure of the polyester resin layer of the invention can be formed relatively easily. This core-shell type elastic rubber is
It has a two-layer structure composed of a core portion and a shell portion, the core portion is in a soft rubber state, and the shell portion on the surface thereof is in a hard resin state.

Taking a core-shell type rubber elastic body as an example, the core portion is made of an acrylic rubber elastic body, a diene rubber elastic body, or a silicon rubber elastic body,
An example is a rubber-like elastic body in which the acrylic polymer mainly composed of acrylate or methacrylate grafted on the shell constitutes the shell portion. The term "graft" means graft copolymerization of the resin of the core portion and the resin of the shell portion.

Specifically, the rubber-like elastic material constituting the core portion is represented by an acrylate polymer, a diene polymer, or dimethylsiloxane which is composed of a unit having the structure of the general formula (c). It is a rubber-like elastic body.

CH ₂ = CR ₁ -CO-OR ₂ (c) Specific examples of the constituent units of the acrylate-based polymer include alkyl acrylate, alkyl methacrylate, and alkyl ethacrylate, and R ₁ is hydrogen. Or an alkyl group having 1 to 12 carbon atoms, and R ₂ has 1 to 12 carbon atoms.
Those having an acrylic group are preferred. More specifically, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, n-octyl methacrylate and the like can be mentioned.
Among them, ethyl acrylate, butyl acrylate, 2-hexyl acrylate, methyl methacrylate, and n-octyl methacrylate are preferable from the viewpoint of imparting impact resistance. The acrylate-based polymer forming the core part may be a homopolymer of these or a copolymer of two or more kinds.

Further, the acrylate-based polymer constituting the core portion may be copolymerized with other vinyl monomers as long as the above-mentioned acrylate is the main component. 50 is the main component
It is at least mass%. Specific examples of vinyl monomers include α-olefin monomers, styrene monomers, and polar vinyl monomers. More specifically,
As the α-olefin monomer, ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-
Examples include hexene, 1-octene, 1-decene, 1-dodecene, and the like.Styrene-based monomers include, in addition to styrene monomers, alkylated styrenes such as o, m, p-ethylstyrene and t-butylstyrene, and monofluorostyrene. Examples include Cl, such as styrene, halogenated styrenes excluding Br, α-methylstyrene, and the like, and acrylic acid as the polar vinyl monomer,
Examples thereof include acrylonitrile, maleic anhydride and imide derivatives thereof, vinyl acetate, vinyl fluoride, vinyl propionate and the like.

Further, it is preferable that the acrylate polymer forming the core portion is partially crosslinked with a crosslinking agent in order to exert rubber elasticity. Examples of the cross-linking agent include vinyl monomers having polyethylenic unsaturation, and include divinylbenzene, butylene diacrylate, ethylene dimethacrylate, butylene dimethacrylate, trimethylolpropane trimethacrylate, triallysyl anurate and triallyl isocyanate. The addition amount of the crosslinking agent is 30% by mass or less, preferably 20% by mass or less, and more preferably 5% by mass or less. If it exceeds 30% by mass, it often hardens to exhibit rubber elasticity.

The diene polymer constituting the core portion is a polymer of a diene monomer or a hydrogenated polymer thereof, specifically, polybutadiene and its hydrogenated polymer,
Examples thereof include a copolymer of butadiene and styrene and a hydrogenated polymer thereof.

The molecular weight of the polymer constituting the core portion is not particularly limited, but a number average molecular weight of 2000 or more is preferable. If it is less than 2000, sufficient rubber elasticity cannot be exhibited.
When the core part is a cross-linked acrylate polymer, the molecular weight between cross-linking points is preferably 2000 or more from the viewpoint of imparting sufficient rubber elasticity.

Glass transition temperature of polymer constituting core
(Raising rate 10 ° C / min, measured with a differential thermal analyzer (DSC))
The temperature is preferably 30 ° C or lower, more preferably 10 ° C or lower, and further preferably -10 ° C or lower. If the glass transition temperature exceeds 30 ° C, rubber elasticity at room temperature or lower is difficult to be exhibited.

Next, the shell portion of the core-shell type rubber-like elastic body will be described. It is important that the shell part is composed of an acrylate-based polymer, and by utilizing the polarity of the acrylate-based polymer, the adhesion when the core-shell type rubber-like elastic body comes into contact with the metal plate is improved. Can be secured.

The acrylate polymer forming the shell portion is a polymer composed of the unit represented by the general formula (c). Specifically, it is a polymer of the above-mentioned monomers and may be copolymerized with the above vinyl monomer as long as the acrylate unit is the main component. Here, the main component is 50% by mass or more. When copolymerized with another vinyl monomer, the composition ratio of the acrylate component is preferably 70% by mass or more. If it is less than 70% by mass, the polarity of the acrylate unit cannot be fully utilized, and the adhesion to the metal plate may be insufficient.

Since the core portion of the core-shell type rubber-like elastic body is a soft rubber-like substance, it is necessary for the resin constituting the shell portion to be hard from the viewpoint of handleability. For this purpose, it is preferable that the glass transition temperature of the acrylate-based polymer constituting the shell part (heating rate 10 ° C./min, measured by a differential thermal analyzer (DSC)) is 30 ° C. or higher,
More preferably, it is 50 ° C or higher.

Most preferred as the acrylate polymer unit constituting the shell portion is methyl methacrylate because the glass transition temperature is in the above range and the polymerization rate is easily controlled.

Furthermore, in order to ensure compatibility with the polyester resin (A), the acrylate-based polymer constituting the shell part has a functional group capable of reacting with the residual terminal functional group of the polyester resin (A) and the ester bond. It is preferable that a group or a bonding group is introduced. Specific examples of the functional group include an epoxy group, a carboxyl group, a hydroxyl group, an acid anhydride group, and an amino group. When a shell portion is grafted, a known vinyl monomer having such a functional group is added. By doing so, a functional group can be introduced. Further, examples of the bonding group include an ester bond, a carbonate bond, an amide bond, etc., and when grafting the shell part, T.
O. Ahn, et al .; J. Polym. Sci. PartA Vol. 31, 435
The linking group can be introduced by using an initiator having these bonds as disclosed in (1993). Among these functional groups and bonding groups, the epoxy group and the aromatic-aromatic ester bond are most preferable from the viewpoint of reactivity, and when polymerizing the shell part, glycidyl methacrylate and TO Ahn, respectively. , et al .; J. Polym. Sc
By adding the polyarylate azo initiator disclosed in i. Part A Vol. 31, 435 (1993), the above epoxy group and ester bond can be introduced.

The introduction amount of the units containing these functional groups and bonding groups is determined by the reactivity, respectively.
There is no particular limitation in the range where the acrylate unit is the main component. However, in the case of a functional group, the amount of the functional group-containing unit introduced is preferably 15% by mass or less, and more preferably 5% by mass or less. 15 mass%
If it exceeds the above range, a comb polymer may be produced in the kneading step, and the compatibility with the polyester resin (A) may not be sufficiently improved. In the case of a bonding group, the amount of the bonding group-containing unit introduced is preferably 15% by mass or less. If it exceeds 15% by mass, the unit having a bonding group may form a domain, and the compatibility with the polyester resin (A) may not be improved.

It is desirable that the core-shell type rubber-like elastic body contains a core portion which is a rubber-like polymer in an amount of 20% by mass or more, preferably 50% by mass or more, more preferably 80% by mass or more. If it is less than 20% by mass, sufficient impact resistance may not be exhibited.

The polyester resin composition of the present invention can be produced by a known mixing method.

Specifically, a polyester resin (A), a rubber-like elastic resin (B) and a vinyl polymer (C) having an appropriate difference in interfacial tension are known at a predetermined temperature, for example, 200 to 350 ° C. By melt-kneading using various mixers, it is possible to form and manufacture a capsule structure by utilizing the difference in interfacial tension.

Alternatively, the rubber-like elastic resin (B) and the vinyl polymer (C) may be grafted to form a core-shell type rubber-like elastic body, and then mixed with the polyester resin (A). Can be manufactured. The core-shell type rubber-like elastic material can be polymerized by a known radical polymerization method. Among them, the emulsion polymerization method as described in US Pat. Is preferred. Specific examples of the polymerization method include the following methods. However, the core-shell type graft rubber-like elastic body may be an acrylate polymer as the shell portion, and the production method is not limited to the production method.

As the first-stage polymerization, the unit monomers constituting the core portion are radically polymerized. At this time, about 0.1 to 5% by mass of a monomer having a polyethyleneic unsaturation and a plurality of double bonds is added as a grafting agent. It is preferable that a plurality of double bonds of the present grafting agent have different reaction rates, and specifically, allyl methacrylate, diallyl malade and the like. After the polymer of the core portion is polymerized, the core-shell type rubbery elastic body is obtained by performing the second step polymerization by adding monomers and an initiator constituting the shell portion and graft-polymerizing the shell portion.

Next, the core-shell type rubber-like elastic material will be specifically exemplified. An MBA in which the core portion is made of polybutyl acrylate and the shell portion is made of polymethylmethacrylate.
Resin, core part is butadiene-styrene copolymer, shell part is MBS resin consisting of polymethylmethacrylate, core part is polydimethylsiloxane, shell part is a polymer consisting of polymethylmethacrylate, and the like. The acrylate-based core-polymerized acrylate shell polymers disclosed in 4096202 can be used in the present invention.

The polyester resin layer (A) composed of the polyester resin (A) and the core-shell type rubber-like elastic material used in the present invention includes a polyester resin (A) and a core-shell type rubber-like elastic material. A known compatibilizer may be added for the purpose of improving the solubility. Addition amount of compatibilizer is 15 mass
% Or less, and more preferably 5% by mass or less. 1
If it exceeds 5% by mass, the compatibilizer may independently form a phase structure, and it is difficult to exert a sufficient effect of improving compatibility. Specific examples of the compatibilizer include reactive compatibilizers and non-reactive compatibilizers, and the reactive compatibilizers include a polyester resin (A which is compatible with the core-shell type rubber-like elastic material). Polymers in which a functional group or a bond capable of reacting with the terminal residual functional group or the bond of (4) is introduced. More specifically, the core
-Shell-type rubber-like elastic body glycidyl methacrylate, a polymer obtained by random copolymerization of maleic anhydride to the polymer constituting the shell portion, or a block copolymer of aromatic polyester to the polymer constituting the shell portion, graft copolymerization polymer Can be mentioned. Examples of the non-reactive compatibilizing agent include block-and-graft copolymers of the polymer and the polyester resin (A) that form the shell portion of the core-shell type rubber-like elastic body.

Since the polyester resin layer of the present invention is a surface material for design purposes, a coloring agent is added. Examples of the colorant include a color pigment, titanium oxide (rutile type, anatase type), zinc oxide, silica, calcium carbonate and the like, and from the viewpoint of adjusting the color tone, it is preferably white.
Of these, titanium oxide is preferable because it has a high level of versatility and is versatile. After making the color white, a dye is added to obtain the desired color tone. As the pigment, there are inorganic pigments such as zinc white, Benji, vermilion, ultramarine blue, cobalt blue, titanium yellow, carbon black, isoindolinone, Hansa yellow A, quinacridone, permanent red 4R, phthalocyanine blue, indanthrene blue RS, anine. Examples include organic pigments (or dyes) such as phosphorus black, metal foil powder pigments such as aluminum and brass, titanium dioxide-coated mica, and pearlescent pigments composed of foil powder such as basic lead carbonate. The coloring by adding the colorant may be transparent coloring or opaque (concealing) coloring. These are added or dispersed as powder or flaky foil pieces. Particularly, for the purpose of concealing the background color of the substrate, a concealing pigment such as red iron oxide or black ink can be preferably used.

For mixing the polyester resin composition of the present invention, known resin mixing methods such as resin kneading method and solvent mixing method can be widely used. As an example of the resin kneading method, there is a method of mixing by dry blending with a tumbler blender, a Henschel mixer, a V-type blender, etc., and then melt-kneading with a uniaxial or biaxial extruder, a kneader, a Banbury mixer, etc. Further, as an example of the solvent mixing method, after dissolving each resin in a common solvent of the polyester resin (A), the rubber-like elastic resin (B) and the vinyl polymer (C), the solvent is evaporated or a common poor solvent is used. There is a method of collecting the mixture by adding it to the solvent.

In the case of kneading by melt mixing, prepare a masterbatch in which any one or a plurality of resins are premixed with a color pigment, and use these masterbatches in part or in whole. You may melt-mix. On the contrary, after melt mixing only the resin components in advance,
Color pigments may be added and melt mixed.

Further, in the polyester resin layer of the present invention,
For the purpose of improving rigidity and linear expansion characteristics, fiber reinforcing agents such as glass fiber, metal fiber, potassium whisker, carbon fiber, talc, calcium carbonate, mica, glass flake, milled fiber, metal flake, metal powder. You may mix a filler type strengthening agent like this. Among these fillers, the shapes of glass fiber and carbon fiber are 6 to 6
It is desirable to have a fiber diameter of 0 μm and a fiber length of 30 μm or more. The addition amount of these is preferably 5 to 15 parts by mass with respect to the total amount of the resin composition substance.

Further, in the polyester resin layer, a heat stabilizer, an antioxidant, a light stabilizer, a release agent, a lubricant, a flame retardant, a plasticizer, an antistatic agent, an antibacterial and antifungal agent, etc. may be added to the polyester resin layer according to the purpose. It is also possible to add an appropriate amount.

The thickness of the polyester resin layer used in the present invention is preferably 40 μm or more, more preferably 75 μm or more, in consideration of the hiding property of the substrate and the embossing depth when laminating on a metal plate. . Although the upper limit of the film thickness is not limited at times, it is 200 μm in terms of cost.
It is not preferable to exceed.

The polyester resin layer of the present invention may be applied to the surface of a metal plate for the purpose of producing a decorative metal plate, but in the present invention, it may be laminated on the metal plate after forming a resin film. It is preferable in terms of productivity. In particular, a method of laminating a resin film for laminating a decorative metal plate to which an emboss is applied in advance on a metal plate is a simple and preferable manufacturing method.

To produce the polyester resin film, the resin composition may be melt extruded.

The method of embossing the polyester resin film may be any of a method of applying during film formation, a method of heating after winding once and a method of cold embossing (shot blasting). The method of imparting embossing during film formation is to impart embossing before the extruded film is cooled, but this is difficult unless it is a non-stretched film. However, the conventional unstretched polyester resin film is insufficient in boiling water resistance and adhesion. On the other hand, the stretching stress relaxation agent finely dispersed polyester resin film of the present invention has boiling water resistance and adhesiveness even though it is a non-stretched polyester resin film, so that embossing can be imparted during film formation. Further, the method of heating the film once and then heating and embossing it could not be adopted because the conventional polyester resin film has a large heat shrinkage, but in the stretch stress relaxation agent fine dispersion polyester resin film of the present invention, the heat shrinkage Since it has a property that can be prevented, it can be adopted.

Further, the polyester resin layer of the present invention may be embossed in the step of laminating it on a metal plate, or may be embossed after being laminated on a metal plate. Also in these cases, the polyester resin layer of the present invention is effective in preventing heat shrinkage during lamination and embossing.

The stretching stress relaxation agent finely dispersed polyester resin film of the present invention can be embossed and laminated in a single layer, and the obtained embossed decorative metal plate is excellent in boiling water resistance and is suitable for use in a unit bath or the like. It can be used.

For embossing, known methods and conditions can be adopted. Typically, the resin is formed by heat-softening, pressurizing and shaping with an embossing plate, and cooling and solidifying. A sheet-like or rotary embossing machine is known. The embossed concavo-convex shape includes wood grain conduit grooves, lithographic surface irregularities, satin, sand,
There are spatula lines, etc. After embossing, matte,
Other films may be laminated or coated as long as the embossed design is not damaged. Generally, the temperature of the embossing roll during film formation is 25 to 30 ° C (normal temperature), and the temperature of the film-shaped embossing film is the melting temperature of the resin (measured with a differential thermal analyzer (DSC) at a heating rate of 10 ° C / min). From the start temperature to the crystal melting temperature (melting point Tm), the roll temperature is 25 to 30 ° C. (normal temperature), the plate temperature is the melting end temperature or more in the copper plate laminating simultaneous embossing, the roll temperature is the melting end temperature or more, and the copper plate laminating embossing is Plate temperature is above melting end temperature, roll temperature is 2
The temperature is generally 5 to 30 ° C. (normal temperature), but is not limited to this.

The polyester resin, which is the matrix resin of the finely dispersed polyester resin for stretching stress relaxation agent of the present invention, is a polyethylene terephthalate resin, or a part of the acid component of polyethylene terephthalate is isophthalic acid from the viewpoint of adhesion to a metal material. Substituted modified polyethylene terephthalate resins are preferred.

The polyester resin film of the present invention is 100 to 10 ° C. above the melting point of the film for embossing.
Since it is heated to a low temperature, it is preferable that it does not heat-shrink at that time.
Shrinkage at 20 ° C lower temperature is 20% or less, further 10
% Or less, and particularly preferably 5% or less.

When the difference between the crystal melting temperature Tm during embossing and the crystallization temperature Tc during solidification from a high temperature is small, the embossed groove is easily fixed, which is suitable for embossing makeup. Is preferably a polybutylene terephthalate resin, or a modified polybutylene terephthalate resin obtained by substituting a part of the acid component of polybutylene terephthalate with isophthalic acid. In addition, PET, modified PET and PBT, modified PBT, in order to have both adhesion and embossability,
You can blend it.

When it is used as an interior material for a unit bath, it is exposed to high temperature and high humidity, especially boiling water for a long period of time. Therefore, the polyester resin has a glass transition temperature higher than 100 ° C., and further higher than 110 ° C. It is preferably crystalline. Since the glass transition temperature of the resin is lower than the measured value under the normal condition under the high humidity condition, the normally measured value is more preferably 105 ° C. or higher.

In the case of a crystalline material, if the glass transition temperature of the amorphous portion exceeds 100 ° C., there is no thermal deformation even under the conditions of contact with high temperature, high humidity and boiling water, and such a material is suitable. .

In the crystalline polyester resin layer, if the degree of crystallinity of the resin is 10% or more of the saturated crystallization rate, even if crystallization proceeds in boiling water, the degree is small, so that the density change Since it is small, it is possible to prevent deformation and whitening. The crystallinity of the film is more preferably 20% or more, and further preferably 50% or more of the saturated crystallization rate. As the resin film satisfying such conditions, polybutylene terephthalate, modified polybutylene terephthalate, and polyethylene terephthalate or modified polyethylene terephthalate added to these may be used alone or in combination of two or more, preferably polybutylene terephthalate. Can be mentioned.

If necessary, an adhesive layer (or an adhesion improving layer) may be provided between the finely dispersed polyester resin for stretching stress relaxation agent of the present invention and the metal plate. As the adhesive, for example, a one-component or two-component polyester resin adhesive, a polyurethane resin adhesive, or the like can be used. If necessary, a color pigment, a rust preventive pigment, an extender pigment, etc. may be added to the adhesive layer. The thickness of the adhesive material after drying is preferably about 2 to 10 μm.

The embossed decorative metal plate of the present invention is developed especially for the purpose of coating a metal plate.
Although the metal plate is not particularly limited, for example, the interior material of the inner wall of the unit bath and other buildings, the exterior of home appliances such as electric refrigerator doors and air conditioner covers, steel furniture, and elevators, especially those with embossed patterns It is suitable for applications requiring a design.

The metal plate is not particularly limited, but hot dip galvanized steel plate, hot dip galvanized steel plate, hot dip galvanized aluminum-magnesium alloy plated steel plate, tin plate, thin tin plated steel plate, electrolytic chromic acid treatment steel sheet
(Tin-free steel), nickel-plated steel sheets, hot-dip aluminum-silicon alloy-plated steel sheets, hot-dip lead-tin alloy-plated steel sheets, electro-galvanized steel sheets, electro-galvanized-nickel-plated steel sheets, electro-galvanized-iron. Surface-treated steel sheets such as alloy plated steel sheets, electroplated steel sheets such as electrolytic zinc-chromium alloy plated steel sheets, cold rolled steel sheets and aluminum,
Examples thereof include metal plates made of copper, nickel, zinc, magnesium and the like. Stainless steel plates are most suitable for use as interior materials for unit baths.

The metal plate may be treated with phosphate, if necessary.
Pretreatment such as chromate treatment may be performed.

The thickness of the metal plate is not particularly limited and may be selected according to the application, but generally 0.01 to 5
It is preferably mm. If it is less than 0.01 mm, it is difficult to develop strength, and if it exceeds 5 mm, it is difficult to process it.

According to the present invention, the resin film for laminating the embossed decorative board may be coated on the metal plate by thermocompression bonding with or without an adhesive agent on the metal plate. The method of thermocompression bonding may be such that a metal plate is heated to a predetermined temperature, a resin film is laminated, and a roller or the like is pressed as necessary. When an adhesive is used, it may be applied to the surface of the metal plate or the surface of the resin film, or an adhesive layer may be previously formed on the surface of the film. The thermocompression bonding temperature depends on the film thickness, but a temperature at which color tone protection and emboss return do not occur is preferable.

The metal plate having the embossed pattern design of the present invention can be obtained by a method of coating a resin film for laminating an embossed decorative plate on a metal plate, or by a fine dispersion polyester of stretching stress relaxation agent in which the metal plate is not embossed. As described above, the resin may be laminated (baked) on the metal plate and embossed during or after the laminating step.

[0113]

EXAMPLES Next, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples without departing from the gist thereof.

In the following Examples and Comparative Examples, polyethylene terephthalate (PET) was used as the polyester resin (A) [SA-1346P, MA manufactured by Unitika Ltd.].
-1344], polybutylene terephthalate (PBT)
[DURANEX 2001 manufactured by Polyplastics Co., Ltd.
And Toray Co., Ltd., Trecon 1200S], a vinyl polymer (B) having 1% by mass or more of a unit having a polar group.
As an ethylene-glycidyl methacrylate copolymer [Sumitomo Chemical Co., Ltd. Bondfast 2C], ethylene-alkyl acrylate-glycidyl methacrylate copolymer [Sumitomo Chemical Co., Ltd. Bondfast 7L], ethylene ionomer [HIMIRAN 1706 manufactured by Mitsui DuPont Co., Ltd.], ethylene-butene rubber (EBM) as a rubber-like elastic resin (C) [EBM204 manufactured by JSR Co., Ltd.]
1P] was used. When melt-kneading, a blended antioxidant [Adeka Stab A-61 manufactured by Asahi Denka Co., Ltd.
2] was used. As the polyester resin (A), polybutylene terephthalate (PBT) [Duranex 2001 manufactured by Polyplastics Co., Ltd. and Toray Co., Ltd.]
A masterbatch polybutylene terephthalate containing 50% by mass of titanium dioxide (average particle size 0.2 to 0.3 μm) was prepared in advance for each of the manufactured Trecon 1200S].

(Example 1-10) Titanium dioxide masterbatch resins corresponding to the respective resins were dry-blended using a V-type blender so that the composition ratios shown in Table 1 were obtained. The final composition ratio of each resin is as shown in Table 1,
In each case, the blended antioxidant A-612 was added in an amount of 0.5 part by mass based on 100 parts by mass of the resin composition.
An ivory color pigment was added to the mixture for toning, and the mixture was melt-kneaded at 260 ° C. with a twin-screw extruder to obtain ivory color resin composition pellets.

After cutting an ultrathin section from the resin composition with a microtome, it was dyed with ruthenic acid to determine the dispersion state of the vinyl polymer (B) and the rubber-like elastic resin (C) in the polyester resin (A). It was analyzed by a transmission electron microscope. As a result, almost 100% of the rubber-like elastic resin (C) is encapsulated with the vinyl polymer (B), and the equivalent spherical equivalent diameter of the rubber-like elastic resin (C) is 1 μm or less and the polyester resin It was finely dispersed in (A).

[0117]

[Table 1]

Using this pellet, 90μ with T-die
After forming m-thick film (extrusion temperature: 250-280
C.) and a satin embossing roll having a surface temperature of 20 to 30.degree. C. as a cooling roll was used to obtain an ivory color resin composition film having a satin embossing appearance.

The ivory color resin composition film layer side having a satin embossed appearance and a two-component polyester adhesive (for vinyl chloride resin, adhesive thickness after drying 4 μm)
m) was applied and heated to 210 ° C. to one side of a hot-dip galvanized steel sheet having a thickness of 450 μm, which was pressure-bonded using a rubber roll-rubber roll, and rapidly cooled to 100 ° C. or less within 5 seconds by water cooling on the back surface of the steel sheet, and Obtained. These surface hardness is
From H to 2B, it was found that the film hardness was harder than the PVC steel plate.

The room temperature decorative steel sheet thus obtained was evaluated for each item of adhesion, boiling water resistance, workability, stain resistance, solvent resistance, embossing workability by the following evaluation methods. went.

<Adhesion> A cross-cut was put on the above decorative steel plate and immersed in distilled water at 50 ° C. for 10 days, and then the peeling width (mm) of the film at the cross-cut portion (average of 10 samples) was evaluated. The evaluation is ◎: 0.0 mm, ○: 0.0 to
0.5 mm, Δ: 0.5 to 2.0 mm, and ×: more than 2.0 mm. The results of the adhesion test are shown in Table 2.

<Boiling resistance> The above decorative steel sheet was continuously immersed in boiling water for 48 hours, and the peeling condition of the film and the appearance change (concavities, shrinkage, peeling, etc.) were visually confirmed. Evaluation,
⊚: No abnormality, ◯: Slight change, Δ: Surface significantly changed, and ×: Base was exposed. The results of the boiling water resistance test are shown in Table 2.

<Workability> The above decorative steel sheet was subjected to O
T bending was performed, and the quality of workability such as cracking and whitening was visually confirmed. Evaluation: ◎: no abnormality, ○: slight change, △:
The surface changes considerably, and x: the base is exposed. The results of the workability test are shown in Table 2.

<Staining resistance> After drawing with a black oil-based magic ink on the film surface of the above decorative steel sheet and leaving it for 24 hours, it was wiped with a cloth impregnated with ethanol to remove the remaining magic ink on the film surface. The degree was visually confirmed. The evaluation is ◎: No magic ink is recognized at all, ○: A very small amount of magic ink remains, which is not a problem in practical use, Δ: A slight amount of magic ink remains, which is a problem in practical use Yes, and x: The remaining of the magic ink was recognized to a considerable extent. The results of the stain resistance test are shown in Table 2.

<Solvent resistance> A sponge impregnated with methyl ethyl ketone was placed on the film surface of the above decorative steel plate,
After standing for 24 hours, the degree of discoloration and swelling of the film surface was visually observed. The evaluation was ⊚: no discoloration or swelling was observed at all, ∘: very slight discoloration or swelling was observed to the extent that there was no practical problem.
Δ: slight discoloration and swelling, which are practically problematic, were observed, and x: discoloration and swelling, to a considerable extent, were observed. The results of the solvent resistance test are shown in Table 2.

<Embossability> The quality of the embossability of the film surface of the above decorative steel sheet was visually observed to determine the following 3 items.
Judgment was made according to the criteria of stages. ○: Good, △: Somewhat bad, ×:
The defective results are shown in Table 2.

Example 11 Pellets having the resin composition ratio of Example 5 shown in Table 1 were used and 80 μm with a T-die.
A m-thick film was formed (extrusion temperature: 260 ° C.) to obtain an ivory color resin composition film. The obtained film was heated to about 200 ° C. and processed with a satin embossing roll having a surface temperature of 25 ° C. to obtain an ivory color resin composition film having a satin embossed appearance.

A ivory color resin composition film having a satin embossed appearance was coated with a two-pack type polyester adhesive (for vinyl chloride resin, adhesive coating thickness after drying was 4 μm).
Was applied to one surface of a hot-dip galvanized steel sheet having a thickness of 450 μm and heated at 210 ° C., using a rubber roll-rubber roll, and then rapidly cooled to 100 ° C. or less within 5 seconds by water cooling on the back surface of the steel sheet to obtain a decorative steel sheet. These surface hardness is 2B
It was found that the film hardness was higher than that of PVC steel plate.

With respect to the decorative steel sheet at room temperature thus obtained, each of adhesion, boiling water resistance, workability, stain resistance, solvent resistance and embossability was evaluated by the evaluation methods shown in Examples 1 to 10. The item was evaluated. The results are shown in Table 2.

Example 12 The ivory-colored resin composition film shown in Example 11 was heated to 260 ° C. 450.
One side of a μm-thick galvanized steel sheet was crimped and embossed using a satin embossed metal roll (film side) -rubber roll (steel sheet side) heated to 240 ° C., and backside water cooling was performed at 100 ° C. within 5 seconds. By rapidly cooling to the following, an ivory resin composition film decorative steel sheet having a satin embossed appearance was obtained. The surface hardness of this decorative steel sheet is
It was 2B, and it was found that the film hardness was higher than that of the vinyl chloride steel plate.

With respect to the decorative steel sheet at room temperature thus obtained, each of adhesion, boiling water resistance, workability, stain resistance, solvent resistance and embossability was evaluated by the evaluation methods shown in Examples 1 to 10. The item was evaluated. The results are shown in Table 2.

(Example 13) The ivory color resin composition film shown in Example 11 was applied to a two-pack type polyester adhesive (for vinyl chloride resin, and the dried adhesive coating thickness was 4).
μm) and heated to 210 ° C. to one side of a 450 μm-thick hot-dip galvanized steel plate, which is pressure-bonded using a rubber roll-rubber roll and heated to 230 ° C. or higher in a heating oven, and then a satin finish with a surface temperature of 30 ° C. Embossed by embossing roll and water-cooled on the back side for 10 seconds within 5 seconds
It was rapidly cooled to 0 ° C. or lower to obtain an ivory color resin composition film decorative steel sheet having a satin embossed appearance. The back surface hardness of this decorative steel plate was 2B, and it was found that the film hardness was higher than that of the vinyl chloride steel plate.

With respect to the decorative steel sheet at room temperature thus obtained, each of adhesion, boiling water resistance, workability, stain resistance, solvent resistance and embossability was evaluated by the evaluation methods shown in Examples 1 to 10. The item was evaluated. The results are shown in Table 2.

[0134]

[Table 2]

As shown in Table 2, the colored film-laminated steel sheet exhibiting the embossed appearance of the present invention has a harder film hardness than the vinyl chloride steel sheet, has an embossed appearance, and has an excellent adhesion,
It has boiling water resistance, processability, stain resistance, and solvent resistance.

[0136]

EFFECTS OF THE INVENTION According to the present invention, a resin having no environmental load such as a vinyl chloride resin is used, and there are no problems such as flaws and whitening like a polyolefin resin, and there is no stretching stress as compared with a conventional polyester resin. By finely dispersing the relaxation agent, it is possible to prevent heat shrinkage deformation during embossing and laminating processes, and to have stability that it does not deform even when used in a hot and humid environment, and a rubber elastic resin used as a stretching stress relaxation agent. By encapsulating the vinyl polymer with a vinyl polymer, the adhesion to a metal plate can be excellent, and thus an excellent embossed decorative metal plate that can be used as an interior material for a unit bath is provided. In addition, the polyester resin layer (film) of the present invention can cover the metal plate with a single layer to exhibit the above-mentioned excellent effects, and thus has an effect of low cost.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Hiroshi Kamishiro             20-1 Shintomi, Futtsu-shi, Chiba Nippon Steel shares             Company Technology Development Division (72) Inventor Kazunari Niki             20-1 Shintomi, Futtsu-shi, Chiba Nippon Steel shares             Company Technology Development Division (72) Inventor Yoshihiro Nami             20-1 Shintomi, Futtsu-shi, Chiba Nippon Steel shares             Company Technology Development Division (72) Inventor Akihiro Kikuchi             20-1 Shintomi, Futtsu-shi, Chiba Nippon Steel shares             Company Technology Development Division F-term (reference) 4F100 AB01A AK41B AK42B AL05B                       AL06B AR00B BA02 BA07                       CA30B DD01B GB08 GB48                       JB07 JJ03 JK07B JK08B                       JL01 JL10B JL11 YY00B                 4J002 AC032 AC062 AC072 AC082                       BB022 BB052 BB063 BB073                       BB083 BB093 BB112 BB152                       BB162 BB233 BC063 BC073                       BE023 BF023 BG063 BN142                       BN152 BP012 CD193 CF051                       CF061 CF071 CF081 CF172                       CL002 CP032 GF00

Claims (12)

[Claims] 1. An embossed decorative metal plate, which is formed by coating the surface of a metal plate with a colored polyester resin layer in which a stretching stress relaxation agent is finely dispersed, and the surface of the polyester resin layer is embossed. . 2. The polyester resin layer is obtained by finely dispersing a rubber-like elastic resin (B) as a stretching stress relaxation agent in a polyester resin (A) as a matrix, and at least a rubber-like elastic resin ( The embossed decorative metal plate according to claim 1, wherein a part of B) has a structure encapsulated with a vinyl polymer (C) having a polar group. 3. The embossed decorative metal plate according to claim 1, wherein the equivalent spherical equivalent diameter of the stretching stress relaxation agent finely dispersed in the polyester resin is 1 μm or less. 4. The embossed decorative metal plate according to claim 1, wherein the matrix resin of the polyester resin layer is polyethylene terephthalate, modified polyethylene terephthalate, polybutylene terephthalate, modified polybutylene terephthalate, or a combination thereof. 5. A resin film for laminating an embossed decorative metal plate, wherein the surface of a colored polyester resin film in which a stretching stress relaxation agent is finely dispersed is embossed. 6. The polyester resin film is obtained by finely dispersing a rubber-like elastic body resin (B) as a stretching stress relaxation agent in a polyester resin (a) as a matrix, and at least a rubber-like elastic body resin ( The resin film for laminating an embossed decorative metal plate according to claim 5, wherein a part of B) has a structure encapsulated with a vinyl polymer (C) having a polar group. 7. The resin film for embossing decorative metal plate lamination according to claim 5, wherein the equivalent spherical equivalent diameter of the stretching stress relaxation agent finely dispersed in the polyester resin is 1 μm or less. 8. The matrix resin of the polyester resin film is polyethylene terephthalate, modified polyethylene terephthalate, polybutylene terephthalate,
The resin film for laminating embossed decorative metal plates according to claim 5, 6 or 7, which is a modified polybutylene terephthalate or a combination thereof. 9. The polyester resin film according to claim 5, wherein the polyester resin film is composed of a resin film having a shrinkage ratio of 20% or less at a temperature lower than the melting point by 100 to 10 ° C.
The resin film for laminating the embossed decorative metal plate according to item. 10. The resin film for embossing decorative metal plate lamination according to claim 5, wherein the polyester resin film is an amorphous resin film having a glass transition temperature of 100 ° C. or higher. 11. The polyester resin film is made of a crystalline resin, and the glass transition temperature of the crystalline resin is 100.
The resin film for embossing decorative metal plate lamination according to any one of claims 5 to 9, which has a crystallization rate of 10 ° C or higher or a crystallization rate of 10% or more of a saturated crystallization rate. 12. A colored polyester resin film in which a stretching stress relaxation agent is finely dispersed is laminated on a metal plate, and the surface of the polyester resin film is embossed during or after the lamination. The manufacturing method of the embossed decorative metal plate in any one of Claims 1-4.